Chemistry of Electronic Materials

Chemistry of Electronic Materials
Collection Editor: Andrew R. Barron
Collection Editor: Andrew R. Barron Authors: Andrew R. Barron Pinn-Tsong Chiang Christopher E. Hamilton Jason Holden Christopher Kelty Inna Kurganskaya Andreas Luttge Avishek Saha Carissa Smith Elizabeth Whitsitt Bill Wilson
Online: < http://cnx.org/content/col10719/1.6/ >
CONNEXIONS
Rice University, Houston, Texas
This selection and arrangement of content as a collection is copyrighted by Andrew R. Barron. It is licensed under the Creative Commons Attribution 3.0 license (http://creativecommons.org/licenses/by/3.0/). Collection structure revised: February 10, 2010 PDF generated: June 29, 2010 For copyright and attribution information for the modules contained in this collection, see p. 308.
Table of Contents
Preface to the Chemistry of Electronic Materials 1 Background to Electronic Materials 1.1 1.2 1.3 1.4 1.5
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sntrodution to emiondutors F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F Q hoped emiondutors F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F W hi'usion F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IT grystl truture F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PH trutures of ilement nd gompound emiondutors F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F QV
2 Device Fundamentals 2.1 sntrodution to fipolr rnsistors F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F SI 2.2 fsi wy truture F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F SQ 2.3 sntrodution to the wy rnsistor nd wypis F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F F SV 2.4 vight imitting hiode F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F F TP 2.5 olymer vight imitting hiodes F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F TT 2.6 vser F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F US 2.7 olr gells F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F UV 3 Bulk Materials 3.1 roperties of qllium ersenide F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F VS 3.2 ynthesis nd uri(tion of fulk emiondutors F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F VW 3.3 germi roessing of elumin F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F IHI 3.4 iezoeletri wterils ynthesis F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F IHR 4 Wafer Formation and Processing 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9
pormtion of ilion nd qllium ersenide fers F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IIQ hoping F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IPW epplitions for ili hin pilms F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IQH yxidtion of ilion F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IQR hotolithogrphy F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F IQV yptil sssues in hotolithogrphy F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IRQ gomposition nd hotohemil wehnisms of hotoresists F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F IRU sntegrted giruit ell nd qte gretion F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F ISQ epplying wetlliztion y puttering F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F ITH
5 Thin Film Growth 5.1 woleulr fem ipitxy F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F ITQ 5.2 etomi vyer heposition F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F ITW 5.3 ghemil por heposition F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F IUR 5.4 viquid hse heposition F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F IVR 6 Chemical Vapor Deposition 6.1 6.2 6.3 6.4 6.5 6.6 6.7
eleting woleulr reursor for ghemil por heposition F F F F F F F F F F F F F F F F F F F F F F F F F F F F IWI hetermintion of ulimtion inthlpy nd por ressure for snorgni nd wetlEyrgni gompounds y hermogrvimetri enlysis F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IWP IQEIS @sssEA emiondutor ghemil por heposition F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F PHH yxide ghemil por heposition F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PHV xitride ghemil por heposition F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PPP wetl yrgni ghemil por heposition of glium pluoride F F F F F F F F F F F F F F F F F F F F F F F F F F F F PQH reursors for ghemil por heposition of gopper F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PQP
7 Materials Characterization
iv
7.1 7.2
utherford fksttering of hin pilms F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PQW he epplition of s @ertil nning snterferometryA to the tudy of grystl urfe roesses F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PRU sntrodution to xnoprtile ynthesis F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PSW emiondutor xnoprtiles F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PSW gron xnomterils F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F PTI qrphene F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PUP olling woleules on urfes nder w smging F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PUU wnufturing of eminondutors F F F F F F F F F F F F F F F F F F F F F F PVU
8 Nanotechnology 8.1 8.2 8.3 8.4 8.5
9 Economic and Environmental Issues 9.1 he invironmentl smpt of the
Index F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F QHH Attributions F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FQHV
Preface to the Chemistry of Electronic Materials

1
he intention of this text is not to provide omprehensive referene to ll spets of semiondutor devie frition or review of reserh results thtD irrespetive of their promiseD hve not een dopted into minstrem produtionF snsted it is imed to provide useful referene for those interested in the hemil spets of the eletronis industryF qiven the nture of gonnexionsD this ourse is )uid in struture nd ontentF sn dditionD it ontins modules y other uthors where ppropriteF he ontent will e updted nd expnded with timeF sf ny uthors hve suitle ontentD plese ontt me nd s will e gld to ssist in trnsforming the ontent to suitle module strutureF endrew F frron ie niversityD roustonD UUHHSF iEmilX rdrieFedu2
1 2
This content is available online at <http://cnx.org/content/m25528/1.1/>. arb@rice.edu
Chapter 1
Background to Electronic Materials

1.1 Introduction to Semiconductors
tors y fill ilsonF
note:
1
his module is dpted from the gonnexions module entitled Introduction to Semiconduc-
sf we only hd to worry out simple ondutorsD life would not e very omplitedD ut on the other hnd we wouldn9t e le to mke omputersD gh plyersD ell phonesD iEods nd lot of other things whih we hve found to e usefulF e will now move onD nd tlk out nother lss of ondutors lled semiondutorsF sn order to understnd semiondutors nd in ft to get more urte piture of how metlsD or norml ondutors tully workD we relly hve to resort to quntum mehnisF iletrons in solid re very tiny ojetsD nd it turns out tht when things get smll enoughD they no longer extly following the lssil 4xewtonin4 lws of physis tht we re ll fmilir with from everydy experieneF st is not the purpose of this ourse to teh quntum mehnisD so wht we re going to do insted is desrie the results whih ome from looking t the ehvior of eletrons in solid from quntum mehnil point of viewF olids @t lest the ones we will e tlking outD nd espeilly semiondutorsA re rystlline mterilsD whih mens tht they hve their toms rrnged in ordered fshionF e n tke silion @the most importnt semiondutorA s n exmpleF ilion is group IR@sA elementD whih mens it hs four eletrons in its outer or vlene shellF ilion rystllizes in struture lled the dimond rystl lttieD shown in pigure IFIF ih silion tom hs four ovlent ondsD rrnged in tetrhedrl formtion out the tom enterF
1
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CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS
Figure 1.1:
Crystal structure of silicon.
sn two dimensionsD we n shemtilly represent piee of singleErystl silion s shown in pigure IFPF ih silion tom shres its four vlene eletrons with vlene eletrons from four nerest neighorsD (lling the shell to V eletronsD nd forming stleD periodi strutureF yne the toms hve een rrnged like thisD the outer vlene eletrons re no longer strongly ound to the host tomF he outer shells of ll of the toms lend together nd form wht is lled ndF he eletrons re now free to move out within this ndD nd this n led to eletril ondutivity s we disussed erlierF
Figure 1.2:
A 2-D representation of a silicon crystal.
his is not the omplete story howeverD for it turns out tht due to quntum mehnil e'etsD there is not just one nd whih holds eletronsD ut severl of themF ht will follow is very qulittive piture of how the eletrons re distriuted when they re in periodi solidD nd there re neessrily some detils whih we will e fored to gloss overF yn the other hnd this will give you pretty good piture of wht is going onD nd my enle you to hve some understnding of how semiondutor relly worksF iletrons re not only distriuted throughout the solid rystl sptillyD ut they lso hve distriution in energy s wellF he potentil energy funtion within the solid is periodi in ntureF his potentil funtion omes from the positively hrged tomi nulei whih re rrnged in the rystl in regulr rryF e detiled
S nlysis of how eletron wve funtionsD the mthemtil strtion whih one must use to desrie how smll quntum mehnil ojets ehve when they re in periodi potentilD gives rise to n energy distriution somewht like tht shown in pigure IFQF
Figure 1.3:
Schematic of the rst two bands in a periodic solid showing energy levels and bands.
pirstlyD unlike the se for free eletronsD in periodi solidD eletrons re not free to tke on ny energy vlue they wishF hey re fored into spei( energy levels lled llowed sttesD whih re represented y the ups in pigure IFQF he llowed sttes re not distriuted uniformly in energy eitherF hey re grouped into spei( on(gurtions lled energy ndsF here re no llowed levels t zero energy nd for some distne ove thtF woving up from zero energyD we then enounter the (rst energy ndF et the ottom of the nd there re very few llowed sttesD ut s we move up in energyD the numer of llowed sttes (rst inresesD nd then flls o' ginF e then ome to region with no llowed sttesD lled n energy nd gpF eove the nd gpD nother nd of llowed sttes existsF his goes on nd onD with ny given mteril hving mny suh nds nd nd gpsF his sitution is shown shemtilly in pigure IFQD where the smll ups represent llowed energy levelsD nd the vertil xis represents eletron energyF st turns out tht eh nd hs extly PN llowed sttes in itD where N is the totl numer of toms in the prtiulr rystl smple we re tlking outF @ine there re IH ups in eh nd in the (gureD it must represent rystl with just S toms in itF xot very ig rystl t ll3A snto these nds we must now distriute ll of the vlene eletrons ssoited with the tomsD with the restrition tht we n only put one eletron into eh llowed stteF his is the result of something lled the uli exlusion prinipleF ine in the se of silion there re R vlene eletrons per tomD we would just (ll up the (rst two ndsD nd the next would e emptyF sf we mke the logil ssumption tht the eletrons will (ll in the levels with the lowest energy (rstD nd only go into higher lying levels if the ones elow re lredy (lledF his sitution
is shown in pigure IFRD in whih we hve represented eletrons s smll lk lls with 4E4 sign on themF sndeedD the (rst two nds re ompletely fullD nd the next is emptyF ht will hppen if we pply n eletri (eld to the smple of silionc ememer the digrm we hve t hnd right now is n energy sed oneD we re showing how the eletrons re distriuted in energyD not how they re rrnged sptillyF yn this digrm we n not show how they will move outD ut only how they will hnge their energy s result of the pplied (eldF he eletri (eld will exert fore on the eletrons nd ttempt to elerte themF sf the eletrons re elertedD then they must inrese their kineti energyF nfortuntelyD there re no empty llowed sttes in either of the (lled ndsF en eletron would hve to jump ll the wy up into the next @emptyA nd in order to tke on more energyF sn silionD the gp etween the top of the highest most oupied nd nd the lowest unoupied nd is IFI eF @yne e is the potentil energy gined y n eletron moving ross n eletril potentil of one voltFA he men free pth or distne over whih n eletron would normlly move efore it su'ers ollision is only few hundred ngstroms @caF QHH x IH-8 mA nd so you would need very lrge eletri (eld @severl hundred thousnd GmA in order for the eletron to pik up enough energy to 4jump the gp4F his mkes it pper tht silion would e very d ondutor of eletriityD nd in ftD very pure silion is very poor eletril ondutorF
Figure 1.4:
Silicon, with rst two bands full and the next empty.
e metl is n element with n odd numer of vlene eletrons so tht metl ends up with n upper nd whih is just hlf full of eletronsF his is illustrted in pigure IFSF rere we see tht one nd is fullD nd the next is just hlf fullF his would e the sitution for the qroup IQ@sssA element luminum for
U instneF sf we pply n eletri (eld to these rriersD those ner the top of the distriution n indeed move into higher energy levels y quiring some kineti energy of motionD nd esily move from one ple to the nextF sn relityD the whole sitution is it more omplex thn we hve shown hereD ut this is not too fr from how it tully worksF
Figure 1.5:
Electron distribution for a metal or good conductor.
oD k to our silion smpleF sf there re no ples for eletrons to 4move4 intoD then how does silion work s 4semiondutor4c ellD in the (rst pleD it turns out tht not ll of the eletrons re in the ottom two ndsF sn silionD unlike sy qurtz or dimondD the nd gp etween the topEmost full ndD the next empty one is not so lrgeF es we mentioned ove it is only out IFI eF o long s the silion is not t solute zero tempertureD some eletrons ner the top of the full nd n quire enough therml energy tht they n 4hop4 the gpD nd end up in the upper ndD lled the ondution ndF his sitution is shown in pigure IFTF
Figure 1.6:
Thermal excitation of electrons across the band gap.
sn silion t room tempertureD roughly IH10 eletrons per ui entimeter re thermlly exited ross the ndEgp t ny one timeF st should e noted tht the exittion proess is ontinuous oneF iletrons re eing exited ross the ndD ut then they fll k down into empty spots in the lower ndF yn verge howeverD the IH10 in eh m3 of silion is wht you will (nd t ny given instntF xow IH illion eletrons per ui entimeter seems like lot of eletronsD ut lets do simple lultionF he moility of eletrons in silion is out IHHH m2 GFsF ememerD moility times eletri (eld yields the verge veloity of the rriersF iletri (eld hs units of GmD so with these units we get veloity in mGs s we shouldF he hrge on n eletron is IFT x IH-19 oulomsF hus from @IFIAX
@IFIA sf we hve smple of silion I m long y @I mm x ImmA squreD it would hve resistneD @IFPAD whih does not mke it muh of 4ondutor4F sn ftD if this were ll there ws to the silion storyD we ould pk up nd move onD euse t ny resonle tempertureD silion would ondut eletriity very poorlyF
@IFPA
1.2 Doped Semiconductors

note:
his module is dpted from the gonnexions module entitled Doped Semiconductors y fill ilsonF
o see how we n mke silion useful eletroni mterilD we will hve to go k to its rystl struture @pigure IFUAF uppose somehow we ould sustitute few toms of phosphorus for some of the silion tomsF
Figure 1.7:
A two dimensional representation of a silicon crystal lattice "doped" with phosphorus.
sf you snek look t the periodi tleD you will see tht phosphorus is group elementD s ompred with silion whih is group IR@sA elementF ht this mens is the phosphorus tom hs (ve outer or vlene eletronsD insted of the four whih silion hsF sn lttie omposed minly of silionD the extr eletron ssoited with the phosphorus tom hs no 4mting4 eletron with whih it n omplete shellD nd so is left loosely dngling to the phosphorus tomD with reltively low inding energyF sn ftD with the ddition of just little therml energy @from the nturl or ltent het of the rystl lttieA this eletron n rek free nd e left to wnder round the silion tom freelyF sn our 4energy nd4 pitureD we hve something like wht we see in pigure IFVF he phosphorus toms re represented y the dded ups with 9s on themF hey re new llowed energy levels whih re formed within the 4nd gp4 ner the ottom of the (rst empty ndF hey re loted lose enough to the empty @or 4ondution4A ndD so tht the eletrons whih they ontin re esily exited up into the ondution ndF hereD they re free to move out nd ontriute to the eletril ondutivity of the smpleF xote lsoD howeverD tht sine the eletron hs left the viinity of the phosphorus tomD there is now one more proton thn there re eletrons t the tomD nd hene it hs net positive hrge of IqF e hve represented this y putting little 4C4 sign in eh EupF xote tht this positive hrge is (xed t the site of the phosphorous tom lled donor sine it 4dontes4 n eletron up into the ondution ndD nd is not free to move out in the rystlF
2
IH
Figure 1.8:
Silicon doped with phosphorus.
row mny phosphorus toms do we need to signi(ntly hnge the resistne of our silionc uppose we wnted our I mm y I mm squre smple to hve resistne of one ohm s opposed to more thn TH wF urning the resistne eqution round we getD @IFQAF end heneD if we ontinue to ssume n eletron moility of IHHH m2 GvoltFseD @IFRAF
@IFQA
@IFRA xow dding more thn T x IH17 phosphorus toms per ui entimeter might seem like lot of phosphorusD until you relize tht there re lmost IH24 silion toms in ui entimeter nd hene only one in every IFT million silion toms hs to e hnged into phosphorus one to redue the resistne of the smple from severl IHs of w down to only one F his is the rel power of semiondutorsF ou n mke drmti hnges in their eletril properties y the ddition of only minute mounts of impuritiesF his proess is lled doping the semiondutorF st is lso one of the gret hllenges of the semiondutor mnufturing industryD for it is neessry to mintin fntsti levels of ontrol of the impurities in the mteril in order to predit nd ontrol their eletril propertiesF eginD if this were the end of the storyD we still would not hve ny lultorsD ell phonesD or stereosD or t lest they would e very ig nd umersome nd unrelileD euse they would hve to work using vuum tuesF e now hve to fous on the few 4empty4 spots in the lowerD lmost full nd @lled the valence bandFA e will tke nother view of this ndD from somewht di'erent perspetiveF s must onfess t this point tht wht s m giving you is even further from the wy things relly workD then the 4ups t di'erent energies4 piture we hve een using so frF he prolem isD tht in order to do things rightD we hve to get involved in momentum phseEspeD lot more quntum mehnisD nd generlly unh
II of mth nd onepts we don9t relly need in order to hve some ide of how semiondutor devies workF ht follow elow is relly intended s motivtionD so tht you will hve some feeling tht wht we stte s resultsD is tully resonleF gonsider pigure IFWF rere we show ll of the eletrons in the vleneD or lmost full ndD nd for simpliity show one missing eletronF vet9s pply n eletri (eldD s shown y the rrow in the (gureF he (eld will try to move the @negtively hrgedA eletrons to the leftD ut sine the nd is lmost ompletely fullD the only one tht n move is the one right next to the empty spotD or hole s it is lledF
Figure 1.9:
Band full of electrons, with one missing.
yne thing you my e worrying out is wht hppens to the eletrons t the ends of the smpleF his is one of the ples where we re getting somewht distorted view of thingsD euse we should relly e looking in momentumD or wveEvetor spe rther thn 4rel4 speF sn tht pitureD they mgilly drop o' one side nd 4repper4 on the otherF his doesn9t hppen in rel spe of ourseD so there is no esy wy we n del with itF e short time fter we pply the eletri (eld we hve the sitution shown in pigure IFIHD nd little while fter tht we hve pigure IFIIF e n interpret this motion in two wysF yne is tht we hve net )ow of negtive hrge to the leftD or if we onsider the e'et of the ggregte of ll the eletrons in the nd we ould piture wht is going on s single positive hrgeD moving to the rightF his is shown in pigure IFIPF xote tht in either view we hve the sme net e'et in the wy the totl net hrge is trnsported through the smpleF sn the mostly negtive hrge pitureD we hve net )ow of negtive hrge to the leftF sn the single positive hrge pitureD we hve net )ow of positive hrge to the rightF foth give the sme sign for the urrent3
IP
Figure 1.10:
Motion of the "missing" electron with an electric eld.
Figure 1.11:
Further motion of the "missing electron" spot.
Figure 1.12:
Motion of a "hole" due to an applied electric eld.
IQ husD it turns outD we n onsider the onsequenes of the empty spes moving through the oEordinted motion of eletrons in n lmost full nd s eing the motion of positive hrgesD moving wherever these empty spes hppen to eF e ll these hrge rriers 4holes4 nd they too n dd to the totl ondution of eletriity in semiondutorF sing to represent the density @in m-3 of spes in the vlene nd nd e nd h to represent the moility of eletrons nd holes respetively @they re usully not the smeA we n modify to give the ondutivity D when oth eletrons9 holes re presentD @IFSAF @IFSA row n we get smple of semiondutor with lot of holes in itc ht ifD insted of phosphorusD we dope our silion smple with group sss elementD sy oronc his is shown in pigure IFIQF xow we hve some missing oritlsD or ples where eletrons ould go if they were roundF his modi(es our energy piture s follows in pigure IFIRF xow we see set of new levels introdued y the oron tomsF hey re loted within the nd gpD just little wy ove the top of the lmost fullD or vlene ndF iletrons in the vlene nd n e thermlly exited up into these new llowed levelsD reting empty sttesD or holesD in the vlene ndF he exited eletrons re stuk t the oron tom sites lled acceptorsD sine they 4ept4 n eletron from the vlene ndD nd hene t s (xed negtive hrgesD lolized thereF e semiondutor whih is doped predominntly with eptors is lled p-typeD nd most of the eletril ondution tkes ple through the motion of holesF e semiondutor whih is doped with donors is lled n-typeD nd ondution tkes ple minly through the motion of eletronsF
Figure 1.13:
A two dimensional representation of a silicon crystal lattice doped with boron.
IR
Figure 1.14:
P-type silicon, due to boron acceptors.
sn nEtype mterilD we n ssume tht ll of the phosphorous tomsD or donorsD re fully ionized when they re present in the silion strutureF ine the numer of donors is usully muh greter thn the ntiveD or intrinsi eletron onentrtionD @ IH10 m-3 AD if Nd is the density of donors in the mterilD then nD the eletron onentrtionD Nd F sf n eletron de(ient mteril suh s oron is presentD then the mteril is lled p-type silionD nd the hole onentrtion is just Na the onentrtion of acceptorsD sine these toms 4ept4 eletrons from the vlene ndF sf oth donors nd eptors re in the mterilD then whih ever one hs the higher onentrtion wins outF his is lled ompenstionF sf there re more donors thn eptors then the mteril is nEtype nd n Nd - Na F sf there re more eptors thn donors then the mteril is pEtype nd p Na - Nd F st should e noted tht in most ompensted mterilD one type of impurity usully hs muh greter @severl order of mgnitudeA onentrtion thn the otherD nd so the sutrtion proess desried ove usully does not hnge things very muhD eFgFD IH18 E IH16 IH18 F yne other ft whih you might (nd useful is thtD ginD euse of quntum mehnisD it turns out tht the produt of the eletron nd hole onentrtion in mteril must remin onstntF sn silion t room tempertureX @IFTA husD if we hve n nEtype smple of silion doped with IH17 donors per ui entimeterD then nD the eletron onentrtion is just p D the hole onentrtionD is IH20 GIH17 a IH3 m-3 F he rriers whih dominte mteril re lled majority carriersD whih would e the eletrons in the ove exmpleF he other rriers re lled minority carriers @the holes in the exmpleA nd while IH3 might not seem like muh ompred to IH17 the presene of minority rriers is still quite importnt nd n not e ignoredF xote tht if the mteril is undopedD then it must e tht n a p nd n a p a IH10 F he piture of 4ups4 of di'erent llowed energy levels is useful for gining pitoril understnding of wht is going on in semiondutorD ut eomes somewht wkwrd when you wnt to strt looking t devies whih re mde up of oth n nd p type silionF husD we will introdue one more wy of desriing wht is going on in our mterilF he piture shown in pigure IFIS is lled nd digrmF e band diagram is just representtion of the energy s funtion of position with semiondutor devieF sn nd digrmD positive energy for eletrons is upwrdD while for holesD positive energy is downwrdsF ht
IS isD if n eletron moves upwrdD its potentil energy inreses just s with norml mss in grvittionl (eldF elsoD just s mss will 4fll down4 if given hneD n eletron will move down slope shown in nd digrmF yn the other hndD holes gin energy y moving downwrd nd so they hve tendny to 4)ot4 upwrd if given the hne E muh like ule in liquidF he line leled Ev in pigure IFIS shows the edge of the ondution ndD or the ottom of the lowest unoupied llowed ndD while Ev is the top edge of the vleneD or highest oupied ndF he nd gpD Eg for the mteril is oviously Ec E Ev F he dotted line leled Ef is lled the Fermi level nd it tells us something out the hemil equilirium energy of the mterilD nd lso something out the type nd numer of rriers in the mterilF wore on this lterF xote tht there is no zero energy level on digrm suh s thisF e often use either the permi level or one or other of the nd edges s referene level on lieu of knowing extly where 4zero energy4 is lotedF
Figure 1.15:
An electron band-diagram for a semiconductor.
he distne @in energyA etween the permi level nd either Ec nd Ev gives us informtion onerning the density of eletrons nd holes in tht region of the semiondutor mterilF he detilsD one ginD will hve to e egged o' on grounds of mthemtil omplexityF st turns out tht you n syX @IFUA
@IFVA foth Nc nd Nv re onstnts tht depend on the mteril you re tlking outD ut re typilly on the order of IH19 m-3 F he expression in the denomintor of the exponentil is just foltzmn9s onstnt @VFTQ x IH-5 eGuAD kD times the temperture T of the mteril @in solute temperture or uelvinAF et room temperture kT a 1 G40 of n eletron voltF vook refully t the numertors in the exponentilF xote (rst tht there is minus sign in frontD whih mens the igger the numer in the exponentD the fewer rriers we hveF husD the top expression sys tht if we hve nEtype mterilD then Ef must not e too fr wy from the ondution ndD while if we hve pEtype mterilD then the permi levelDEf must e down lose to the vlene ndF he loser Ef gets to Ec the more eletrons we hveF he loser Ef gets to Ev D the more holes we hveF pigure IFIS therefore must e for smple of nEtype mterilF xote lso tht if we know how hevily smple is doped @iFeFD we know wht Nd isA nd from the ft tht n Nd we n use to (nd out how fr wy the permi level is from the ondution ndD @IFWAF @IFWA
IT
o help further in our ility to piture wht is going onD we will often dd to this nd digrmD some smll signed irles to indite the presene of moile eletrons nd holes in the mterilF xote tht the eletrons re spred out in energyF prom our 4ups4 piture we know they like to sty in the lower energy sttes if possileD ut some will e distriuted into the higher levels s wellF ht is distorted here is the sleF he ndEgp for silion is IFI eD while the tul spred of the eletrons would proly only e few tenths of n eD not nerly s muh s is shown in pigure IFITF vets look t smple of pEtype mterilD just for omprisonF xote tht for holesD inresing energy goes down not upD so their distriution is inverted from tht of the eletronsF ou n kind of think of holes s ules in glss of sod or eerD they wnt to )ot to the top if they nF xote lso for oth n nd pEtype mteril there re lso few 4minority4 rriersD or rriers of the opposite typeD whih rise from therml genertion ross the ndEgpF
Figure 1.16:
Band diagram for an n-type semiconductor.
1.3 Diusion
note:
his module is dpted from the gonnexions module entitled Diusion y fill ilsonF
1.3.1 Introduction
vet us turn our ttention to wht hppens to the eletrons nd holes one they hve een injeted ross forwrdEised juntionF e will onentrte just on the eletrons whih re injeted into the pEside of the juntionD ut keep in mind tht similr things re lso hppening to the holes whih enter the nEsideF hen eletrons re injeted ross juntionD they move wy from the juntion region y di'usion proessD while t the sme timeD some of them re disppering euse they re minority rriers @eletrons in silly pEtype mterilA nd so there re lots of holes round for them to reomine withF his is ll shown shemtilly in pigure IFIUF
3
IU
Figure 1.17:
Processes involved in electron transport across a p-n junction.
1.3.2 Diusion process quantied

st is tully firly esy to quntify thisD nd ome up with n expression for the eletron distriution within the pEregionF pirst we hve to look little it t the di'usion proess howeverF smgine tht we hve series of insD eh with di'erent numer of eletrons in themF sn given timeD we ould imgine tht ll of the eletrons would )ow out of their ins into the neighoring onesF ine there is no reson to expet the eletrons to fvor one side over the otherD we will ssume tht extly hlf leve y eh sideF his is ll shown in pigure IFIVF e will keep things simple nd only look t three insF smgine there re RD TD nd V eletrons respetively in eh of the insF efter the required 4emptying timeD4 we will hve net )ux of extly one eletron ross eh oundry s shownF
Figure 1.18:
A schematic representation of a diusion problem.
xow let9s rise the numer of eletrons to VD IP nd IT respetively @pigure IFIWAF e (nd tht the net )ux ross eh oundry is now P eletrons per emptying timeD rther thn oneF xote tht the grdient @slopeA of the onentrtion in the oxes hs lso douled from one per ox to two per oxF his leds us to rther ovious sttement tht the )ux of rriers is proportionl to the grdient of their densityF his is stted formlly in wht is known s pik9s pirst vw of hi'usionD @IFIHAF here De is simply proportionlity onstnt lled the di'usion oe0ientF ine we re tlking out the motion of eletronsD this di'usion )ux must give rise to urrent density Jediff F ine n eletron hs hrge q ssoited
IV with itD @IFIIAF
Flux = (De ) Jediff = qDe
d n (x) dx
@IFIHA @IFIIA
d (n) dx
Figure 1.19:
A schematic representation of a diusion from bins.
xow we hve to invoke something lled the ontinuity equtionF smgine we hve volume @V A whih is (lled with some hrge @Q AF st is firly ovious tht if we dd up ll of the urrent density whih is )owing out of the volume tht it must e equl to the time rte of derese of the hrge within tht volumeF his ides is expressed in the formul elow whih uses losedEsurfe integrlD long with the ll the other integrls to followX
JdS =
S
d (Q) dt
@IFIPA
e n write Q sD @IFIQAD where we re doing volume integrl of the hrge density @ A over the volume @V AF xow we n use quss9 theorem whih sys we n reple surfe integrl of quntity with volume integrl of its divergeneD @IFIRAF
Q=
V
(v) dV
@IFIQA @IFIRA
JdS =
S V
divJdV
oD omining @IFIPAD @IFIQA nd @IFIRAD we hveD @IFISAF
d () dV dt
@IFISA
divJdV =
V V
pinllyD we let the volume V shrink down to pointD whih mens the quntities inside the integrl must e equlD nd we hve the di'erentil form of the ontinuity eqution @in one dimensionAD @IFITAF
divJ
(J)
d dt (x)
@IFITA
IW
1.3.3 What about the electrons?

xow let9s go k to the eletrons in the diodeF he eletrons whih hve een injeted ross the juntion re lled excess minority carriersD euse they re eletrons in pEregion @hene minorityA ut their onentrtion is greter thn wht they would e if they were in smple of pEtype mteril t equiliriumF e will designte them s n'D nd sine they ould hnge with oth time nd position we shll write them s n' @xDtAF xow there re two wys in whih n' @xDtA n hnge with timeF yne would e if we were to stop injeting eletrons in from the nEside of the juntionF e resonle wy to ount for the dey whih would our if we were not supplying eletrons would e to writeX
d n (x, t) = dt
n (x, t) r
@IFIUA
here r lled the minority rrier reomintion lifetimeF st is pretty esy to show tht if we strt out with n exess minority rrier onentrtion n0 ' t t a HD then n' @xDtA will go sD @IFIVAF futD the eletron onentrtion n lso hnge euse of eletrons )owing into or out of the region xF he eletron onentrtion n' @xDtA is just (x,t) F husD due to eletron )ow we hveD @IFIWAF q
n (x, t) = n 0 e r
d dt n
@IFIVA @IFIWA
(x, t)
= =
1 d q dt (x, t) 1 q div (J (x, t))
futD we n get n expression for J (x, t) from @IFIIAF eduing the divergene in @IFIWA to one dimension @we just hve x (J)A we (nlly end up withD @IFPHAF
d d2 n (x, t) = De 2 n (x, t) @IFPHA dt dx gomining @IFPHA nd @IFIUA @eletrons willD fter llD su'er from oth reomintion nd di'usionA nd we end up withX d n (x, t) d2 n (x, t) = De 2 n (x, t) @IFPIA dt dx r his is somewht speilized form of n eqution lled the mipolr di'usion equtionF st seems kind of omplited ut we n get some nie results from it if we mke some simply oundry ondition ssumptionsF
1.3.3.1 Using the ambipolar diusion equation
por nything we will e interested inD we will only look t stedy stte solutionsF his mens tht the time derivtive on the vr of @IFPIA is zeroD nd so letting n (x, t) eome simply n (x) sine we no longer hve ny time vrition to worry outD we hveX
d2 1 n (x) n (x) = 0 2 dt De r
@IFPPA
iking the not unresonle oundry onditions tht n (0) = n0 @the onentrtion of exess eletrons just t the strt of the di'usion regionA nd n (x) 0 s x @the exess rriers go to zero when we get fr from the juntionA thenX
he expression in the rdil De r is lled the eletron di'usion lengthD Le D nd gives us some ide s to how fr wy from the juntion the exess eletrons will exist efore they hve more or less ll reominedF
n (x) = n0 e
x De r
@IFPQA
PH
his will e importnt for us when we move on to ipolr trnsistorsF e typil vlue for the di'usion oe0ient for eletrons in silion would e De a PS m2 Gse nd the minority rrier lifetime is usully round miroseondF es shown in @IFPRA this is not very fr t llF
Le
= = =
De r 25 106
@IFPRA
3
5 10
cm
1.4 Crystal Structure

1.4.1 Introduction
sn ny sort of disussion of rystlline mterilsD it is useful to egin with disussion of rystllogrphyX the study of the formtionD strutureD nd properties of rystlsF e rystl struture is de(ned s the prtiulr repeting rrngement of toms @moleules or ionsA throughout rystlF truture refers to the internl rrngement of prtiles nd not the externl pperne of the rystlF roweverD these re not entirely independent sine the externl pperne of rystl is often relted to the internl rrngementF por exmpleD rystls of ui rok slt @xglA re physilly ui in pperneF ynly few of the possile rystl strutures re of onern with respet to simple inorgni slts nd these will e disussed in detilD howeverD it is importnt to understnd the nomenlture of rystllogrphyF
1.4.2 Crystallography
1.4.2.1 Bravais lattice
he frvis lttie is the si uilding lok from whih ll rystls n e onstrutedF he onept originted s topologil prolem of (nding the numer of di'erent wys to rrnge points in spe where eh point would hve n identil tmosphereF ht is eh point would e surrounded y n identil set of points s ny other pointD so tht ll points would e indistinguishle from eh otherF wthemtiin euguste frvis disovered tht there were IR di'erent olletions of the groups of pointsD whih re known s frvis lttiesF hese ltties fll into seven di'erent 4rystl systemsD s di'erentited y the reltionship etween the ngles etween sides of the unit ell nd the distne etween points in the unit ellF he unit ell is the smllest group of tomsD ions or moleules thtD when repeted t regulr intervls in three dimensionsD will produe the lttie of rystl systemF he lttie prmeter is the length etween two points on the orners of unit ellF ih of the vrious lttie prmeters re designted y the letters aD bD nd cF sf two sides re equlD suh s in tetrgonl lttieD then the lengths of the two lttie prmeters re designted a nd cD with b omittedF he ngles re designted y the qreek letters D D nd D suh tht n ngle with spei( qreek letter is not sutended y the xis with its omn equivlentF por exmpleD is the inluded ngle etween the b nd c xisF le IFI shows the vrious rystl systemsD while pigure IFPH shows the IR frvis lttiesF st is importnt to distinguish the hrteristis of eh of the individul systemsF en exmple of mteril tht tkes on eh of the frvis ltties is shown in le IFPF
System Axial lengths and angles Unit cell geometry
continued on next page
PI ui a a D a a a WH
tetrgonl
a = D a a a WH
orthorhomi
= = D a a a WH
rhomohedrl
a a D a a = WH
hexgonl
a = D a a WH D a IPH = = D a a WH D = WH
monolini
trilini
= = D = =
Table 1.1
X qeometril hrteristis of the seven rystl systemsF
PP
Figure 1.20:
Bravais lattices.
PQ
Crystal system
Example
trilini monolini rhomohedrl hexgonl orthorhomi tetrgonl ui

Table 1.2
u2 2 y8 es4 4 D uxy2 rgD nD goD xies qD pe3 g snD iy2 euD iD xgl
X ixmples of elements nd ompounds tht dopt eh of the rystl systemsF
he ui lttie is the most symmetril of the systemsF ell the ngles re equl to WH D nd ll the sides re of the sme length @a a b a c AF ynly the length of one of the sides @aA is required to desrie this system ompletelyF sn ddition to simple uiD the ui lttie lso inludes odyEentered ui nd feEentered ui @pigure IFPHAF fodyEentered ui results from the presene of n tom @or ionA in the enter of ueD in ddition to the toms @ionsA positioned t the verties of the ueF sn similr mnnerD feEentered ui requiresD in ddition to the toms @ionsA positioned t the verties of the ueD the presene of toms @ionsA in the enter of eh of the ues feF he tetrgonl lttie hs ll of its ngles equl to WH D nd hs two out of the three sides of equl length @a a bAF he system lso inludes odyEentered tetrgonl @pigure IFPHAF sn n orthorhomi lttie ll of the ngles re equl to WH D while ll of its sides re of unequl lengthF he system needs only to e desried y three lttie prmetersF his system lso inludes odyEentered orthorhomiD seEentered orthorhomiD nd feEentered orthorhomi @pigure IFPHAF e seEentered lttie hsD in ddition to the toms @ionsA positioned t the verties of the orthorhomi lttieD toms @ionsA positioned on just two opposing fesF he rhomohedrl lttie is lso known s trigonlD nd hs no ngles equl to WH D ut ll sides re of equl length @a a b a c AD thus requiring only y one lttie prmeterD nd ll three ngles re equl @ a a AF e hexgonl rystl struture hs two ngles equl to WH D with the other ngle @ A equl to IPH F por this to hppenD the two sides surrounding the IPH ngle must e equl @a a bAD while the third side @c A is t WH to the other sides nd n e of ny lengthF he monolini lttie hs no sides of equl lengthD ut two of the ngles re equl to WH D with the other ngle @usully de(ned s A eing something other thn WH F st is tilted prllelogrm prism with retngulr sesF his system lso inludes seEentered monolini @pigure IFPHAF sn the trilini lttie none of the sides of the unit ell re equlD nd none of the ngles within the unit ell re equl to WH F he trilini lttie is hosen suh tht ll the internl ngles re either ute or otuseF his rystl system hs the lowest symmetry nd must e desried y Q lttie prmeters @aD bD nd c A nd the Q ngles @D D nd AF
1.4.2.2 Atom positions, crystal directions and Miller indices 1.4.2.2.1 Atom positions and crystal axes
he struture of rystl is de(ned with respet to unit ellF es the entire rystl onsists of repeting unit ellsD this de(nition is su0ient to represent the entire rystlF ithin the unit ellD the tomi rrngement is expressed using oordintesF here re two systems of oordintes ommonly in useD whih n use some onfusionF foth use orner of the unit ell s their originF he (rstD lessEommonly seen system is tht of grtesin or orthogonl oordintes @D D AF hese usully hve the units of engstroms nd relte to the distne in eh diretion etween the origin of the ell nd the tomF hese oordintes my e
PR
mnipulted in the sme fshion re used with twoE or threeEdimensionl grphsF st is very simpleD thereforeD to lulte interEtomi distnes nd ngles given the grtesin oordintes of the tomsF nfortuntelyD the repeting nture of rystl nnot e expressed esily using suh oordintesF por exmpleD onsider ui ell of dimension QFSP F retend tht this ell ontins n tom tht hs the oordintes @IFSD PFID PFRAF ht isD the tom is IFS wy from the origin in the x diretion @whih oinides with the a ell xisAD PFI in the y @whih oinides with the b ell xisA nd PFR in the z @whih oinides with the c ell xisAF here will e n equivlent tom in the next unit ell long the xEdiretionD whih will hve the oordintes @IFS C QFSPD PFID PFRA or @SFHPD PFID PFRAF his ws rther simple lultionD s the ell hs very high symmetry nd so the ell xesD aD b nd cD oinide with the grtesin xesD D nd F roweverD onsider lower symmetry ells suh s trilini or monolini in whih the ell xes re not mutully orthogonlF sn suh sesD expressing the repeting nture of the rystl is muh more di0ult to omplishF eordinglyD tomi oordintes re usully expressed in terms of frtionl oordintesD @xD yD zAF his oordinte system is oinident with the ell xes @aD bD c A nd reltes to the position of the tom in terms of the frtion long eh xisF gonsider the tom in the ui ell disussion oveF he tom ws IFS in the a diretion wy from the originF es the a xis is QFSP longD the tom is @1.5 G3.52 A or HFRQ of the xis wy from the originF imilrlyD it is @2.1 G3.52 A or HFTH of the b xis nd @2.4 G3.5 A or HFTV of the c xisF he frtionl oordintes of this tom reD thereforeD @HFRQD HFTHD HFTVAF he oordintes of the equivlent tom in the next ell over in the a diretionD howeverD re esily lulted s this tom is simply I unit ell wy in aF husD ll one hs to do is dd I to the x oordinteX @IFRQD HFTHD HFTVAF uh trnsformtions n e performed regrdless of the shpe of the unit ellF prtionl oordintesD thereforeD re used to retin nd mnipulte rystl informtionF
1.4.2.2.2 Crystal directions
he designtion of the individul vetors within ny given rystl lttie is omplished y the use of whole numer multipliers of the lttie prmeter of the point t whih the vetor exits the unit ellF he vetor is indited y the nottion hkl D where hD kD nd l re reiprols of the point t whih the vetor exits the unit ellF he origintion of ll vetors is ssumed de(ned s HHHF por exmpleD the diretion long the aExis ording to this sheme would e IHH euse this hs omponent only in the aEdiretion nd no omponent long either the b or c xil diretionF e vetor digonlly long the fe de(ned y the a nd b xis would e IIHD while going from one orner of the unit ell to the opposite orner would e in the III diretionF pigure IFPI shows some exmples of the vrious diretions in the unit ellF he rystl diretion nottion is mde up of the lowest omintion of integers nd represents unit distnes rther thn tul distnesF e PPP diretion is identil to IIID so III is usedF prtions re not usedF por exmpleD vetor tht interepts the enter of the top fe of the unit ell hs the oordintes x a IGPD y a IGPD z a IF ell hve to e inversed to onvert to the lowest omintion of integers @whole numersAY iFeFD PPI in pigure IFPIF pinllyD ll prllel vetors hve the sme rystl diretionD eFgFD the four vertil edges of the ell shown in pigure IFPI ll hve the rystl diretion hkl a HHIF
PS
Figure 1.21:
Some common directions in a cubic unit cell.
grystl diretions my e grouped in fmiliesF o void onfusion there exists onvention in the hoie of rkets surrounding the three numers to di'erentite rystl diretion from fmily of diretionF por diretionD squre rkets hkl re used to indite n individul diretionF engle rkets <hkl > indite fmily of diretionsF e fmily of diretions inludes ny diretions tht re equivlent in length nd types of toms enounteredF por exmpleD in ui lttieD the IHHD HIHD nd HHI diretions ll elong to the <IHH> fmily of plnes euse they re equivlentF sf the ui lttie were rotted WH D the aD bD nd c diretions would remin indistinguishleD nd there would e no wy of telling on whih rystllogrphi positions the toms re situtedD so the fmily of diretions is the smeF sn hexgonl rystlD howeverD this is not the seD so the IHH nd HIH would oth e <IHH> diretionsD ut the HHI diretion would e distintF pinllyD negtive diretions re identi(ed with r over the negtive numer insted of minus signF
1.4.2.2.3 Crystal planes
lnes in rystl n e spei(ed using nottion lled willer indiesF he willer index is indited y the nottion hkl where hD kD nd l re reiprols of the plne with the xD yD nd z xesF o otin the willer indies of given plne requires the following stepsX tep tep tep tep IF PF QF RF he plne in question is pled on unit ellF sts interepts with eh of the rystl xes re then foundF he reiprol of the interepts re tkenF hese re multiplied y slr to insure tht is in the simple rtio of whole numersF
por exmpleD the fe of lttie tht does not interset the y or z xis would e @IHHAD while plne long the ody digonl would e the @IIIA plneF en illustrtion of this long with the @IIIA nd @IIHA plnes is given in pigure IFPPF
PT
Figure 1.22:
Examples of Miller indices notation for crystal planes.
es with rystl diretionsD willer indies diretions my e grouped in fmiliesF sndividul willer indies re given in prentheses @hkl AD while res {hkl } re pled round the indies of fmily of plnesF por exmpleD @HHIAD @IHHAD nd @HIHA re ll in the {IHH} fmily of plnesD for ui lttieF
1.4.3 Description of crystal structures

grystl strutures my e desried in numer of wysF he most ommon mnner is to refer to the size nd shpe of the unit ell nd the positions of the toms @or ionsA within the ellF roweverD this informtion is sometimes insu0ient to llow for n understnding of the true struture in three dimensionsF gonsidertion of severl unit ellsD the rrngement of the toms with respet to eh otherD the numer of other toms they in ontt withD nd the distnes to neighoring tomsD often will provide etter understndingF e numer of methods re ville to desrie extended solidEstte struturesF he most pplile with
PU regrd to elementl nd ompound semiondutorD metls nd the mjority of insultors is the lose pking pprohF
1.4.3.1 Close packed structures: hexagonal close packing and cubic close packing
wny rystl strutures n e desried using the onept of lose pkingF his onept requires tht the toms @ionsA re rrnged so s to hve the mximum densityF sn order to understnd lose pking in three dimensionsD the most e0ient wy for equl sized spheres to e pked in two dimensions must e onsideredF he most e0ient wy for equl sized spheres to e pked in two dimensions is shown in pigure IFPQD in whih it n e seen tht eh sphere @the drk gry shded sphereA is surrounded yD nd is in ontt withD six other spheres @the light gry spheres in pigure IFPQAF st should e noted tht ontt with six other spheres the mximum possile is the spheres re the sme sizeD lthough lower density pking is possileF glose pked lyers re formed y repetition to n in(nite sheetF ithin these lose pked lyersD three lose pked rows re presentD shown y the dshed lines in pigure IFPQF
Figure 1.23: Schematic representation of a close packed layer of equal sized spheres. The close packed rows (directions) are shown by the dashed lines.
he most e0ient wy for equl sized spheres to e pked in three dimensions is to stk lose pked lyers on top of eh other to give lose pked strutureF here re two simple wys in whih this n e doneD resulting in either hexgonl or ui lose pked struturesF
1.4.3.1.1 Hexagonal close packed
sf two lose pked lyers e nd f re pled in ontt with eh other so s to mximize the densityD then the spheres of lyer f will rest in the hollow @vnyA etween three of the spheres in lyer eF his is demonstrted in pigure IFPRF etoms in the seond lyerD f @shded light gryAD my oupy one of two possile positions @pigure IFPR or A ut not oth together or mixture of ehF sf third lyer is pled on top of lyer f suh tht it extly overs lyer eD susequent plement of lyers will result in the following sequene FFFefefefFFFF his is known s hexgonl lose pking or hcpF
PV
Schematic representation of two close packed layers arranged in A (dark grey) and B (light grey) positions. The alternative stacking of the B layer is shown in (a) and (b).
Figure 1.24:
he hexgonl lose pked ell is derivtive of the hexgonl frvis lttie system @pigure IFPHA with the ddition of n tom inside the unit ell t the oordintes @1 G3 D2 G3 D1 G2 AF he sl plne of the unit ell oinides with the lose pked lyers @pigure IFPSAF sn other words the lose pked lyer mkesEup the {HHI} fmily of rystl plnesF
Figure 1.25:
A schematic projection of the basal plane of the hcp unit cell on the close packed layers.
he pking frtion in hexgonl lose pked ell is URFHS7Y tht is URFHS7 of the totl volume is oupiedF he pking frtion or density is derived y ssuming tht eh tom is hrd sphere in ontt with its nerest neighorsF hetermintion of the pking frtion is omplished y lulting the numer of whole spheres per unit ell @P in hpAD the volume oupied y these spheresD nd omprison with the totl volume of unit ellF he numer gives n ide of how open or (lled struture isF fy omprisonD the pking frtion for odyEentered ui @pigure IFPHA is TV7 nd for dimond ui @n importnt semiondutor struture to e desried lterA is it QR7F
1.4.3.1.2 Cubic close packed: face-centered cubic
sn similr mnner to the genertion of the hexgonl lose pked strutureD two lose pked lyers re stked @pigure IFPQA howeverD the third lyer @gA is pled suh tht it does not extly over lyer eD
PW while sitting in set of troughs in lyer f @pigure IFPTAD then upon repetition the pking sequene will e FFFefgefgefgFFFF his is known s ui lose pking or ccpF
Schematic representation of the three close packed layers in a cubic close packed arrangement: A (dark grey), B (medium grey), and C (light grey).
Figure 1.26:
he unit ell of ui lose pked struture is tully tht of feEentered ui @fcc A frvis lttieF sn the fcc lttie the lose pked lyers onstitute the {III} plnesF es with the hcp lttie pking frtion in ui lose pked @fcc A ell is URFHS7F ine fe entered ui or fcc is more ommonly used in preferene to ui lose pked @ccp A in desriing the struturesD the former will e used throughout this textF
1.4.3.2 Coordination number
he oordintion numer of n tom or ion within n extended struture is de(ned s the numer of nerest neighor toms @ions of opposite hrgeA tht re in ontt with itF e slightly di'erent de(nition is often used for toms within individul moleulesX the numer of donor toms ssoited with the entrl tom or ionF roweverD this distintion is rther rti(ilD nd oth n e employedF he oordintion numers for metl toms in moleule or omplex re ommonly RD SD nd TD ut ll vlues from P to W re known nd few exmples of higher oordintion numers hve een reportedF sn ontrstD ommon oordintion numers in the solid stte re QD RD TD VD nd IPF por exmpleD the tom in the enter of odyEentered ui lttie hs oordintion numer of VD euse it touhes the eight toms t the orners of the unit ellD while n tom in simple ui struture would hve oordintion numer of TF sn oth fcc nd hcp ltties eh of the toms hve oordintion numer of IPF
1.4.3.3 Octahedral and tetrahedral vacancies
es ws mentioned oveD the pking frtion in oth fcc nd hcp ells is URFHS7D leving PSFWS7 of the volume un(lledF he un(lled lttie sites @interstiesA etween the toms in ell re lled interstitil sites or vniesF he shpe nd reltive size of these sites is importnt in ontrolling the position of dditionl tomsF sn oth fcc nd hcp ells most of the spe within these toms lies within two di'erent sites known s othedrl sites nd tetrhedrl sitesF he di'erene etween the two lies in their oordintion numerD or the numer of toms surrounding eh siteF etrhedrl sites @vniesA re surrounded y four toms rrnged t the orners of tetrhedronF imilrlyD othedrl sites re surrounded y six toms whih mkeEup the pies of n othedronF por given lose pked lttie n othedrl vny will e lrger thn tetrhedrl vnyF ithin fe entered ui lttieD the eight tetrhedrl sites re positioned within the ellD t the generl frtionl oordinte of @n G4 Dn G4 Dn G4 A where n a I or QD eFgFD @1 G4 D1 G4 D1 G4 AD @1 G4 D1 G4 D3 G4 AD etF he
QH
othedrl sites re loted t the enter of the unit ell @1 G2 D1 G2 D1 G2 AD s well s t eh of the edges of the ellD eFgFD @1 G2 DHDHAF sn the hexgonl lose pked systemD the tetrhedrl sites re t @HDHD3 G8 A nd @1 G3 D2 G3 D7 G8 AD nd the othedrl sites re t @1 G3 D1 G3 D1 G4 A nd ll symmetry equivlent positionsF
1.4.3.4 Important structure types
he mjority of rystlline mterils do not hve struture tht (ts into the one tom per site simple frvis lttieF e numer of other importnt rystl strutures re foundD howeverD only few of these rystl strutures re those of whih our for the elementl nd ompound semiondutors nd the mjority of these re derived from fcc or hcp lttiesF ih struturl type is generlly de(ned y n rhetypeD mteril @often nturlly ourring minerlA whih hs the struture in question nd to whih ll the similr mterils re reltedF ith regrd to ommonly used elementl nd ompound semiondutors the importnt strutures re dimondD zin lendeD urtziteD nd to lesser extent hlopyriteF roweverD rok sltD EtinD innr nd esium hloride re oserved s high pressure or high temperture phses nd re therefore lso disussedF he following provides summry of these struturesF hetils of the full rnge of solidEstte strutures re given elsewhereF
1.4.3.4.1 Diamond Cubic
he dimond ui struture onsists of two interpenetrting feEentered ui lttiesD with one o'set 1 G4 of ue long the ue digonlF st my lso e desried s fe entered ui lttie in whih hlf of the tetrhedrl sites re (lled while ll the othedrl sites remin vntF he dimond ui unit ell is shown in pigure IFPUF ih of the toms @eFgFD gA is four oordinteD nd the shortest intertomi distne @gEgA my e determined from the unit ell prmeter @aAF @IFPSA
Figure 1.27:
Unit cell structure of a diamond cubic lattice showing the two interpenetrating facecentered cubic lattices.
QI
1.4.3.4.2 Zinc blende
his is inry phse @wiA nd is nmed fter its rhetypeD ommon minerl form of zin sul(de @nAF es with the dimond lttieD zin lende onsists of the two interpenetrting fcc lttiesF roweverD in zin lende one lttie onsists of one of the types of toms @n in nAD nd the other lttie is of the seond type of tom @ in nAF st my lso e desried s fe entered ui lttie of toms in whih hlf of the tetrhedrl sites re (lled with n tomsF ell the toms in zin lende struture re REoordinteF he zin lende unit ell is shown in pigure IFPVF e numer of interEtomi distnes my e lulted for ny mteril with zin lende unit ell using the lttie prmeter @aAF @IFPTA
@IFPUA
Unit cell structure of a zinc blende (ZnS) lattice. Zinc atoms are shown in green (small), sulfur atoms shown in red (large), and the dashed lines show the unit cell.
Figure 1.28:
1.4.3.4.3 Chalcopyrite
he minerl hlopyrite gupe2 is the rhetype of this strutureF he struture is tetrgonl @a a b = cD a a a WH D nd is essentilly superlttie on tht of zin lendeF husD is esiest to imgine tht the hlopyrite lttie is mdeEup of lttie of sulfur toms in whih the tetrhedrl sites re (lled in lyersD FFFpegugupeFFFD etF @pigure IFPWAF sn suh n idelized struture c a PaD howeverD this is not true of ll mterils with hlopyrite struturesF
QP
Unit cell structure of a chalcopyrite lattice. Copper atoms are shown in blue, iron atoms are shown in green and sulfur atoms are shown in yellow. The dashed lines show the unit cell.
Figure 1.29:
1.4.3.4.4 Rock salt
es its nme implies the rhetypl rok slt struture is xgl @tle sltAF sn ommon with the zin lende strutureD rok slt onsists of two interpenetrting feEentered ui lttiesF roweverD the seond lttie is o'set IGPa long the unit ell xisF st my lso e desried s fe entered ui lttie in whih ll of the othedrl sites re (lledD while ll the tetrhedrl sites remin vntD nd thus eh of the toms in the rok slt struture re TEoordinteF he rok slt unit ell is shown in pigure IFQHF e numer of interEtomi distnes my e lulted for ny mteril with rok slt struture using the lttie prmeter @aAF @IFPVA
@IFPWA
QQ
Unit cell structure of a rock salt lattice. Sodium ions are shown in purple (small spheres) and chloride ions are shown in red (large spheres).
Figure 1.30:
1.4.3.4.5 Cinnabar
ginnrD nmed fter the rhetype merury sul(deD rgD is distorted rok slt struture in whih the resulting ell is rhomohedrl @trigonlA with eh tom hving oordintion numer of sixF
1.4.3.4.6 Wurtzite
his is hexgonl form of the zin sul(deF st is identil in the numer of nd types of tomsD ut it is uilt from two interpenetrting hcp ltties s opposed to the fcc ltties in zin lendeF es with zin lende ll the toms in wurtzite struture re REoordinteF he wurtzite unit ell is shown in pigure IFQIF e numer of inter tomi distnes my e lulted for ny mteril with wurtzite ell using the lttie prmeter @aAF @IFQHA
@IFQIA roweverD it should e noted tht these formule do not neessrily pply when the rtio aGc is di'erent from the idel vlue of IFTQPF
QR
Figure 1.31: Unit cell structure of a wurtzite lattice. Zinc atoms are shown in green (small spheres), sulfur atoms shown in red (large spheres), and the dashed lines show the unit cell.
1.4.3.4.7 Cesium Chloride
he esium hloride struture is found in mterils with lrge tions nd reltively smll nionsF st hs simple @primitiveA ui ell @pigure IFPHA with hloride ion t the orners of the ue nd the esium ion t the ody enterF he oordintion numers of oth gs+ nd gl- D with the inner tomi distnes determined from the ell lttie onstnt @aAF @IFQPA
@IFQQA
1.4.3.4.8
-Tin.
he room temperture llotrope of tin is Etin or white tinF st hs tetrgonl strutureD in whih eh tin tom hs four nerest neighors @nEn a QFHIT A rrnged in very )ttened tetrhedronD nd two next nerest neighors @nEn a QFIUS AF he overll struture of Etin onsists of fused hexgonsD eh eing linked to its neighor vi fourEmemered n4 ringF
1.4.4 Defects in crystalline solids

p to this point we hve only een onerned with idel strutures for rystlline solids in whih eh tom oupies designted point in the rystl lttieF nfortuntelyD defets ordinrily exist in equilirium etween the rystl lttie nd its environmentF hese defets re of two generl typesX point defets nd extended defetsF es their nmes implyD point defets re ssoited with single rystl lttie siteD while extended defets our over greter rngeF
QS
1.4.4.1 Point defects: too many or too few or just plain wrong
oint defets hve signi(nt e'et on the properties of semiondutorD so it is importnt to understnd the lsses of point defets nd the hrteristis of eh typeF pigure IFQP summrizes vrious lsses of ntive point defetsD howeverD they my e divided into two generl lssesY defets with the wrong numer of toms @de(ieny or surplusA nd defets where the identity of the toms is inorretF
Figure 1.32:
Point defects in a crystal lattice.
1.4.4.1.1 Interstitial Impurity
en interstitil impurity ours when n extr tom is positioned in lttie site tht should e vnt in n idel struture @pigure IFQPAF ine ll the djent lttie sites re (lled the dditionl tom will hve to squeeze itself into the interstitil siteD resulting in distortion of the lttie nd ltertion in the lol
QT
eletroni ehvior of the strutureF mll tomsD suh s ronD will prefer to oupy these interstitil sitesF snterstitil impurities redily di'use through the lttie vi interstitil di'usionD whih n result in hnge of the properties of mteril s funtion of timeF yxygen impurities in silion generlly re loted s interstitilsF
1.4.4.1.2 Vacancies
he onverse of n interstitil impurity is when there re not enough toms in prtiulr re of the lttieF hese re lled vniesF nies exist in ny mteril ove solute zero nd inrese in onentrtion with tempertureF sn the se of ompound semiondutorsD vnies n e either tion vnies @pigure IFQPA or nion vnies @pigure IFQPdAD depending on wht type of tom re missingF
1.4.4.1.3 Substitution
ustitution of vrious toms into the norml lttie struture is ommonD nd used to hnge the eletroni properties of oth ompound nd elementl semiondutorsF eny impurity element tht is inorported during rystl growth n oupy lttie siteF hepending on the impurityD sustitution defets n gretly distort the lttie ndGor lter the eletroni strutureF sn generlD tions will try to oupy tion lttie sites @pigure IFQPeAD nd nion will oupy the nion site @pigure IFQPfAF por exmpleD zin impurity in qes will oupy gllium siteD if possileD while sulfurD selenium nd tellurium toms would ll try to sustitute for n rseniF ome impurities will oupy either site indisrimintelyD eFgFD i nd n oupy oth q nd es sites in qesF
1.4.4.1.4 Antisite Defects
entisite defets re prtiulr form of sustitution defetD nd re unique to ompound semiondutorsF en ntisite defet ours when tion is mispled on n nion lttie site or vie vers @pigure IFQPg nd hAF hependnt on the rrngement these re designted s either eB ntisite defets or fA ntisite defetsF por exmpleD if n rseni tom is on gllium lttie site the defet would e n esGa defetF entisite defets involve (tting into lttie site toms of di'erent size thn the rest of the lttieD nd therefore this often results in lolized distortion of the lttieF sn dditionD tions nd nions will hve di'erent numer of eletrons in their vlene shellsD so this sustitution will lter the lol eletron onentrtion nd the eletroni properties of this re of the semiondutorF
1.4.4.2 Extended Defects: Dislocations in a Crystal Lattice
ixtended defets my e reted either during rystl growth or s onsequene of stress in the rystl lttieF he plsti deformtion of rystlline solids does not our suh tht ll onds long plne re roken nd reformed simultneouslyF snstedD the deformtion ours through dislotion in the rystl lttieF pigure IFQQ shows shemti representtion of dislotion in rystl lttieF wo fetures of this type of dislotion re the presene of n extr rystl plneD nd lrge void t the dislotion oreF smpurities tend to segregte to the dislotion ore in order to relieve strin from their preseneF
QU
Figure 1.33:
Dislocation in a crystal lattice.
1.4.5 Epitaxy
ipitxyD is trnslitertion of two qreek words epiD mening 4upon4D nd taxisD mening 4ordered4F ith respet to rystl growth it pplies to the proess of growing thin rystlline lyers on rystl sustrteF sn epitxil growthD there is preise rystl orienttion of the (lm in reltion to the sustrteF he growth of epitxil (lms n e done y numer of methods inluding moleulr em epitxyD tomi lyer epitxyD nd hemil vpor depositionD ll of whih will e desried lterF ipitxy of the sme mterilD suh s gllium rsenide (lm on gllium rsenide sustrteD is lled homoepitxyD while epitxy where the (lm nd sustrte mteril re di'erent is lled heteroepitxyF glerlyD in homoepitxyD the sustrte nd (lm will hve the identil strutureD howeverD in heteroepitxyD it is importnt to employ where possile sustrte with the sme struture nd similr lttie prmetersF por exmpleD zin selenide @zin lendeD a a SFTTV A is redily grown on gllium rsenide @zin lendeD a a SFTSQ AF elterntivelyD epitxil rystl growth n our where there exists simple reltionship etween the strutures of the sustrte nd rystl lyerD suh s is oserved etween el2 y3 @IHHA on i @IHHAF hihever route is hosen lose mth in the lttie prmeters is requiredD otherwiseD the strins indued y the lttie mismth results in distortion of the (lm nd formtion of dislotionsF sf the mismth is signi(nt epitxil growth is not energetilly fvorleD using textured (lm or polyrystlline untextured (lm to e grownF es generl rule of thumD epitxy n e hieved if the lttie prmeters of the two mterils re within out S7 of eh otherF por good qulity epitxyD this should e less thn I7F he lrger the mismthD the lrger the strin in the (lmF es the (lm gets thiker nd thikerD it will try to relieve the strin in the (lmD whih ould inlude the loss of epitxy of the growth of dislotionsF st is importnt to note tht the <IHH> diretions of (lm must e prllel to the <IHH> diretion of the sustrteF sn some sesD suh s pe on wgyD the III diretion is prllel to the sustrte IHHF he epitxil reltionship is spei(ed y giving (rst the plne in the (lm tht is prllel to the sustrte IHHF
1.4.6 Bibliography
International Tables for X-ray CrystallographyF olF sY uynoh ressX firminghmD u @IWURAF fF pF qF tohnsonD in Comprehensive Inorganic ChemistryD ergmon ressD olF RD ghpter SP @IWUQAF eF F estD Solid State Chemistry and its ApplicationsD ileyD xew ork @IWVRAF
QV

5
1.5 Structures of Element and Compound Semiconductors

1.5.1 Introduction
e single rystl of either n elementl @eFgFD silionA or ompound @eFgFD gllium rsenideA semiondutor forms the sis of lmost ll semiondutor deviesF he ility to ontrol the eletroni nd optoEeletroni properties of these mterils is sed on n understnding of their strutureF sn dditionD the metls nd mny of the insultors employed within miroeletroni devie re lso rystllineF
1.5.2 Group IV (14) elements

ih of the semionduting phses of the group s @IRA elementsD g @dimondAD iD qeD nd EnD dopt the dimond ui struture @pigure IFQRAF heir lttie onstnts @aD A nd densities @D gGm3 A re given in le IFQF
Figure 1.34:
Unit cell structure of a diamond cubic lattice showing the two interpenetrating facecentered cubic lattices.
Element
Lattice parameter,
()
Density (g/cm3 )
ron @dimondA silion germnium tin @EnA

Table 1.3
QFSTTVQ@IA SFRQIHPHI@QA SFTSUWHT@IA TFRVWP@IA
QFSISPS PFQIWHHP SFQPQR UFPVS
X vttie prmeters nd densities @mesured t PWV uA for the dimond ui forms of the group s @IRA elementsF
es would e expeted the lttie prmeter inrese in the order g < i < qe < EnF ilion nd germnium form ontinuous series of solid solutions with grdully vrying prmetersF st is worth noting the high degree of ury tht the lttie prmeters re known for high purity rystls of these elementsF sn dditionD it is importnt to note the temperture t whih struturl mesurements re mdeD sine the
5
QW lttie prmeters re temperture dependent @pigure IFQSAF he lttie onstnt @aAD in D for high purity silion my e lulted for ny temperture @A over the temperture rnge PWQ E IHUQ u y the formul shown elowF aT a SFRQHR C IFVIQV IH-5 @ E PWVFIS uA C IFSRP IH-9 @ ! PWVFIS uA
Figure 1.35:
Temperature dependence of the lattice parameter for (a) Si and (b) Ge.
iven though the dimond ui forms of i nd qe re the only forms of diret interest to semiondutor deviesD eh exists in numerous rystlline high pressure nd metEstle formsF hese re desried long with their interonversionsD in le IFRF
RH

Phase Structure Remarks
i s i ss i sss i s i i s qe s qe ss qe sss qe s
dimond ui grey tin struture ui hexgonl unidenti(ed hexgonl lose pked dimond ui
stle t norml pressure formed from i s or i ove IR q metstleD formed from i ss ove IH q stle ove QR qD formed from i ss ove IT q stle ove RS q lowEpressure phse formed from qe s ove IH q formed y quenhing qe ss t low pressure formed y quenhing qe ss to I tm t PHH u
Etin struture
tetrgonl ody entered ui
Table 1.4
X righ pressure nd metstle phses of silion nd germniumF
1.5.3 Group III-V (13-15) compounds

he stle phses for the rsenidesD phosphides nd ntimonides of luminumD gllium nd indium ll exhiit zin lende strutures @pigure IFQTAF sn ontrstD the nitrides re found s wurtzite strutures @eFgFD pigure IFQUAF he strutureD lttie prmetersD nd densities of the sssE ompounds re given in le IFSF st is worth noting tht ontrry to expettion the lttie prmeter of the gllium ompounds is smller thn their luminum homologY for qes a a SFTSQ Y eles a a SFTTH F es with the group s elements the lttie prmeters re highly temperture dependentY howeverD dditionl vrition rises from ny devition from solute stoihiometryF hese e'ets re shown in pigure IFQVF
Unit cell structure of a zinc blende (ZnS) lattice. Zinc atoms are shown in green (small), sulfur atoms shown in red (large), and the dashed lines show the unit cell.
Figure 1.36:
RI
Unit cell structure of a wurtzite lattice. Zinc atoms are shown in green (small), sulfur atoms shown in red (large), and the dashed lines show the unit cell.
Figure 1.37:
Compound
Structure
Lattice parameter ()
Density (g/cm3 )
elx el eles el qx q qes snx sn snes sn

Table 1.5
wurtzite zin lende zin lende zin lende wurtzite zin lende zin lende wurtzite zin lende zin lende zin lende
a a QFII@IAD a RFWV@IA a a SFRTQS@RA a a SFTTH a a TFIQSS@IA a a QFIWHD a SFIVU a a SFRSHS@PA a a SFTSQPS@PA a a QFSRRTD c a SFUHQR a a SFVTV@IA a a TFHSVQ a a TFRUWQU
QFPSS PFRH@IA QFUTH RFPT RFIQV SFQIUT@QA TFVI RFVI SFTTU SFUURU@RA
X vttie prmeters nd densities @mesured t PWV uA for the sssE @IQEISA ompound semiondutorsF istimted stndrd devitions given in prenthesesF
RP
Figure 1.38: Temperature dependence of the lattice parameter for stoichiometric GaAs and crystals with either Ga or As excess.
he homogeneity of strutures of lloys for wide rnge of solid solutions to e formed etween sssE ompounds in lmost ny omintionF wo lsses of ternry lloys re formedX sssx Esss1-x E @eFgFD elx Eq1-x EesA nd sssE1-x Ex @eFgFD qEes1-x Ex A F hile quternry lloys of the type sssx Esss1-x Ey E1-y llow for the growth of mterils with similr lttie prmetersD ut rod rnge of nd gpsF e very importnt ternry lloyD espeilly in optoeletroni pplitionsD is elx Eq1-x Ees nd its lttie prmeter @aA is diretly relted to the omposition @xAF a a SFTSQQ C HFHHUV x xot ll of the sssE ompounds hve well hrterized highEpressure phsesF howeverD in eh se where highEpressure phse is oserved the oordintion numer of oth the group sss nd group element inreses from four to sixF husD el undergoes zin lende to rok slt trnsformtion t high pressure ove IUH krD while el nd qes form orthorhomi distorted rok slt strutures ove UU nd IUP krD respetivelyF en orthorhomi struture is proposed for the highEpressure form of sn @>IQQ krAF sndium rsenide @snesA undergoes twoEphse trnsformtionsF he zin lende struture is onverted to rok slt struture ove UU krD whih in turn forms Etin struture ove IUH krF
1.5.4 Group II-VI (12-16) compounds

he strutures of the ssEs ompound semiondutors re less preditle thn those of the sssE ompounds @oveAD nd while zin lende struture exists for lmost ll of the ompounds there is stronger tendeny towrds the hexgonl wurtzite formF sn severl ses the zin lende struture is oserved under mient onditionsD ut my e onverted to the wurtzite form upon hetingF sn generl the wurtzite form predomE intes with the smller nions @eFgFD oxidesAD while the zin lende eomes the more stle phse for the lrger nions @eFgFD telluridesAF yne exeption is merury sul(de @rgA tht is the rhetype for the trigonl innr phseF le IFT lists the stle phse of the hlogenides of zinD dmium nd meruryD long with their high temperture phses where pplileF olid solutions of the ssEs ompounds re not s esily formed s for the sssE ompoundsY howeverD two importnt exmples re nx e1-x nd gdx rg1-x eF
RQ
Density (g/cm3 )
Compound
Structure
Lattice parameter ()
n ne ne gd gde gde rg rge rge

Table 1.6
zin lende wurtzite in lende in lende wurtzite wurtzite in lende innr in lende in lende in lende
a a SFRIH a a QFVPPD c a a SFTTV a a TFIH a a RFIQTD c a a RFQHHD c a a TFRVP a a RFIRWD c a a SFVSI a a TFHVS a a TFRT
RFHUS a TFPTH RFHVU SFPU SFTQT a TFUIR a UFHII a WFRWS UFUQ VFPS VFHU RFVP SFVI SFVU
X vttie prmeters nd densities @mesured t PWV uA for the ssEs @IPEITA ompound semiondutorsF
he zin hlogenides ll trnsform to esium hloride struture under high pressuresD while the dmium ompounds ll form rok slt highEpressure phses @pigure IFQWAF werury selenide @rgeA nd merury telluride @rgeA onvert to the merury sul(de rhetype strutureD innrD t high pressureF
Figure 1.39: Unit cell structure of a rock salt lattice. Sodium ions are shown in purple and chloride ions are shown in red.
1.5.5 I-III-VI2 (11-13-16) compounds

xerly ll sEsssEs2 ompounds t room temperture dopt the hlopyrite struture @pigure IFRHAF he ell onstnts nd densities re given in le IFUF elthough there re few reports of high temperture or
RR
highEpressure phsesD egsn2 hs een shown to exist s high temperture orthorhomi polymorph @a a TFWSRD b a VFPTRD nd c a TFTVQ AD nd egsne2 forms ui phse t high pressuresF
Unit cell structure of a chalcopyrite lattice. Copper atoms are shown in blue, iron atoms are shown in green and sulfur atoms are shown in yellow. The dashed lines show the unit cell.
Figure 1.40:
RS
Density (g.cm3 )
Compound
Lattice parameter
()
Lattice parameter
()
guel2 guele2 guele2 guq2 guqe2 guqe2 gusn2 gusne2 gusne2 egel2 egq2 egqe2 egqe2 egsn2 egsne2 egsne2
Table 1.7
SFQP SFTI SFWT SFQS SFTI TFHH SFSP SFUV TFIU TFQH SFUS SFWV TFPW SFVP TFHWS TFRQ
IHFRQH IHFWP IIFUU IHFRT IIFHH IIFWQ IIFHV IIFSS IPFQR IIFVR IHFPW IHFVV IIFWS IIFIU IIFTW IPFSW
QFRS RFTW SFRU RFQV SFSU SFWS RFUR SFUU TFIH TFIS RFUH SFUH TFHV RFWU SFVP TFWT
X ghlopyrite lttie prmeters nd densities @mesured t PWV uA for the sEsssEs ompound semiondutorsF vttie prmeters for tetrgonl ellF
yf the sEsssEs2 ompoundsD the opper indium hlogenides @gusni2 A re ertinly the most studied for their pplition in solr ellsF yne of the dvntges of the opper indium hlogenide ompounds is the formtion of solid solutions @lloysA of the formul gusni2-x i9x D where the omposition vrile @xA vries from H to PF he gusn2-x ex nd gusne2-x ex systems hve lso een exminedD s hs the guqy sn1-y 2-x ex quternry systemF es would e expeted from onsidertion of the reltive ioni rdii of the hlogenides the lttie prmeters of the gusn2-x ex lloy should inrese with inresed selenium ontentF ergrd9s lw requires the lttie onstnt for liner solution of two semiondutors to vry linerly with omposition @eFgFD s is oserved for elx q1-x esAD howeverD the vrition of the tetrgonl lttie onstnts @a nd c A with omposition for gusn2-x x re est desried y the proli reltionshipsF a a SFSQP C HFHVHI x C HFHPTH x2 c a IIFIST C HFIPHR x C HFHTII x2 e similr reltionship is oserved for the gusne2-x ex lloysF a a SFUVQ C HFISTH x C HFHPIP x2 c a IIFTPV C HFQQRH x C HFHPUU x2 he lrge di'erene in ioni rdii etween nd e @HFQU A prevents formtion of solid solutions in the gusn2-x ex systemD howeverD the single lloy gusn1.5 e0.5 hs een reportedF
1.5.6 Orientation eects

yne single rystls of high purity silion or gllium rsenide re produed they re ut into wfers suh tht the exposed fe of these wfers is either the rystllogrphi {IHH} or {III} plnesF he reltive struture of these surfes re importnt with respet to oxidtionD ething nd thin (lm growthF hese proesses re orienttionEsensitiveY tht isD they depend on the diretion in whih the rystl slie is utF
RT
1.5.6.1 Atom density and dangling bonds
he priniple plnes in rystl my e di'erentited in numer of wysD howeverD the tom ndGor ond density re useful in prediting muh of the hemistry of semiondutor surfesF ine oth silion nd gllium rsenide re fcc strutures nd the {IHH} nd {III} re the only tehnologilly relevnt surfesD disussions will e limited to fcc {IHH} nd {III}F he tom density of surfe my e de(ned s the numer of toms per unit reF pigure IFRI shows shemti view of the {III} nd {IHH} plnes in fcc lttieF he {III} plne onsists of hexgonl lose pked rry in whih the rystl diretions within the plne re oriented t TH to eh otherF he hexgonl pking nd the orienttion of the rystl diretions re indited in pigure IFRI s n overlid hexgonF qiven the intrEplnr interEtomi distne my e de(ned s funtion of the lttie prmeterD the re of this hexgon my e redily lultedF por exmple in the se of silionD the hexgon hs n re of QVFQH 2 F he numer of toms within the hexgon is threeX the tom in the enter plus IGQ of eh of the six toms t the verties of the hexgon @eh of the toms t the hexgons verties is shred y three other djent hexgonsAF husD the tom density of the {III} plne is lulted to e HFHUVQ -2 F imilrlyD the tom density of the {IHH} plne my e lultedF he {IHH} plne onsists of squre rry in whih the rystl diretions within the plne re oriented t WH to eh otherF ine the squre is oinident with one of the fes of the unit ell the re of the squre my e redily lultedF por exmple in the se of silionD the squre hs n re of PWFRW 2 F he numer of toms within the squre is PX the tom in the enter plus IGR of eh of the four toms t the verties of the squre @eh of the toms t the orners of the squre re shred y four other djent squresAF husD the tom density of the {IHH} plne is lulted to e HFHTUV -2 F hile these vlues for the tom density re spei( for silionD their rtio is onstnt for ll dimond ui nd zin lende struturesX {IHH}X{III} a IXIFISSF sn generlD the fewer dngling onds the more stle surfe strutureF
Schematic representation of the (111) and (100) faces of a face centered cubic (fcc) lattice showing the relationship between the close packed rows.
Figure 1.41:
en tom inside rystl of ny mteril will hve oordintion numer @nA determined y the struture of the mterilF por exmpleD ll toms within the ulk of silion rystl will e in tetrhedrl fourE oordinte environment @n a RAF roweverD t the surfe of rystl the toms will not mke their full ompliment of ondsF ih tom will therefore hve less nerest neighors thn n tom within the ulk of the mterilF he missing onds re ommonly lled dngling ondsF hile this desription is not prtiulrly urte it isD howeverD widely employed nd s suh will e used hereinF he numer of dngling onds my e de(ned s the di'erene etween the idel oordintion numer @determined y the ulk rystl strutureA nd the tul oordintion numer s oserved t the surfeF pigure IFRP shows setion of the {III} surfes of dimond ui lttie viewed perpendiulr to the
RU {III} plneF he toms within the ulk hve oordintion numer of fourF sn ontrstD the toms t the surfe @eFgFD the tom shown in lue in pigure IFRPA re eh onded to just three other toms @the toms shown in red in pigure IFRPAD thus eh surfe tom hs one dngling ondF es n e seen from pigure IFRQD whih shows the toms t the {IHH} surfe viewed perpendiulr to the {IHH} plneD eh tom t the surfe @eFgFD the tom shown in lue in pigure IFRQA is only oordinted to two other toms @the toms shown in red in pigure IFRQAD leving two dngling onds per tomF st should e noted tht the sme numer of dngling onds re found for the {III} nd {IHH} plnes of zin lende lttieF he rtio of dngling onds for the {IHH} nd {III} plnes of ll dimond ui nd zin lende strutures is {IHH}X{III} a PXIF purthermoreD sine the tom densities of eh plne re known then the rtio of the dngling ond densities is determined to eX {IHH}X{III} a IXHFSUUF
Figure 1.42:
{111} plane.
A section of the {111} surfaces of a diamond cubic lattice viewed perpendicular to the
RV
Figure 1.43:
{100} plane.
A section of the {100} surface of a diamond cubic lattice viewed perpendicular to the
1.5.6.2 Silicon
por silionD the {III} plnes re loser pked thn the {IHH} plnesF es resultD growth of silion rystl is therefore slowest in the <III> diretionD sine it requires lying down lose pked tomi lyer upon nother lyer in its losest pked formF es onsequene <III> i is the esiest to growD nd therefore the lest expensiveF he dissolution or ething of rystl is relted to the numer of roken onds lredy present t the surfeX the fewer onds to e roken in order to remove n individul tom from rystlD the esier it will e to dissolve the rystlF es onsequene of hving only one dngling ond @requiring three onds to e rokenA ething silion is slowest in the <III> diretionF he eletroni properties of silion wfer re lso relted to the numer of dngling ondsF ilion miroiruits re generlly formed on single rystl wfer tht is died fter frition y either swing prt wy through the wfer thikness or soring @sriingA the surfeD nd then physilly rekingF he physil rekge of the wfer ours long the nturl levge plnesD whih in the se of silion re the {III} plnesF
1.5.6.3 Gallium arsenide
he zin lende lttie oserved for gllium rsenide results in dditionl onsidertions over tht of silionF elthough the {IHH} plne of qes is struturlly similr to tht of silionD two possiilities existX fe onsisting of either ll gllium toms or ll rseni tomsF sn either se the surfe toms hve two dngling ondsD nd the properties of the fe re independent of whether the fe is gllium or rseniF he {III} plne lso hs the possiility of onsisting of ll gllium or ll rseniF roweverD unlike the {IHH} plnes there is signi(nt di'erene etween the two possiilitiesF pigure IFQT shows the gllium rsenide struture represented y two interpenetrting fcc lttiesF he III xis is vertil within the plne of the pgeF elthough the struture onsists of lternte lyers of gllium nd rseni stked long the III xisD the distne etween the suessive lyers lterntes etween lrge nd smllF essigning rseni s the prent lttie the order of the lyers in the III diretion is esEqEesEqEesEqD while in the
III
RW diretion the lyers re orderedD qEesEqEesEqEes @pigure IFRRAF sn silion these two diretions re of ourse identilF he surfe of rystl would e either rseniD with three dngling ondsD or glliumD with one dngling ondF glerlyD the ltter is energetilly more fvorleF husD the @IIIA plne shown in pigure IFRR is lled the @IIIA q feF gonverselyD the the

III
plne would e either glliumD with three
dngling ondsD or rseniD with one dngling ondF eginD the ltter is energetilly more fvorle nd III plne is therefore lled the @IIIA es feF
The (111) Ga face of GaAs showing a surface layer containing gallium atoms (green) with one dangling bond per gallium and three bonds to the arsenic atoms (red) in the lower layer.
Figure 1.44:
he @IIIA es is distint from tht of @IIIA q due to the di'erene in the numer of eletrons t the surfeF es onsequeneD the @IIIA es fe ethes more rpidly thn the @IIIA q feF sn dditionD surfe evportion elow UUH g ours more rpidly t the @IIIA es feF
1.5.7 Bibliography

wF fulitz nd eF vF uo'D J. Appl. Phys.D IWVPD 53D TIUWF tF gF tmiesonD ScienceD IWTQD 139D VRSF gF gF vndryD tF vokwoodD nd eF F frronD Chem. Mater.D IWWSD 7D TWWF wF oinsD tF gF hillipsD nd F qF vmrehtD J. Phys. Chem. SolidsD IWUQD 34D IPHSF hF ridevi nd uF F eddyD Mat. Res. Bull.D IWVSD 20D WPWF F uF ohrD F F eirD nd eF vF uo'D Phys. Rev. BD IWVSD 31D UQRRF F wF in nd F tF 'D J. Appl. Phys.D IWUQD 45D IRSTF
SH
Chapter 2
Device Fundamentals
2.1 Introduction to Bipolar Transistors
sistors y fill ilsonF
note:
1
his module is dpted from the gonnexions module entitled Introduction to Bipolar Tran-
vet9s leve the world of two terminl devies @whih re ll lled diodes y the wyY diode just mens twoEterminlsA nd venture into the muh more interesting world of three terminlsF he (rst devie we will look t is lled the bipolar transistorF gonsider the struture shown in pigure PFIX
Figure 2.1:
Structure of a npn bipolar transistor.
he devie onsists of three lyers of silionD hevily doped nEtype lyer lled the emitterD modertely doped pEtype lyer lled the seD nd thirdD more lightly doped lyer lled the olletorF sn ising @pplied hg potentilA on(gurtion lled forward active biasingD the emitterEse juntion is forwrd isedD nd the seEolletor juntion is reverse isedF pigure PFP shows the ising onventions we will useF foth is voltges re referened to the se terminlF ine the seEemitter juntion is forwrd isedD nd sine the se is mde of pEtype mterilD EB must e negtiveF yn the other hndD in order to reverse is the seEolletor juntion CB will e positive voltgeF
1
SI
SP
CHAPTER 2. DEVICE FUNDAMENTALS
Figure 2.2:
Forward active biasing of a npn bipolar transistor.
xowD let9s drw the ndEdigrm for this devieF et (rst this might seem hrd to doD ut we know wht forwrd nd reverse ised nd digrms look likeD so we9ll just stik one of eh togetherF e show this in pigure PFQD whih is very usy (gureD ut it is lso very importntD euse it shows ll of the importnt fetures in the opertion the trnsistorF ine the seEemitter juntion is forwrd isedD eletrons will go from the @nEtypeA emitter into the seF vikewiseD some holes from the se will e injeted into the emitterF
Figure 2.3:
Band diagram and carrier uxes in a bipolar transistor.
sn pigure PFQD we hve two di'erent kinds of rrowsF he open rrows whih re tthed to the rriersD show us whih wy the rrier is movingF he solid rrows whih re leled with some kind of susripted ID represent urrent )owF e need to do this euse for holesD motion nd urrent )ow re in the sme diretionD while for eletronsD rrier motion nd urrent )ow re in opposite diretionsF tust s we sw in the lst hpterD the eletrons whih re injeted into the se di'use wy from the emitterEse juntion towrds the @reverse isedA seEolletor juntionF es they move through the seD some of the eletrons enounter holes nd reomine with themF hose eletrons whih do get to the seE
SQ olletor juntion run into lrge eletri (eld whih sweeps them out of the se nd into the olletorF hey 4fll4 down the lrge potentil drop t the juntionF hese e'ets re ll seen in pigure PFQD with rrows representing the vrious urrents whih re ssoited with eh of the rriers )uxesF IEe represents the urrent ssoited with the eletron injetion into the seD iFeFD it points in the opposite diretion from the motion of the eletronsD sine eletrons hve negtive hrgeF IEh represents the urrent ssoited with holes injetion into the emitter from the seF IBr represents reomintion urrent in the seD while ICe represents the eletron urrent going into the olletorF st should e esy for you to see thtX
IE = IEe + IEh IB = IEh + IBr IC = ICe
@PFIA @PFPA @PFQA
sn 4good4 trnsistorD lmost ll of the urrent ross the seEemitter juntion onsists of eletrons eing injeted into the seF he trnsistor engineer works hrd to design the devie so tht very little emitter urrent is mde up of holes oming from the se into the emitterF he trnsistor is lso designed so tht lmost ll of those eletrons whih re injeted into the se mke it ross to the seEolletor reverseEised juntionF ome reomintion is unvoidleD ut things re rrnged so s to minimize this e'etF
2.2 Basic MOS Structure
note: his module is dpted from the gonnexions module entitled Basic MOS Structure y fill ilsonF
pigure PFR shows the si steps neessry to mke the wy strutureF st will help us in our understnding if we now rotte our piture so tht it is pointing sidewys in our next few drwingsF pigure PFS shows the rotted strutureF xote tht in the pEsilion we hve positively hrged moile holesD nd negtively hrgedD (xed eptorsF feuse we will need it lterD we hve lso shown the nd digrm for the semiondutor elow the sketh of the devieF xote tht sine the sustrte is pEtypeD the permi level is loted down lose to the vlne ndF
Figure 2.4:
Formation of the metal-oxide-semiconductor (MOS) structure.
SR
Figure 2.5:
Basic metal-oxide-semiconductor (MOS) structure.
vet us now ple potentil etween the gte nd the silion sustrteF uppose we mke the gte negtive with respet to the sustrteF ine the sustrte is pEtypeD it hs lot of moileD positively hrged holes in itF ome of them will e ttrted to the negtive hrge on the gteD nd move over to the surfe of the sustrteF his is lso re)eted in the nd digrm shown in pigure PFTF ememer tht the density of holes is exponentilly proportionl to how lose the permi level is to the vlene nd edgeF e see tht the nd digrm hs een ent up slightly ner the surfe to re)et the extr holes whih hve umulted thereF
Figure 2.6:
Applying a negative gate voltage to a basic metal-oxide-semiconductor (MOS) structure.
SS en eletri (eld will develop etween the positive holes nd the negtive gte hrgeF xote tht the gte nd the sustrte form kind of prllel plte pitorD with the oxide ting s the insulting lyer inEetween themF he oxide is quite thin ompred to the re of the devieD nd so it is quite pproprite to ssume tht the eletri (eld inside the oxide is uniform oneF @e will ignore fringing t the edgesFA he integrl of the eletri (eld is just the pplied gte voltge Vg F sf the oxide hs thikness xox then sine Eox is uniformD it is given yD @PFRAF
Eox =
Vg xox
@PFRA
sf we fous in on smll prt of the gteD we n mke little 4pill4 ox whih extends from somewhere in the oxideD ross the oxideGgte interfe nd ends up inside the gte mteril somepleF he pillEox will hve n re sF xow we will invoke quss9 lw whih we reviewed erlierF quss9 lw simply sys tht the surfe integrl over losed surfe of the displement vetor D @whih isD of ourseD x E A is equl to the totl hrge enlosed y tht surfeF e will ssume tht there is surfe hrge density -Qg goulomsGm2 on the surfe of the gte eletrode @pigure PFUAF he integrl form of quss9 vw is justX
ox EdS
= Qencl
@PFSA
Figure 2.7:
Finding the surface charge density.
xote tht we hve used ox E in ple of DF sn this prtiulr setEup the integrl is esy to performD sine the eletri (eld is uniformD nd only pointing in through one surfe E it termintes on the negtive surfe hrge inside the pillEoxF he hrge enlosed in the pill ox is just E@Qg s AD nd so we hve @keeping in mind tht the surfe integrl of vetor pointing into the surfe is negtiveAD @PFTAD or @PFUAF
ox EdS
= =
ox Eox
ox Eox s)
(Qg s) = Qg
@PFTA @PFUA
xowD we n use @PFRA to get @PFVA or @PFWAF

ox Vg
xox
= Qg
@PFVA
ST

Qg ox = cox Vg xox
@PFWA
he quntity c ox is lled the oxide pitneF st hs units of prdsGm2 D so it is relly pitne per unit re of the oxideF he dieletri onstnt of silion dioxideD ox D is out QFQ x IH-13 pGmF e typil oxide thikness might e PSH @or PFS x IH-6 mAF sn this seD c ox would e out IFQH x IH-7 pGm2 F he units we re using hereD while they might seem little ritrry nd onfusingD re the ones most ommonly used in the semiondutor usinessF he most useful form of @PFWA is when it is turned roundD @PFIHAD s it gives us wy to (nd the hrge on the gte in terms of the gte potentilF e will use this eqution lter in our development of how the wy trnsistor relly worksF
Qg = cox Vg
@PFIHA
st turns out we hve not done nything very useful y pply negtive voltge to the gteF e hve drwn more holes there in wht is lled n umultion lyerD ut tht is not helping us in our e'ort to rete lyer of eletrons in the wypi whih ould eletrilly onnet the two nEregions togetherF vet9s turn the ttery round nd pply positive voltge to the gte @pigure PFVAF etullyD let9s tke the ttery out for nowD nd just let Vg e positive vlueD reltive to the sustrte whih will tie to groundF wking Vg positive puts positive Qg on the gteF he positive hrge pushes the holes wy from the region under the gte nd unovers some of the negtivelyEhrged (xed eptorsF xow the eletri (eld points the other wyD nd goes from the positive gte hrgeD terminting on the negtive eptor hrge within the silionF
Figure 2.8:
Increasing the voltage extends the depletion region further into the device.
he eletri (eld now extends into the semiondutorF e know from our experiene with the pEn juntion tht when there is n eletri (eldD there is shift in potentilD whih is represented in the nd digrm y ending the ndsF fending the nds down @s we should moving towrds positive hrgeA uses the vlene nd to pull wy from the permi level ner the surfe of the semiondutorF sf you rememer the expression we hd for the density of holes in terms of Ev nd Ef it is esy to see tht indeedD @PFIIAD there
SU is depletion region @region with lmost no holesA ner the region under the gteF @yne Ef E Ev gets lrge with respet to kTD the negtive exponent uses p 0FA
p = Nv e
E E v f kT
@PFIIA
Figure 2.9:
Threshold,
Ef
is getting close to
Ec
he eletri (eld extends further into the semiondutorD s more negtive hrge is unovered nd the nds end further downF fut now we hve to rell the eletron density equtionD whih tells us how mny eletrons we hveX
n = Nc e
E E c f kT
@PFIPA
e glne t pigure PFW revels tht with this muh nd endingD Ec the ondution nd edgeD nd Ef the permi level re strting to get lose to one nother @t lest ompred to kT AD whih mens tht nD the eletron onentrtionD should soon strt to eome signi(ntF sn the sitution represented y pigure PFWD we sy we re t thresholdD nd the gte voltge t this point is lled the threshold voltageD VT F xowD let9s inrese Vg ove VT F rere9s the sketh in pigure PFIHF iven though we hve inresed Vg eyond the threshold voltgeD VT D nd more positive hrge ppers on the gteD the depletion region no longer moves k into the sustrteF snsted eletrons strt to pper under the gte regionD nd the dditionl eletri (eld lines terminte on these new eletronsD insted of on dditionl eptorsF e hve reted n inversion layer of eletrons under the gteD nd it is this lyer of eletrons whih we n use to onnet the two nEtype regions in our initil devieF
SV
Figure 2.10:
Inversion - electrons form under the gate.
here did these eletrons ome fromc e do not hve ny donors in this mterilD so they n not ome from thereF he only ple from whih eletrons ould e found would e through therml genertionF ememerD in semiondutorD there re lwys few eletron hole pirs eing generted y therml exittion t ny given timeF iletrons tht get reted in the depletion region re ught y the eletri (eld nd re swept over to the edge y the gteF s hve tried to suggest this with the eletron genertion event shown in the nd digrm in the (gureF sn rel wy devieD we hve the two nEregionsD nd it is esy for eletrons from one or oth to 4fll4 into the potentil well under the gteD nd rete the inversion lyer of eletronsF
2.3 Introduction to the MOS Transistor and MOSFETs

note:
his module is dpted from the gonnexions modules entitled Introduction to MOSFETs nd MOS Transistor y fill ilsonF
e now move on to nother three terminl devie E lso lled trnsistorF his trnsistorD howeverD works on muh di'erent priniples thn does the ipolr juntion trnsistor of the lst hpterF e will now fous on devie lled the eld eect transistorD or metal-oxide-semiconductor eld eect transistor or simply wypiF sn pigure PFII we hve lok of silionD doped pEtypeF snto it we hve mde two regions whih re doped nEtypeF o eh of those nEtype regions we tth wireD nd onnet ttery etween themF sf we try to get some urrentD ID to )ow through this strutureD nothing will hppenD euse the nEp juntion on the r is reverse isedD iFeFD the positive led from the ttery going to the nEside of the pEn juntionF sf we ttempt to remedy this y turning the ttery roundD we will now hve the vr juntion reverse isedD nd ginD no urrent will )owF sfD for whtever resonD we wnt urrent to )owD we will need to ome up
3
SW with some wy of forming lyer of nEtype mteril etween one nEregion nd the otherF his will then onnet them togetherD nd we n run urrent in one terminl nd out the otherF
Figure 2.11:
The start of a eld eect transistor.
o see how we will do thisD let9s do two thingsF pirst we will grow lyer of iy2 @silion dioxide or siliD ut tully refered to s 4oxide4A on top of the silionF o do this the wfer is pled in n oven under n oxygen tmosphereD nd heted to IIHH gF he result is nieD highEqulity insulting iy2 lyer on top of the silionAF yn top of the oxide lyer we then deposit ondutorD whih we ll the gteF sn the 4old dys4 the gte would hve een lyer of luminumY hene the 4metlEoxideEsilion4 or wy nmeF odyD it is muh more likely tht hevily doped lyer of polyrystlline silion @polysilionD or more often just 4poly4A would e deposited to form the gte strutureF olysilion is mde from the redution of gsD suh s silne @ir4 AD @PFIQAF @PFIQA he silion is polyrystlline @omposed of lots of smll silion rystllitesA euse it is deposited on top of the oxideD whih is morphousD nd so it does not provide single rystl 4mtrix4 whih would llow the silion to orgnize itself into one single rystlF sf we hd deposited the silion on top of single rystl silion wferD we would hve formed single rystl lyer of silion lled n epitxil lyerF his is sometimes done to mke strutures for prtiulr pplitionsF por instneD growing nEtype epitxil lyer on top of pEtype sustrte permits the frition of very rupt pEn juntionF
note: ipitxyD is trnslitertion of two qreek words epiD mening 4upon4D nd taxisF mening 4ordered4F hus n epitxil lyer is one tht follows the order of the sustrte on whih it is grownF
xow we n go k now to our initil strutureD shown in pigure PFIID only this time we will dd n oxide lyerD gte strutureD nd nother ttery so tht we n invert the region under the gte nd onnet the two nEregions togetherF ell lso identify some nmes for prts of the strutureD so we will know wht we re tlking outF por resons whih will e ler lterD we ll the nEregion onneted to the negtive side of the ttery the soureD nd the other one the drinF e will ground the soureD nd lso the pEtype sustrteF e dd two tteriesD Vgs etween the gte nd the soureD nd Vds etween the drin nd the soureF
TH
Figure 2.12:
Biasing a MOSFET transistor
st will e helpful if we lso mke nother skethD whih gives us perspetive view of the devieF por this we strip o' the gte nd oxideD ut we will imgine tht we hve pplied voltge greter thn VT to the gteD so there is nEtype regionD lled the hnnel whih onnets the twoF e will ssume tht the hnnel region is L long nd W wideD s shown in pigure PFIQF
Figure 2.13:
The inversion channel and its resistance.
xext we wnt to tke look t little setion of hnnelD nd (nd its resistne dRD when the little setion is dx longD @PFIRAF
dR =
dx s W
@PFIRA
e hve introdued slightly di'erent form for our resistne formul hereF xormllyD we would hve simple in the denomintorD nd n re AD for the rossEsetionl re of the hnnelF st turns out to e very hrd to (gure out wht tht ross setionl re of the hnnel is howeverF he eletrons whih form the inversion lyer rowd into very thin sheet of surfe hrge whih relly hs little or no thiknessD or penetrtion into the sustrteF sfD on the other hnd we onsider surfe ondutivity @unitsX simply mhosAD s D @PFISAD then we will hve n expression whih we n evluteF rereD s is surfe moilityD with units of m2 GFseD tht is the quntity whih represented the proportionlity etween the verge rrier veloity nd the eletri (eldD
TI @PFITA nd @PFIUAF
s = s Qchan v = E =
@PFISA @PFITA
q @PFIUA m he surfe moility is quntity whih hs to e mesured for given systemD nd is usully just numer whih is given to youF omething round QHH m2 GFse is out right for silionF Qchan is lled the surfe hrge density or hnnel hrge density nd it hs units of goulomsGm2 F his is like sheet of hrgeD whih is di'erent from the ulk hrge densityD whih hs units of goulomsGm2 F xote thtX
cm2 Coulombs Voltsec cm2
= = =
Coul sec
Volt I V
@PFIVA
mhos
st turns out tht it is pretty simple to get n expression for Qchan D the surfe hrge density in the hnnelF por ny given gte voltge Vgs D we know tht the hrge density on the gte is given simply sX
Qg = cox Vgs
@PFIWA
roweverD until the gte voltge Vgs gets lrger thn VT we re not reting ny moile eletrons under the gteD we re just uilding up depletion regionF e9ll de(ne QT s the hrge on the gte neessry to get to thresholdF QT = cox VT F eny hrge dded to the gte ove QT is mthed y hrge Qchan in the hnnelF husD it is esy to syX @PFPHA or @PFPIAF
Qchannel = Qg QT Qchan = cox (Vg VT )

husD putting @PFPHA nd @PFISA into @PFIRAD we getX
@PFPHA @PFPIA
dR =
dx s cox (Vgs VT ) W
@PFPPA
sf you look k t pigure PFIPD you will see tht we hve de(ned urrent Id )owing into the drinF ht urrent )ows through the hnnelD nd hene through our little inrementl resistne dRD reting voltge drop dVc ross itD where Vc is the hnnel voltgeD @PFPQAF
dVc (x)
= Id dR =
Id dx s cox (Vgs VT )W
@PFPQA
vet9s move the denomintor to the leftD nd integrteF e wnt to do our integrl ompletely long the hnnelF he voltge on the hnnel Vc (x) goes from H on the left to Vds on the rightF et the sme timeD x is going from H to LF hus our limits of integrtion will e H nd Vds for the voltge integrl dVc (x) nd from H to L for the x integrl dxF
Vds L
s cox (Vgs VT ) W dVc =

0 0
Id dx
@PFPRA
TP
foth integrls re pretty trivilF vet9s swp the eqution orderD sine we usully wnt Id s funtion of pplied voltgesF
Id L = s cox W (Vgs VT ) Vds
@PFPSA
e now simply divide oth sides y LD nd we end up with n expression for the drin urrent Id D in terms of the drinEsoure voltgeD Vds D the gte voltge Vgs nd some physil ttriutes of the wy trnsistorF
Id =
s cox W (Vgs VT ) Vds L
@PFPTA
2.4 Light Emitting Diode
note: his module is dpted from the gonnexions module entitled Light Emitting Diode y fill ilsonF
vet9s tlk out the reomining eletrons for minuteF hen the eletron flls down from the ondution nd nd (lls in hole in the vlene ndD there is n ovious loss of energyF he question isY where does tht energy goc sn silionD the nswer is not very interestingF ilion is wht is known s n indirect band-gap mterilF ht this mens is tht s n eletron goes from the ottom of the ondution nd to the top of the vlene ndD it must lso undergo signi(nt hnge in momentumF his ll omes out from the detils of the nd struture for the mterilD whih we will not onern ourselves with hereF es we ll knowD whenever something hnges stteD we must still onserve not only energyD ut lso momentumF sn the se of n eletron going from the ondution nd to the vlene nd in silionD oth of these things n only e onserved if the trnsition lso retes quntized set of lttie virtionsD lled phononsD or 4het4F honons posses oth energy nd momentumD nd their retion upon the reomintion of n eletron nd hole llows for omplete onservtion of oth energy nd momentumF ell of the energy whih the eletron gives up in going from the ondution nd to the vlene nd @IFI eA ends up in phononsD whih is nother wy of sying tht the eletron hets up the rystlF sn some other semiondutorsD something else oursF sn lss of mterils lled direct band-gap semiondutorsD the trnsition from ondution nd to vlene nd involves essentilly no hnge in momentumF hotonsD it turns outD possess fir mount of energy @severl eGphoton in some sesA ut they hve very little momentum ssoited with themF husD for diret nd gp mterilD the exess energy of the eletronEhole reomintion n either e tken wy s hetD or more likelyD s photon of lightF his rditive trnsition then onserves energy nd momentum y giving o' light whenever n eletron nd hole reomineF his gives rise to the light emitting diode @vihAF imission of photon in n vih is shown shemtilly in pigure PFIRF
4
TQ
Figure 2.14:
Radiative recombination in a direct band-gap semiconductor.
st ws lnk who postulted tht the energy of photon ws relted to its frequeny y onstntD whih ws lter nmed fter himF sf the frequeny of osilltion is given y the qreek letter 4nu4 @ AD then the energy of the photon is just given yD @PFPUAD where h is lnk9s onstntD whih hs vlue of RFIR x IH-15 eFseF
E = h
@PFPUA
hen we tlk out light it is onventionl to speify its wvelengthD D insted of its frequenyF isile light hs wvelength on the order of nnometersD eFgFD red is out THH nmD green out SHH nm nd lue is in the RSH nm regionF e hndy 4rule of thum4 n e derived from the ft tht c a D where c is the speed of light @Q x IH3 mGse or Q x IH17 nmGseD @PFPVAF
(nm)
= =
hc E(eV) 1242 E(eV)
@PFPVA
husD semiondutor with P e ndEgp should give o' light t out TPH nm @in the redAF e Q e ndEgp mteril would emit t RIR nmD in the violetF he humn eyeD of ourseD is not eqully responsive to ll olors @pigure PFISAF he mterils whih re used for importnt light emitting diodes @vihsA for eh of the di'erent spetrl regions re lso shown in pigure PFISF
TR
Figure 2.15:
Relative response of the human eye to various colors.
st is worth noting tht numer of the importnt vihs re sed on the qes systemF qes is diret ndEgp semiondutor with nd gp of IFRP e @in the infrredAF q is n indiret ndEgp mteril with nd gp of PFPT e @SSH nmD or greenAF foth es nd re group elementsF @rene the nomenlture of the mterils s sssE @or IQEISA ompound semiondutorsFA e n reple some of the es with in qes nd mke mixed ompound semiondutor qes1-x x F hen the mole frtion of phosphorous is less thn out HFRS the nd gp is diretD nd so we n 4engineer4 the desired olor of vih tht we wnt y simply growing rystl with the proper phosphorus onentrtion3 he properties of the qes system re shown in pigure PFITF st turns out tht for this systemD there re tully two di'erent nd gpsD s shown in pigure PFITF yne is diret gp @no hnge in momentumA nd the other is indiretF sn qesD the diret gp hs lower energy thn the indiret one @like in the insetA nd so the trnsition is rditive oneF es we strt dding phosphorous to the systemD oth the diret nd indiret nd gps inrese in energyF roweverD the diret gp energy inreses fster with phosphorous frtion thn does the indiret oneF et mole frtion x of out HFRSD the gp energies ross over nd the mteril goes from eing diret gp semiondutor to n indiret gp semiondutorF et x a HFQS the nd gp is out IFWU e @TQH nmAD nd so we would only expet to get light up to the red using the qes system for mking vih9sF portuntelyD people disovered tht you ould dd n impurity @nitrogenA to the qes systemD whih introdued new level in the systemF en eletron ould go from the indiret ondution nd @for mixture with mole frtion greter thn HFRSA to the nitrogen siteD hnging its momentumD ut not its energyF st ould then mke diret trnsition to the vlene ndD nd light with olors ll the wy to the green eme possileF he use of nitrogen reomintion enter is depited in the pigure PFIUF
TS
Figure 2.16:
Band gap for the GaAsP system
Figure 2.17:
Addition of a nitrogen recombination center to indirect GaAsP.
sf we wnt olors with wvelengths shorter thn the greenD we must ndon the qes system nd look for more suitle mterilsF e ompound semiondutor mde from the ssEs elements n nd e mke up one promising systemD nd severl reserh groups hve suessfully mde lue nd lueEgreen vihs from neF ig is nother @wekA lue emitter whih is ommerilly ville on the mrketF eentlyD workers t tinyD unknown hemil ompny stunned the 4disply world4 y nnouning tht they hd suessfully frited lue vih using the ssE mteril qxF e good lue vih ws the 4holy gril4 of the disply nd
TT
gh yw reserh ommunity for numer of yersF yviouslyD dding lue to the lredy working green nd red vih9s ompletes the set of Q primry olors neessry for fullEolor )t pnel displyF purthermoreD using lue vih or lser in gh yw would more thn qudruple its dt pityD s it dimeter sles s D nd hene the re s 2 F
2.5 Polymer Light Emitting Diodes

2.5.1 Introduction
his module ws developed s prt of ie niversity ourse griwRWTX Chemistry of Electronic MaterialsF his module ws prepred with the ssistne of ui ee rungF
sn IWWHD eletroluminesent @ivA from onjugted polymers ws (rst reported y furroughes et lF of gmridge niversityF e lyer of poly@paraEphenylenevinyleneA @A ws sndwihed etween lyers of indium tin oxide @syA nd luminumF hen this devie is under IR d isD the emits yellowishE green light with quntum e0ieny of HFHS7F his report ttrted lot of ttentionD euse the potentil tht polymer light emitting diodes @vihsA ould e inexpensively mss produed into lrge re disply reF he proessing steps in mking polymer vihs re redily sleleF he industril oting tehniques is well developed to mss produe polymer lyers of IHH nm thiknessD nd the devie ould e ptterned onto lrge surfe re y pixelltion of metlF ine the initil disoveryD nd inresing mount of reserhes hs een performedD nd signi(nt progress hs een mdeF sn IWWH the polymer vih only emitted yellowish green olorD now the emission olor rnged from deep lue to ner infr redF he e0ieny of the multiElyer polymer vih even rehed quntum e0ieny of >R7 nd the operting voltge hs een redued signi(ntlyF sn term of e0ienyD olor seletion nd operting voltgeD polymer vihs hve ttined dequte levels for ommeriliztionF fut there re reliility prolems tht re symptomti of ny orgni deviesF
2.5.2 Device physics and materials science of polymer LEDs

e shemti digrm of polymer vih is shown in pigure PFIVF e polymer vih n e divided into three di'erent omponentsX eF AnodeX the hole supplierD mde of metl of high working funtionF ixmples of the ommon node re indium tin oxide @syAD gold etF he node is usully trnsprent so tht light n e emitted throughF fF CathodeX the eletron supplierD mde of metl of low working funtionF ixmples of the ommon thode re luminum or liumF gF PolymerX mde of onjugted polymer (lm with thikness of IHH nmF
5
TU
Figure 2.18:
Schematic set-up of polymer LED.
hen polymer vih is under diret urrent @dA isD holes re injeted from the node @syA nd eletrons re injeted from the thode @luminumAF nder the in)uenes of the eletril (eldD the eletrons nd holes will migrte towrd eh otherF hen they reomine in the onjugted polymer lyerD ound exited sttes @exitonsA will e formedF ome of the exitons @singletsA then deys in the onjugted polymer lyer to emit light through the trnsprent sustrtes @glssAF he emission olor will e depended on the energy gp of the polymersF here is energy gp in onjugted polymer euse the eletron re not ompletely delolized over the entire polymer hinF snsted there re lternte region in the polymer hin tht hs higher eletron density @pigure PFIWAF he hin length of this region is out ISEPH multiple ondsF he emission olor n e ontrolled y tuning this energy nd gp @pigure PFIWAF st shows tht ond lterntion limits the extent of deloliztionF le PFI summrizes the struture nd emission olor of some ommon onjugted polymersF
Alternation of bond lengths along a conjugated polymer chain (a) results in a material with properties of a large band gap semiconductor (b), where CB is the conductive band gap, and VB is the valence band, and Eg is the band gap.
Figure 2.19:
TV
Polymer Chemical name Structure

- * energy gap (eV)
IFS IFU
Emission (nm) peak
e he
trans E
polyetylene polydietylene
THH
poly@paraE phenyleneA oly@paraE phenylenevinyleneA poly@PDSE dilkoxyEpE phenlyenevinylenA
QFH @redA PFS @greenA
RTS STS
yE
PFP @lueA
SVH
Qe
polythiophene oly@QE lkythiopheneA oly@PDSE thiophenevinyleneA olypyrrole
PFH @redA PFH @redA TWH
IFV
QFI
eni
olyniline
QFP
Table 2.1
X ixmple of ommon onjugted polymersF
2.5.3 Approaches to improve the eciency

i0ieny for ny vih is de(nedX next a nesc B nint where next is the externl quntum e0ienyD nint is the internl e0ieny @represents the frtion of injeted rrierD usully eletronD tht is onverted to photonAD nd nesc is the espe e0ieny @represent frtion of photons tht n reh to the outsideAF he most ommon wy to improve the internl e0ieny is to lne the numer of eletrons nd holes whih rrives t the polymer lyerF yriginllyD there re more holes thn eletron tht rrive of the polymer lyer euse onjugted polymers hve higher eletron 0nityD nd s onsequene will fvor the trnsport of hole thn eletronF here re two wys to mintins the lneX
TW IA wth the work funtion of eletrode with the eletron 0nity nd ioniztion potentil of the polymerF PA une the polymer9s eletron 0nity nd ioniztion potentil to mth the work funtion of the eleE trodeF he espe e0ieny is lso importnt euse polymer vih is mde up of lyers of mterils tht hve di'erent refrtive indexD nd some of the photon generted from the exition my e re)eted t the oundry nd trpped inside the devieF
2.5.3.1 Improvement in internal quantum eciency using low working function cathode
gonjugted polymer is eletron rihD the moility for hole is higher thn eletronD nd more holes will rrive in the polymer lyer thn eletronsF yne wy to inrese the popultion of the eletron is to use lower working funtion metl s thodeF frun nd reeger hve repled the luminum thode with lium results in improved internl e0ieny y ftor of tenD to HFI7F his pproh is diret nd fst ut low working funtion eletrode like lium will e oxidized esily nd shorten the devies9 lifeF
2.5.3.2 Improvement in internal quantum eciency using multiple polymer layers
e lyer of polyPDSEdi@hexyloxyAynoterephthlylidene @gxED pigure PFPHA is oted on top of to improve the trnsport nd reomintion of eletron nd holes @pigure PFPIAF
Figure 2.20:
Structure of CN-PPV.
UH
Figure 2.21:
Schematic representation of a CN-PPV and PPV multi-layer LED.
he nitrile group in the gxE hs two e'et on the polymerF IA st inreses the eletron 0nity so eletrons n trvel more e0ient from the luminum to the polymer lyerF end metl of reltive high working funtion like luminum nd gold n e now e used s thode insted of liumF PA st inreses the inding energy of the oupied nd unoupied B stte ut mintin similr E B gpF o when the nd gxE is pled togetherD holes nd eletron will e on(ned t the heterojuntionF he resulting energy levels re shown in pigure PFPPF
UI
Figure 2.22: Schematic energy-level diagram for a PPV and CN-PPV under foreword bias. Adapted from N. C. Greenham, S. C. Maratti, D. D. C. Bradley, R. H. Friend, and A. B. Holmes, Nature,1993, 365, 62.
he solute energies of levels re not known urtelyD ut the digrm show the reltive position of the rywy nd vwy levels in the polymersD nd the permi levels of the vrious possile metl onttsD the di'erenes in eletron 0nity @ieA nd ioniztion potentil @sA etween nd gxE re lso shown @pigure PFPPAF et the polymers interfe there is sizle o'set in the energies of rywy nd vwy of nd gxE D the holes trnsported from the sy nd the eletrons trnsport from the luminum will e on(ned in the heterojuntionF he lol hrge density will e su0iently high to ensure the holes nd eletrons will pss within ollision pture rdiusF his setEup inreses the hne for n eletrons to omine with holes to form n exitionF sn dditionD the emission will e lose to the juntionD fr wy from the eletrode juntion whih will quenh the singlet exitionsF he result is tht multiElyers vih hs n internl quntum e0ieny of IH7 nd externl quntum e0ieny @for light emitted in foreword diretionA of PS7F fsed on this pprohD ouple of polymers hve een developed or modi(ed to produe the desirle emission olor nd proessing propertyF he drwk of this method is tht desirle properties my not e ommentry to eh otherF por exmpleD in wirE n lkoxy side group @yA is introdued to so tht it n e dissolved in orgni solventF fut the undesirle e'et is tht wirE is less thermlly stleF woreover in multiple lyers vihsD di'erent polymer lyers hve di'erent refrtive indies nd frtion of the photons will undergo totl internl re)etion t the refrtive oundries nd nnot espe s lightF his prolem n e overome y peryEert mirovity strutureF
2.5.3.3 Improvement in external quantum eciency using microcavity
pryEerot resonnt strutures re lso used in inorgni vihD nd re is sed on permi9s golden ruleX ur | <w > | r(v) where w @the mtrix element of the perturtion etween (nl nd initil sttesA depends on the nture of the mterilD nd r(v) n e ltered y hnging the density of vrious density sttesD eFgF using luminesent thin (lms to selet ertin vlue of F sn uilding mirovity for polymer vihD the polymer is pled etween two mirrorsF @pigure PFPQAD in whih one of the mirrors is mde up of luminumD the other mirror @ frgg wirrorA is form y epitxil
UP multilyer stks of ix xy nd iy2 F
Figure 2.23:
Schematic set-up of micro-cavity.
2.5.3.4 Improvement in internal quantum eciency: doping of polymer
hoping is proess tht retes rrier y purposely introduing impurities nd is very populr method in the semiondutor industryF roweverD this tehnique ws not used in polymer vih until IWWSD when oEpolymer polystyreneEpoly@QEhexylthipheneA @EQrA ws doped with pegl3. hoping of wirE with iodine hs improved the e0ieny y PHH7 nd the polymer vih n e operted under oth forwrd nd reverse is @le PFPAF he doping is omplsihed y mixing I wt7 wirE with HFP wt7 s2 F he molr rtio of wirE to s2 is SXIF ht is huge doping rtio when you ompre the doping onentrtion in the semiondutorF
Un-doped Doped
urn on voltge @A ixternl e0ieny @7A

Table 2.2
IH R x IH
-4
foreword SD reversed IP V x IH-3
X esults of iodine doping of n elGwirEGsyEsed vihF
2.5.4 Polymer LEDs on a silicon substrate: an application advantage over inorganic LEDs
sn the initil reserh polymer vihs were in diret ompetition with the inorgni vihs nd tried to hieve the existing vih stndrdF his is di0ult tsk s polymer vihs hve lower long term stilityF roweverD there re some pplitions in whih polymer vihs hve ler dvntge over their more trditionl inorgni nlogsF yne of these is to inorporte vihs with the silion integrted iruits for interEhip ommunitionF st is di0ult to uild inorgni vihs on silion sustrteD euse of the therml stress developing etween the inorgni vih @usully sssE sed devieA nd the silion interfeF fut polymer vihs o'er solutionD sine polymers n e esily spinEoted on the silionF he operting voltge of polymer vih is less thn R D nd the turn on voltge n e s low s P F ogether with swithing time of less thn SH nsD mke polymer vih perfet ndidteF
UQ
2.5.5 Reliability and degradation of polymer LEDs

sn terms of the e0ienyD olor seletionD nd driving voltgeD polymer vih hve ttined dequte level for ommeriliztionF roweverD the devie lifetime is still fr from stisftoryF eserh into understnding the reliility nd degredtion mehnisms of polymer vihs hs generlly een divided into two reX IA hotoEdegrdtion of polymerF PA snterfe degrdtionF
2.5.5.1 Polymer photo degradation
hotoluminesee @vA studies of the photoEoxidtion of hve een undertkenD sine it is elieves tht iv is losely relted with vF st ws found tht there is rpid dey in emission when is exposed to oxygenF sing time resolved ps spetrosopy n inrese in the ronyl signl nd derese in gag signl with time @pigure PFPRAF st ws suggested tht the ronyl group hs strong eletron 0nity level to hrge trnsfer etween moleules segment in the polymerD therey dissoiting the exition nd quenhing the vF
Figure 2.24:
FTIR as a function of photo-oxidation of PPV. Adapted from M. Yan, L. J. Rothberg, F. Papadimitrakopoulos, M. E. Galvin and T. M. Miller, Phys. Rev. Lett., 1994, 73, 744.
imilr reserh ws performed y gumpston nd tensen using fgreE nd Qy @pigure PFPSA nd exposing them to dry ir in irrditionF sn fgreED there is n inrese in ronyl signl with timeD while the Qy remin inttF e mehnism proposed for the degrdtion of fgreE involves the trnsfer of energy from the exited triplet stte of the to oxygen to from singlet oxygen whih ttk the vinyl doule ond in the koneF end Qy dose not hs vinyl ond so it n resist the oxidtion F
UR
Figure 2.25:
Structure of (a) BCHA-PPV and (b) P3OT.
he reserh desried ove ws ll performed on polymer thin (lms deposited on n inert surfeF he presene of thode nd node my lso 'et the oxidtion mehnismF ott et lF hve tken s spetr from wirE vih in the sene of oxygenF hey otined similr result s in n et lFD howeverD derese in sy9s oxygen signl ws notied suggesting tht the sy node ts like oxygen reservoir nd supplies the oxygen for the degrdtion proessF
2.5.5.2 Polymer LED interface degradation
here re few interfe degredtion studies in polymer vihsF yne of them y ott et lF took iw imge of the thode from filed polymer vihF he polymer vih used sy s the nodeD wirE s the polymer lyerD nd n luminum lium lloy s thodeF iw imges showed rters formed in the thodeF he rters re formed when the thode metl is melted nd pull wy from the polymer lyerF st ws suggested tht high urrent density will generte het nd result in lol hot spotF he temperture in the hot spot is high enough to melt the thodeF end when it meltD it will pull wy from the polymerF his proess will derese the e'etive thode reD nd redue the luminesene grdullyF
2.5.6 Bibliography
hF F figentD xF gF qreenhmD tF qrunerD F xF wrksD F rF priendsD F gF worttiD nd eF fF rolmesD Synth.Met., IWWRD 67D QF fF rF gumpston nd uF pF tensenD Synth. Met., IWWSD 73D IWSF tF rF furroughesD hF hF gF frdleyD eF F frownD F xF wrksD uF wkyD F rF priendD F vF furnsD nd eF fF rolmesD NatureD IWWHD 347D SQWF xF gF qreenhmD F gFwrttiD hF hF gF frdleyD F rF priendD nd eF fF rolmesD NatureD IWWQD 365D TPVF tF qrunerD pF gilliD sF hF F muelD F rF priendD Synth. Met, IWWTD 76, IWUF wF reroldD tF qmeinerD F iessD nd wF hwoererD Synth. Met.D IWWTD 76D IHWF F rF tordnD eF hodlpurD vF tF othergD nd F iF lusherD Proceeding of SPIED IWWUD 3002D WPF
US
sF hF rker nd rF rF uimD Appl. Phys. Lett.D IWWRD 64D IUURF tF gF ottD tF uufmnD F tF frokD F hiietroD tF lemD nd tF eF qoitiD J. Appl. Phys.D IWWTD 79D PURSF wF F everD hF qF vidzeyD F eF pisherD wF eF teD hF y9frienD eF fleyerD eF jkhshD hF hF gF frdleyD wF F kolnikD nd qF rillD Thin solid Films, IWWTD 273D QWF wF nD vF tFothergD pF pdimitrkopoulosD wF iF qlvinD nd F wF willerD Phys. Rev. Lett.D IWWRD 73D URRF
2.6 Laser
note:
his module is dpted from the gonnexions module entitled LASER y fill ilsonF
ht is the di'erene etween n vih nd solid stte lserc here re some di'erenesD ut oth devies operte on the sme priniple of hving exess eletrons in the ondution nd of semiondutorD nd rrnging it so tht the eletrons reomine with holes in rditive fshionD giving o' light in the proessF ht is di'erent out lserc sn n vihD the eletrons reomine in rndom nd unorgnized mnnerF hey give o' light y wht is known s spontaneous emissionD whih simply mens tht the ext time nd ple where photon omes out of the devie is up to eh individul eletronD nd things hppen in rndom wyF here is nother wy in whih n exited eletron n emit photon howeverF sf (eld of light @or set of photonsA hppens to e pssing y n eletron in high energy stteD tht light (eld n indue the eletron to emit n dditionl photon through proess lled stimulted emissionF he photon (eld stimulates the eletron to emit its energy s n dditionl photonD whih omes out in phase with the stimulating eldF his is the ig di'erene etween incoherent light @wht omes from n vih or )shlightA nd coherent light whih omes from lserF ith oherent lightD ll of the eletri (elds ssoited with eh phonon re ll extly in phseF his oherene is wht enles us to keep lser em in tight fousD nd to llow it to trvel lrge distne without muh divergene or spreding outF o how do we restruture n vih so tht the light is generted y stimulted emission rther thn spontneous emissionc pirstlyD we uild wht is lled heterostrutureF ell this mens is tht we uild up sndwih of somewht di'erent mterilsD with di'erent hrteristisF sn this seD we put two wide ndEgp regions round region with nrrower nd gpF he most importnt system where this is done is the elqesGqes systemF e nd digrm for suh set up is shown in pigure PFPTF elqes @pronouned 4elEqs4A hs lrger ndEgp then does qesF he potentil 4well4 formed y the qes mens tht the eletrons nd holes will e on(ned thereD nd ll of the reomintion will our in very nrrow stripF his gretly inreses the hnes tht the rriers n intertD ut we still need some wy for the photons to ehve in the proper mnnerF pigure PFPU is digrm of wht typil diode might look likeF e hve the tive qes lyer sndwih inEetween the two heterostruture on(nement lyersD with ontt on top nd ottomF yn either end of the devieD the rystl hs een 4leved4 or roken long rystl lttie plneF his results in shiny 4mirrorElike4 surfeD whih will re)et photonsF he k surfe @whih we n not see hereA is lso leved to mke mirror surfeF he other surfes re purposely roughened so tht they do not re)et lightF xow let us look t the devie from the sideD nd drw just the nd digrm for the qes region @pigure PFPVAF e strt things o' with n eletron nd hole reomining spontneouslyF his emits photon whih heds towrds one of the mirrorsF es the photon goes y other eletronsD howeverD it my use one of them to dey y stimulted emissionF he two @in phseA photons hit the mirror nd re re)eted nd strt k the other wy F es they pss dditionl eletronsD they stimulte them into trnsition s wellD nd the optil (eld within the lser strts to uild upF efter itD the photons get down to the other end of the vityF he leved fetD while it ts like mirrorD is not perfet oneF ome light is not re)etedD ut rther 4leks4Y thoughD nd so eomes the output em from the lserF he detils of (nding wht the rtio of re)eted to trnsmitted light is will
6
UT
hve to wit until lter in the ourse when we tlk out dieletri interfesF he rest of the photons re re)eted k into the vity nd ontinue to stimulte emission from the eletrons whih ontinue to enter the gin region euse of the forwrd is on the diodeF
Figure 2.26:
The band diagram for a double heterostructure GaAs/AlGaAs laser.
Figure 2.27:
A schematic diagram of a typical laser diode.
UU
Figure 2.28:
Build up of a photon eld in a laser diode.
sn relityD the photons do not move k nd forth in ig 4lump4 s we hve desried hereD rther they re distriuted uniformly long the gin region @pigure PFPWAF he (eld within the vity will uild up to the point where the loss of energy y light leking out of the mirrors just equls the rte t whih energy is repled y the reomining eletronsF
Figure 2.29:
Output coupling in a diode laser.
UV

7
2.7 Solar Cells

note:
his module is dpted from the gonnexions module entitled Solar Cells y fill ilsonF
xow let us look t the opposite proess of light genertion for momentF gonsider the following sitution where we hve just plin old norml pEn juntionD only nowD insted of pplying n externl voltgeD we imgine tht the juntion is eing illuminted with light whose photon energy is greter thn the ndEgp @pigure PFQHAF sn this situtionD insted of reomintionD we will get photoEgenertion of eletron hole pirsF he photons simply exite eletrons from the full sttes in the vlene ndD nd 4kik4 them up into the ondution ndD leving hole ehindF his is similir to the therml exittion proessF es n e seen from pigure PFQHD this retes exess eletrons in the ondution nd in the pEside of the diodeD nd exess holes in the vlene nd of the nEsideF hese rriers n di'use over to the juntionD where they will e swept ross y the uiltEin eletri (eld in the depletion regionF sf we were to onnet the two sides of the diode together with wireD urrent would )ow through tht wire s result of the eletrons nd holes whih move ross the juntionF
Figure 2.30:
A schematic representation of a p-n diode under illlumination.
hih wy would the urrent )owc e quik look t pigure PFQH shows tht holes @positive hrge rriersA generted on the nEside will )ot up to the pEside s they go ross the juntionF rene positive urrent must e oming out of the nodeD or pEside of the juntionF vikewiseD eletrons generted on the pEside will fll down the juntion potentilD nd ome out the nEsideD ut sine they hve negtive hrgeD this )ow represents urrent going into the thodeF e hve onstruted photovoltaic diodeD or solar cellF
7
UW pigure PFQI is piture of wht this would look like shemtillyF e might like to onsider the possiility of using this devie s soure of energyD ut the wy we hve things set up nowD sine the voltge ross the diode is zeroD nd sine power equls urrent times voltgeD we see tht we re getting nd from the ellF ht we needD oviouslyD is lod resistorD so let9s put one inF st should e ler from pigure PFQP tht the photo urrent )owing through the lod resistor will develop voltge whih it ises the diode in the forwrd diretionD whihD of ourse will use urrent to )ow k into the nodeF his omplites thingsD it seems we hve urrent oming out of the diode nd urrent going into the diode ll t the sme time3 row re we going to (gure out wht is going onc
Figure 2.31:
Schematic representation of a photovoltaic cell.
Figure 2.32:
Photovoltaic cell with a load resistor.
he nswer is to mke modelF he urrent whih rises due to the photon )ux n e onveniently represented s urrent soureF e n leve the diode s diodeD nd we hve the iruit shown in pigure PFQQF iven though we show sout oming out of the devieD we know y the usul polrity onvention tht when we de(ne out s eing positive t the topD then we should show the urrent for the photovoltiD spv s urrent going into the topD whih is wht ws done in pigure PFQQF xote tht spv a sdiode E sphoto D so ll we need to do is to sutrt the two urrentsY we do this grphilly in pigure PFQRF xote tht we hve numered the four qudrnts in the sE plot of the totl urrentF sn qudrnt s nd sssD the produt of I nd V is positive numerD mening tht power is eing dissipted in the ellF por qudrnt ss nd sD the
VH
produt of I nd V is negtiveD nd so we re getting power from the devieF glerly we wnt to operte in qudrnt sF sn ftD without the ddition of n externl ttery or urrent soureD the iruitD will only run in the s9th qudrntF gonsider djusting L D the lod resistor from H @ shortA to @n openAF ith L D we would e t point e on pigure PFQRF es L strts to inrese from zeroD the voltge ross oth the diode nd the resistor will strt to inrese lsoD nd we will move to point fD syF es L gets igger nd iggerD we keep moving long the urve untilD t point gD where L is n open nd we hve the mximum voltge ross the devieD utD of ourseD no urrent oming out3
Figure 2.33:
A model of a PV cell.
VI
Figure 2.34:
Combining the diode and the current source.
ower is V I so t f for instneD the power oming out would e represented y the re enlosed y the two dotted lines nd the oordinte xesF omeple out where s hve point f would e where we would e getting the most power out of out solr ellF pigure PFQS shows you wht rel solr ell would look likeF hey re usully mde from omplete wfer of silionD to mximize the usle reF e shllow @HFPS mA juntion is mde on the topD nd top ontts re pplied s stripes of metl ondutor s shownF en ntiEre)etion @eA oting is pplied on top of thtD whih ounts for the luish olor whih typil solr ell hs @pigure PFQTAF
VP
Figure 2.35:
A schematic diagram of a real solar cell.
Figure 2.36:
A solar cell showing the blue tint due to the AR coating.
he solr power )ux on the erth9s surfe is @onvenientlyA out I kGm2 or IHH mGm2 F o if we mde solr ell from R inh dimeter wfer @typilA it would hve n re of out 81cm2 nd so would e reeiving )ux of out VFI ttsF ypil ell e0ienies run from out IH7 to mye IS7 unless speil @nd ostlyA triks re mdeF his mens tht we will get out IFP tts out from single wferF vooking t f on PFSW we ould guess tht Vout will e out HFS to HFT voltsD thus we ould expet to get mye round PFS mps from R inh wfer t HFS volts with IS7 e0ieny under the illumintion of one
VQ sunF
VR
Chapter 3
Bulk Materials
3.1 Properties of Gallium Arsenide
3.1.1 Gallium: the element
he element gllium ws preditedD s ekEluminumD y wendeleev in IVUHD nd susequently disovered y veoq de foisudrn in IVUSY in ft de foisudrn hd een serhing for the missing element for some yersD sed on his own independent theoryF he (rst experimentl indition of gllium me with the oservtion of two new violet lines in the sprk spetrum of smple deposited on zinF ithin month of these initil results de foisudrn hd isolted I g of the metl strting from severl hundred kilogrms of rude zin lende oreF he new element ws nmed in honor of prne @vtin GalliaAD nd the striking similrity of its physil nd hemil properties to those predited y wendeleev @le QFIA did muh to estlish the generl eptne of the periodi vwY indeedD when de foisudrn (rst stted tht the density of q ws RFU gGm3 rther thn the predited SFW gGm3 D wendeleev wrote to him suggesting tht he redetermine the vlue @the orret vlue is SFWHR gGm3 AF
Property Mendeleev's prediction (1871) for eka-aluminum, M Observed properties of gallium (discovered 1875)
1
etomi weight hensityD gFm-3 welting point por pressure lene yxide hensity of oxide @gGm3 A
F TV SFW vow xonEvoltile Q w2 y3 SFS
TWFUP SFWHR PWFUV IH-3 mmrgD IHHH g Q q2 y3 SFVV

VS
VT roperties of metl roperties of hydroxide roperties of slts w should dissolve slowly in ids nd lklis nd e stle in ir w@yrA3 should dissolve in oth ids nd lklis w slts will tend to form E si sltsY the sulfte should form lumsY w2 3 should e preipE itted y r2 or @xr4 A2 Y nE hydrous wgl3 should e more voltile thn ngl2
CHAPTER 3. BULK MATERIALS

q metl dissolves slowly in ids nd lklis nd is stle in ir q@yrA3 dissolves in oth ids nd lklis q slts redily hydrolyze nd form si sltsY lums re knownY q2 3 n e preipE itted under speil onditions y r2 or @xr4 A2 D nhydrous qgl3 is more voltile thn ngl2 F
Table 3.1
X gomprison of predited nd oserved properties of glliumF
qllium hs eutiful silvery lue pperneY it wets glssD porelinD nd most other surfes @exept qurtzD grphiteD nd e)on A nd forms rillint mirror when pinted on to glssF he tomi rdius nd (rst ioniztion potentil of gllium re lmost identil with those of luminum nd the two elements frequently resemle eh other in hemil propertiesF foth re mphoteriD ut gllium is less eletropositive s indited y its lower eletrode potentilF hi'erenes in the hemistry of the two elements n e relted to the presene of (lled set of Qd oritls in glliumF qllium is very muh less undnt thn luminum nd tends to our t low onentrtions in sul(de minerls rther thn s oxidesD lthough gllium is lso found ssoited with luminum in uxiteF he min soure of gllium is s yEprodut of luminum re(ningF et IW ppm of the erth9s rustD gllium is out s undnt s nitrogenD lithium nd ledY it is twie s undnt s oron @W ppmAD ut is more di0ult to extrt due to the lk of ny mjor glliumEontining oreF qllium lwys ours in ssoition either with zin or germniumD its neighors in the periodi tleD or with luminum in the sme groupF husD the highest onentrtions @HFI E I7A re in the rre minerl germnite @ omplex sul(de of nD guD qeD nd esAY onentrtions in sphlerite @nAD uxiteD or olD re hundredEfold lessF
3.1.2 Gallium pnictides

qllium9s min use is in semiondutor tehnologyF por exmpleD qes nd relted ompounds n onvert eletriity diretly into oherent light @lser diodesA nd is employed in eletroluminesent lightEemitting diodes @vih9sAY it is lso used for doping other semiondutors nd in solidEstte devies suh s heteroE juntion ipolr trnsistors @rfsA nd high power high speed metl semiondutor (eld e'et trnsistors @wipisAF he ompound wgq2 y4 is used in ultrvioletEtivted powders s rillint green phosphor used in erox opying mhinesF winor uses re s highEtemperture liquid selsD mnometri )uids nd hetEtrnsfer mediD nd for lowEtemperture soldersF ndoutedly the inry ompounds of gllium with the most industril interest re those of the qroup IS @A elementsD qi @i a xD D esD AF he ompounds whih gllium forms with nitrogenD phosphorusD rseniD nd ntimony re isoeletroni with the qroup IR elementsF here hs een onsiderle interestD prtiulrly in the physil properties of these ompoundsD sine IWSP when elker (rst showed tht they hd semionduting properties nlogous to those of silion nd germniumF qllium phosphideD rsenideD nd ntimonide n ll e prepred y diret retion of the elementsY this is normlly done in seled sili tues or in grphite ruile under hydrogenF hse digrm dt is hrd to otin in the glliumEphosphorus system euse of loss of phosphorus from the ulk mteril t elevted temperturesF husD q hs vpor pressure of more thn IQFS tm t its melting pointY s ompred to HFVW tm for qesF he physil properties of these three ompounds re ompred with those of the nitride in le QFPF ell three dopt the zin lende rystl struture nd re more highly onduting thn gllium nitrideF
VU
Property
GaN
GaP
GaAs
GaSb
welting point @ gA hensity @gGm A grystl struture gell dimenF @A k @ohm-1 m-1 A fnd gp @eA
Table 3.2
> IPSH @deA

F TFI urtzite
IQSH RFIQV zin lende
IPRH SFQIUT zin lende
UIP SFTIQU zin lende
a b
a a QFIVUD c a SFIVT
PFQS IH-9 E IH-7 QFRR
a a SFRSHS
QFIUV IH-2 E IH2 PFPR
a a SFTSQP
QFTTT IH-6 E IH3 IFRPR
a a TFHWSW
RFQVV T E IQ HFUI
efrtive index
c
X hysil properties of IQEIS ompound semiondutorsF a lues given for QHH uF b hependent on photon energyY vlues given for IFS e inident photonsF c hependent on tempertureY vlues given for QHH uF
3.1.3 Gallium arsenide versus silicon

qllium rsenide is ompound semiondutor with omintion of physil properties tht hs mde it n ttrtive ndidte for mny eletroni pplitionsF prom omprison of vrious physil nd eletroni properties of qes with those of i @le QFQA the dvntges of qes over i n e redily sertinedF nfortuntelyD the mny desirle properties of gllium rsenide re o'set to gret extent y numer of undesirle propertiesD whih hve limited the pplitions of qes sed devies to dteF
Properties GaAs Si
pormul weight grystl struture vttie onstnt welting point @ gA
IRRFTQ zin lende SFTSQP IPQV SFQP HFRT IFRPR IFUW x IH6 IH8 R x IH5 IH-8 VSHH
PVFHW dimond SFRQHWS IRIS PFQPV IFS IFIP IFRS x IH10 PFQ x IH5 Q x IH5 PFS x IH-3 ISHH
hensity @gGm A herml ondutivity @GmFuA fnd gp @eA t QHH u sntrinsi rrier onF @m-3 A sntrinsi resistivity @ohmFmA frekdown (eld @GmA winority rrier lifetime @sA woility @m2 GFsA
Table 3.3
X gomprison of physil nd semiondutor properties of qes nd iF
3.1.3.1 Band gap
he nd gp of qes is IFRP eY resulting in photon emission in the infrEred rngeF elloying qes with el to give elx q1-x es n extend the nd gp into the visile red rngeF nlike iD the nd gp of qes
VV
is diretD iFeFD the trnsition etween the vlene nd mximum nd ondution nd minimum involves no momentum hnge nd hene does not require ollortive prtile intertion to ourF hoton genertion y interEnd rditive reomintion is therefore possile in qesF heres in iD with n indiret ndEgpD this proess is too ine0ient to e of useF he ility to onvert eletril energy into light forms the sis of the use of qesD nd its lloysD in optoeletronisY for exmple in light emitting diodes @vihsAD solid stte lsers @light mpli(tion y the stimulted emission of rditionAF e signi(nt drwk of smll nd gp semiondutorsD suh s iD is tht eletrons my e thermlly promoted from the vlene nd to the ondution ndF husD with inresing temperture the therml genertion of rriers eventully eomes dominnt over the intentionlly doped level of rriersF he wider nd gp of qes gives it the ility to remin 9intentionlly9 semionduting t higher temperturesY qes devies re generlly more stle to high tempertures thn similr i deviesF
3.1.3.2 Carrier density
he low intrinsi rrier density of qes in pure @undopedA form indites tht qes is intrinsilly very poor ondutor nd is ommonly referred to s eing semiEinsultingF his property is usully ltered y dding dopnts of either the pE @positiveA or nE @negtiveA typeF his semiEinsulting property llows mny tive devies to e grown on single sustrteD where the semiEinsulting qes provides the eletril isoltion of eh devieY n importnt feture in the minituriztion of eletroni iruitryD iFeFD vs @veryE lrgeEsleEintegrtionA involving over IHHDHHH omponents per hip @one hip is typilly etween I nd IH mm squreAF
3.1.3.3 Electron mobility
he higher eletron moility in qes thn in i potentilly mens tht in devies where eletron trnsit time is the ritil performne prmeterD qes devies will operte with higher response times thn equivlent i deviesF roweverD the ft tht hole moility is similr for oth qes nd i mens tht devies relying on oopertive eletron nd hole movementD or hole movement loneD show no improvement in response time when qes sedF
3.1.3.4 Crystal growth
he ulk rystl growth of qes presents prolem of stoihiometri ontrol due the lossD y evportionD of rseni oth in the melt nd the growing rystl @> ca. THH gAF welt growth tehniques reD thereforeD designed to enle n overpressure of rseni ove the melt to e mintinedD thus preventing evportive lossesF he loss of rseni lso negtes di'usion tehniques ommonly used for wfer doping in i tehnologyY sine the di'usion tempertures required exeed tht of rseni lossF
3.1.3.5 Crystal Stress
he therml grdient ndD heneD stress generted in melt grown rystls hve limited the mximum dimeter of qes wfers @urrently T4 dimeter ompred to over IP4 for iAD euse with inresed wfer dimeters the therml stress generted dislotion @rystl imperfetionsA densities eventully eomes uneptle for devie pplitionsF
3.1.3.6 Physical strength
qllium rsenide single rystls re very rittleD requiring tht onsiderly thiker sustrtes thn those employed for i deviesF
VW
3.1.3.7 Native oxide
qllium rsenide9s ntive oxide is found to e mixture of nonEstoihiometri gllium nd rseni oxides nd elementl rseniF husD the eletroni nd struture is found to e severely disrupted using rekdown in 9norml9 semiondutor ehvior on the qes surfeF es onsequeneD the qes wspi @metlEinsultorEsemiondutorE(eldEe'etEtrnsistorA equivlent to the tehnologilly importnt i sed wypi @metlEoxideEsemiondutorE(eldEe'etEtrnsistorA isD thereforeD presently unvilleF he pssivtion of the surfe of qes is therefore key issue when endevoring to utilize the pi tehnology using qesF ssivtion in this disussion mens the redution in midEgp nd sttes whih destroy the semionduting properties of the mterilF edditionllyD this lso mens the prodution of hemilly inert oting whih prevents the formtion of dditionl retive sttesD whih n e'et the properties of the devieF
3.1.4 Bibliography
F uF qhndhiD VLSI Fabrication Principles: Silicon and Gallium Arsenide. ileyEsntersieneD xew orkD @IWWRAF Properties of Gallium Arsenide. idF wF F frozel nd qF iF tillmnF Qrd idF snstitution of iletril ingineersD vondon @IWWTAF
3.2 Synthesis and Purication of Bulk Semiconductors

3.2.1 Introduction
he synthesis nd puri(tion of ulk polyrystlline semiondutor mteril represents the (rst step towrds the ommeril frition of n eletroni devieF his polyrystlline mteril is then used s the rw mteril for the formtion of single rystl mteril tht is proessed to semiondutor wfersF he strong in)uene on the eletri hrteristis of semiondutors exhiited y smll mounts of some impurities requires tht the ulk rw mteril e of very high purity @> WWFWWWW7AF elthough some level of puri(tion is possile during the rystlliztion proess it is importnt to use s high purity strting mteril s possileF hile wide rnge of sustrte mterils re ville from ommeril vendorsD silion nd qes represent the only lrgeEsle ommeril semiondutor sustrtesD nd thus the disussion will e limited to the synthesis nd puri(tion of these mterilsF
3.2.2 Silicon
pollowing oxygen @RT7AD silion @vF siliis )intA is the most undnt element in the erth9s rust @PV7AF roweverD silion does not our in its elementl formD ut s its oxide @iy2 A or s silitesF ndD qurtzD methystD gteD )intD nd opl re some of the forms in whih the oxide ppersF qrniteD hornlendeD sestosD feldsprD ly nd miD etF re few of the numerous silite minerlsF ith suh oundless supplies of the rw mterilD the osts ssoited with the prodution of ulk silion is not one of strtion nd onversion of the oxide@sAD ut of puri(tion of the rude elementl silionF hile WV7 elementl silionD known s metllurgilEgrde silion @wqAD is redily produed on lrge sleD the requirements of extreme purity for eletroni devie frition require dditionl puri(tion steps in order to produe eletroniEgrde silion @iqAF iletroniEgrde silion is lso known s semiondutorEgrde silion @qAF sn order for the purity levels to e eptle for susequent rystl growth nd devie fritionD iq must hve ron nd oxygen impurity levels less thn few prts per million @ppmAD nd metl impurities t the prts per illion @ppA rnge or lowerF le QFR nd le QFS give typil impurity onentrtions in wq nd iqD respetivelyF fesides the purityD the prodution ost nd the spei(tions must meet the industry desiresF
2
WH

Element Concentration (ppm) Element Concentration (ppm)
luminum oron lium hromium opper iron mgnesium

Table 3.4
IHHHERQSH RHETH PRSESHH SHEPHH ISERS ISSHETSHH IHESH
mngnese molydenum nikel phosphorus titnium vndium zironium
SHEIPH
< PH
IHEIHS PHESH IRHEQHH SHEPSH PH
X ypil impurity onentrtions found in metllurgilEgrde silion @wqAF

Concentration (ppb) Element Concentration (ppb)
Element
rseni ntimony oron ron hromium olt opper

Table 3.5
< HFHHI < HFHHI HFI

IHHEIHHH
gold iron nikel oxygen phosphorus silver zin
< HFHHHHI
HFIEIFH HFIEHFS IHHERHH
< HFHI
HFHHI HFI
HFQ
HFHHI
< HFI
X ypil impurity onentrtions found in eletroniEgrde silion @iqAF
3.2.2.1 Metallurgical-grade silicon (MGS)
he typil soure mteril for ommeril prodution of elementl silion is qurtzite grvelY reltively pure form of snd @iy2 AF he (rst step in the synthesis of silion is the melting nd redution of the sili in sumergedEeletrode r furneF en exmple of whih is shown shemtilly in pigure QFID long with the pproprite hemil retionsF e mixture of qurtzite grvel nd ron re heted to high tempertures @F IVHH gA in the furneF he ron ed onsists of mixture of olD okeD nd wood hipsF he ltter providing the neessry porosity suh tht the gses reted during the retion @iy nd gyA re le to )ow through the edF
WI
Schematic of submerged-electrode arc furnace for the production of metallurgical-grade silicon (MGS).
Figure 3.1:
he overll redution retion of iy2 is expressed in @QFIAD howeverD the retion sequene is more omplex thn this overll retion impliesD nd involves the formtion of ig nd iy intermeditesF he initil retion etween molten iy2 nd g @@QFPAA tkes ple in the r etween djent eletrodesD where the lol temperture n exeed PHHH gF he iy nd gy thus generted )ow to ooler zones in the furne where ig is formed @@QFQAAD or higher in the ed where they reform iy2 nd g @@QFPAAF he ig rets with molten iy2 @@QFRAA produing the desired silion long with iy nd gyF he molten silion formed is drwnEo' from the furne nd solidi(edF @QFIA
@QFPA
@QFQA
@QFRA he sEprodued wq is pproximtely WVEWW7 pureD with the mjor impurities eing luminum nd iron @le QFRAD howeverD otining low levels of oron impurities is of prtiulr importneD euse it is di0ult to remove nd serves s dopnt for silionF he drwks of the ove proess re tht it is energy nd rw mteril intensiveF st is estimted tht the prodution of one metri ton @IDHHH kgA of wq requires PSHHEPUHH kg qurtziteD THH kg hrolD THHEUHH kg ol or okeD QHHESHH kg wood hipsD nd SHHDHHH kh
WP
of eletri powerF gurrentlyD pproximtely SHHDHHH metri tons of wq re produed per yerD worldwideF wost of the prodution @F UH7A is used for metllurgil pplitions @eFgFD luminumEsilion lloys re ommonly used for utomotive engine loksA from whene its nme is derivedF epplitions in vriety of hemil produts suh s silione resins ount for out QH7D nd only I7 or less of the totl prodution of wq is used in the mnufturing of highEpurity iq for the eletronis industryF he urrent worldwide onsumption of iq is pproximtely S x IH6 kg per yerF
3.2.2.2 Electronic-grade silicon (EGS)
iletroniEgrde silion @iqA is polyrystlline mteril of exeptionlly high purity nd is the rw mteE ril for the growth of singleErystl silionF iq is one of the purest mterils ommonly villeD see le QFSF he formtion of iq from wq is omplished through hemil puri(tion proessesF he si onept of whih involves the onversion of wq to voltile silion ompoundD whih is puri(ed y distilE ltionD nd susequently deomposed to reEform elementl silion of higher purity @iFeFD iqAF srrespetive of the puri(tion route employedD the (rst step is physil pulveriztion of wq followed y its onversion to the voltile silion ompoundsF e numer of ompoundsD suh s monosilne @ir4 AD dihlorosilne @ir2 gl2 AD trihlorosilne @irgl3 AD nd silion tetrhloride @igl4 AD hve een onsidered s hemil intermeditesF emong theseD irgl3 hs een used predominntly s the intermedite ompound for susequent iq formtionD lthough ir4 is used to lesser extentF ilion tetrhloride nd its lower hlorinted derivtives re used for the hemil vpor deposition @ghA growth of i nd iy2 F he oiling points of silne nd its hlorinted produts @le QFTA re suh tht they re onveniently seprted from eh other y frtionl distilltionF
Compound Boiling point ( C)
ir4 ir3 gl ir2 gl2 irgl3 igl4

Table 3.6
EIIPFQ EQHFR VFQ QIFS SUFT
X foiling points of silne nd hlorosilnes t UTH mmrg @I tmosphereAF
he resons for the predominnt use of irgl3 in the synthesis of iq re s followsX IF irgl3 n e esily formed y the retion of nhydrous hydrogen hloride with wq t resonly low tempertures @PHH E RHH gAY PF it is liquid t room temperture so tht puri(tion n e omplished using stndrd distilltion tehniquesY QF it is esily hndled nd if dry n e stored in ron steel tnksY RF its liquid is esily vporized ndD when mixed with hydrogen it n e trnsported in steel lines without orrosionY SF it n e redued t tmospheri pressure in the presene of hydrogenY TF its deposition n tke ple on heted silionD thus eliminting ontt with ny foreign surfes tht my ontminte the resulting silionY nd UF it rets t lower tempertures @IHHH E IPHH gA nd t fster rtes thn does igl4 F
WQ
3.2.2.2.1 Chlorosilane (Seimens) process
rihlorosilne is synthesized y heting powdered wq with nhydrous hydrogen hloride @rglA t round QHH g in )uidizedEed retorD @QFSAF
@QFSA ine the retion is tully n equilirium nd the formtion of irgl3 highly exothermiD e0ient removl of generted het is essentil to ssure mximum yield of irgl3 F hile the stoihiometri retion is tht shown in iqF SD mixture of hlorinted silnes is tully prepred whih must e seprted y frtionl distilltionD long with the hlorides of ny impuritiesF sn prtiulr ironD luminumD nd oron re removed s pegl3 @FpF a QIT gAD elgl3 @mFpF a IWH g sulFAD nd fgl3 @FpF a IPFTS gAD respetivelyF prtionl distilltion of irgl3 from these impurity hlides result in gretly inresed purity with onentrtion of eletrilly tive impurities of less thn I ppF iq is prepred from puri(ed irgl3 in hemil vpor deposition @ghA proess similr to the epiE txil growth of iF he highEpurity irgl3 is vporizedD diluted with highEpurity hydrogenD nd introdued into the eimens deposition retorD shown shemtilly in pigure QFPF ithin the retorD thin silion rods lled slim rods @F R mm dimeterA re supported y grphite eletrodesF esistne heting of the slim rods uses the deomposition of the irgl3 to yield silionD s desried y the reverse retion shown in iqF SF
Figure 3.2:
Schematic representation of a Seimens deposition reactor.
he shift in the equilirium from forming irgl3 from i t low tempertureD to forming i from irgl3 t high temperture is s onsequene of the temperture dependene @@QFTAA of the equilirium onstnt @@QFUAD where a prtil pressureA for @QFSAF ine the formtion of irgl3 is exothermiD iFeFD r < HD n inrese in the temperture uses the prtil pressure of irgl3 to dereseF husD the iemens proess is typilly run t F IIHH gD while the reverse )uidized ed proess is rried out t QHH gF @QFTA
WR
@QFUA he slim rods t s nuletion point for the deposition of silionD nd the resulting polyrystlline rod onsists of olumnr grins of silion @polysilionA grown perpendiulr to the rod xisF qrowth ours t less thn I mm per hourD nd fter deposition for PHH to QHH hours highEpurity @iqA polysilion rods of ISHEPHH mm in dimeter re produedF por susequent )otEzone re(ning the polysilion iq rods re ut into long ylindril rodsF elterntivelyD the sEformed polysilion rods re roken into hunks for single rystl growth proessesD for exmple gzohrlski melt growthF sn ddition to the formtion of silionD the rgl oprodut rets with the irgl3 retnt to form silion tetrhloride @igl4 A nd hydrogen s mjor yproduts of the proessD @QFVAF his retion represents mjor disdvntge with the eimens proessX poor e0ieny of silion nd hlorine onsumptionF ypillyD only QH7 of the silion introdued into gh retor is onverted into highEpurity polysilionF @QFVA sn order to improve e0ieny the rglD igl4 D r2 D nd unreted irgl3 re seprted nd reovered for reylingF pigure QFQ illustrtes the entire hlorosilne proess strting with wq nd inluding the reyling of the retion yproduts to hieve high overll proess e0ienyF es onsequeneD the prodution ost of highEpurity iq depends on the ommeril usefulness of the yprodutD igl4 F edditionl disdvntges of the eimens proess re derived from its reltively smll th sizeD slow growth rteD nd high power onsumptionF hese issues hve led to the investigtion of lterntive ost e0ient routes to iqF
Schematic representation of the reaction pathways for the formation of EGS using the chlorosilane process.
Figure 3.3:
WS
3.2.2.2.2 Silane process
en lterntive proess for the prodution of iq tht hs egun to reeive ommeril ttention is the pyrolysis of silne @ir4 AF he dvntges of produing iq from ir4 insted of irgl3 re potentilly lower osts ssoited with lower retion temperturesD nd less hrmful yprodutsF ilne deomposes < WHH g to give silion nd hydrogenD @QFWAF @QFWA ilne my e prepred y numer of routesD eh hving dvntges with respet to purity nd prodution ostF he simplest proess involves the diret retion of wq powders with mgnesium t SHH g in hydrogen tmosphereD to form mgnesium siliide @wg2 iAF he mgnesium siliide is then reted with mmonium hloride in liquid mmoni elow H gD @QFIHAF @QFIHA his proess is idelly suited to the removl of oron impurities @ pEtype dopnt in iAD euse the diorne @f2 r6 A produed during the retion forms the vewis idEse omplexD r3 f@xr3 AD whose voltility is su0iently lower thn ir4 D llowing for the puri(tion of the ltterF st is possile to prepre iq with oron ontent of PH ppt using ir4 synthesized in this mnnerF roweverD phosphorus @nother dopntA in the form of r3 my e present s ontminnt requiring susequent puri(tion of the ir4 F elterntive routes to ir4 involve the hemil redution of igl4 y either lithium hydride @@QFIIAAD lithium luminum hydride @@QFIPAAD or vi hydrogention in the presene of elementl silion @@QFIQA E @QFITAAF he hydride redution retions my e rriedEout on reltively lrge sles @F SH kgAD ut only th proessesF sn ontrstD nion gride hs dpted the hydrogention to ontinuous proessD involving disproportiontion retions of hlorosilnes @@QFIRA E @QFITAA nd the frtionl distilltion of silne @le QFTAF @QFIIA
@QFIPA
@QFIQA
@QFIRA
@QFISA
@QFITA yrolysis of silne on resistively heted polysilion (lments t UHHEVHH g yields polyrystlline iqF es noted oveD the iq formed hs remrkly low oron impurities ompred with mteril prepred from trihlorosilneF woreoverD the resulting iq is less ontminted with trnsition metls from the retor ontiner euse ir4 deomposition does not use s muh of orrosion prolem s is oserved with hlide preursor ompoundsF
WT
3.2.2.2.3 Granular polysilicon deposition
foth the hlorosilne @eimensA nd silne proesses result in the formtion of rods of iqF roweverD there hs een inresed interest in the formtion of grnulr polyrystlline iqF his proess ws developed in IWVH9sD nd relies on the deomposition of ir4 in )uidizedEed deposition retor to produe freeE)owing grnulr polysilionF iny silion prtiles re )uidized in ir4 Gr2 )owD nd t s seed rystl onto whih polysilion deposits to form freeE)owing spheril prtilesF he size distriution of the prtiles thus formed is over the rnge from HFI to IFS mm in dimeter with n verge prtile size of HFU mmF he )uidizedEed seed prtiles re originlly mde y grinding iq in ll @or hmmerA mill nd lehing the produt with idD hydrogen peroxideD nd wterF his proess is timeEonsuming nd ostlyD nd tended to introdue undesirle impurities from the metl grindersF sn new methodD lrge iq prtiles re (red t eh other y highEspeed strem of inert gs nd the ollision reks them down into prtiles of suitle size for )uidized edF his proess hs the min dvntge tht it introdues no foreign mterils nd requires no lehing or other post puri(tionF he )uidizedEed retors re muh more e0ient thn trditionl rod retors s onsequene of the greter surfe re ville during gh growth of silionF st hs een suggested tht )uidizedEed retors require 1 G5 to 1 G10 the energyD nd hlf the pitl ost of the trditionl proessF he qulity of )uidizedEed polysilion hs proven to e equivlent to polysilion produed y the onventionl methodsF woreoverD grnulr iq in freeE)owing formD nd with high ulk densityD enles rystl growers to otin the highD reproduile prodution yields out of eh rystl growth runF por exmpleD in the gzohrlski rystl growth proessD ruiles n e quikly nd esily (lled to uniform loding with grnulr iqD whih typilly exeed those of rndomly stked polysilion hunks produed y the iemens silne proessF
3.2.2.3 Zone rening
he tehnique of zone re(ning is used to purify solid mterils nd is ommonly employed in metllurgil re(ningF sn the se of silion my e used to otin the desired ultimte purity of iqD whih hs lredy een puri(ed y hemil proessesF one re(ning ws invented y fnnD nd mkes use of the ft tht the equilirium soluility of ny impurity @eFgFD elA is di'erent in the solid nd liquid phses of mteril @eFgFD iAF por the dilute solutionsD s is oserved in iq silionD n equilirium segregtion oe0ient @k0 A is de(ned y k0 a gs Ggl D where gs nd gl re the equilirium onentrtions of the impurity in the solid nd liquid ner the interfeD respetivelyF sf k0 is less thn I then the impurities re left in the melt s the molten zone is moved long the mterilF sn prtil sense molten zone is estlished in solid rodF he zone is then moved long the rod from left to rightF sf k < I then the frozen prt left on the triling edge of the moving molten zone will e purer thn the mteril tht melts in on the rightEside leding edge of the moving molten zoneF gonsequently the solid to the left of the molten zone is purer thn the solid on the rightF et the ompletion of the (rst pss the impurities eome onentrted to the right of the solid smpleF epetition of the proess llows for puri(tion to exeptionlly high levelsF le QFUF lists the equilirium segregtion oe0ients for ommon impurity nd dopnt elements in silionY it should e noted tht they re ll less thn IF
Element k0 Element k0
luminum oron ron opper

Table 3.7
HFHHP HFV HFHU R x IH

-6
iron oxygen phosphorus ntimony
V x IH-6 HFPS HFQS HFHPQ
X egregtion oe0ients for ommon impurity nd dopnt elements in silionF
WU
3.2.3 Gallium arsenide

sn ontrst to eletroni grde silion @iqAD whose use is minor frtion of the glol prodution of elementl silionD gllium rsenide @qesA is produed exlusively for use in the semiondutor industryF roweverD rseni nd its ompounds hve signi(nt ommeril pplitionsF he min use of elementl rseni is in lloys of D nd to lesser extent guD while rseni ompounds re widely used in pestiides nd wood preservtives nd the prodution of ottle glssF husD the eletronis industry represents minor user of rseniF sn ontrstD lthough gllium hs minor uses s highEtemperture liquid selD mnometri )uids nd het trnsfer mediD nd for low temperture soldersD its min use is in semiondutor tehnologyF
3.2.3.1 Isolation and purication of gallium metal
et IW ppm gllium @vF GalliaD prneA is out s undnt s nitrogenD lithium nd ledY it is twie s undnt s oron @W ppmAD ut is more di0ult to extrt due to the lk of ny mjor glliumEontining oreF qllium lwys ours in ssoition either with zin or germniumD its neighors in the periodi tleD or with luminum in the sme groupF husD the highest onentrtions @HFIEI7A re in the rre minerl germnite @ omplex sul(de of nD guD qeD nd esAD while onentrtions in sphlerite @nAD dispore ely@yrAD uxiteD or olD re hundredEfold lessF sndustrillyD gllium ws originlly reovered from the )ue dust emitted during sul(de rosting or ol urning @up to IFS7 qAD howeverD it is now otined s side produt of vst luminum industry nd in prtiulr from the fyer proess for otining lumin from uxiteF he fyer proess involves dissolution of uxiteD elyx yr3-2x D in queous xyrD seprtion of insolule impuritiesD prtil preipittion of the trihydrteD el@yrA3 D nd lintion t IDPHH gF huring proessing the lkline solution is grdully enrihed in gllium from n initil weight rtio qGel of out IGSHHH to out IGQHHF iletrolysis of these extrts with rg thode results in further onentrtionD nd the solution of sodium gllte thus formed is then eletrolyzed with stinless steel thode to give q metlF ine uxite ontins HFHHQEHFHI7 glliumD omplete reovery would yield some SHHEIHHH tons per nnumD however present onsumption is only HFI7 of this out IH tons per nnumF e typil nlysis of the WVEWW7 pure gllium otined s side produt from the fyer proess is shown in le QFVF his mteril is further puri(ed to WWFWW7 y hemil tretment with ids nd y2 t high tempertures followed y rystlliztionF his hemil proess results in the redution of the mjority of metl impurities t the ppm levelD see le QFVF uri(tion to seven nines WWFWWWW7 is possile through zone re(ningD howeverD sine the equilirium distriution oe0ient of the residul impurities k0 ID multiple psses re requiredD typilly > SHHF he low melting point of gllium ensures tht ontmintion from the ontiner wll @whih is signi(nt in silion zone re(ningA is minimizedF sn order to filitte the multiple zone re(ning in suitle timeD simple modi(tion of zone re(ning is employed shown in pigure QFRF he gllium is ontined in plsti tue wrpped round rotting ylinder tht is hlf immersed in ooling thF e heter is positioned ove the gllium plsti oilF husD estlishing series of molten zones tht pss upon rottion of the drum y one helil segment per revolutionF sn this mnnerD SHH psses my e mde in reltively short time periodsF he typil impurity levels of gllium zone re(ned in this mnner re given in le QFVF
Element Bayer process (ppm) After acid/base leaching (ppm) 500 zone (ppm) passes
WV luminum lium opper iron led mgnesium merury nikel silion tin titnium zin
Table 3.8

IHHEIDHHH IHEIHH IHHEIDHHH IHHEIDHHH U not deteted P U QH I not deteted not deteted
<I
not deteted
<I <I
not deteted not deteted not deteted not deteted not deteted not deteted
< PHHH
IHEIHH IHEIHH IHEIHH IHEIHH IHEIHH IHEIHH QHDHHH
I I
I
<I
not deteted
X ypil nlysis of gllium otined s side produt from the fyer proessF
Figure 3.4:
Schematic representation of a zone rening apparatus.
3.2.3.2 Isolation and purication of elemental arsenic
ilementl rseni @vF rseniumD yellow orpimentA exists in two formsX yellow @uiD es4 A nd gry or metlli @rhomohedrlAF et nturl undne of IFV ppm rseni is reltively rreD howeverD this is o'set y its presene in numer of ommon minerls nd the reltive ese of isoltionF erseni ontining minerls re grouped into three min lssesX the sul(des relgr @es4 4 A nd orpiment @es2 3 AD the oxide rsenolite @es2 y3 AD nd the rsenides nd sulfresenides of the ironD oltD nd nikelF winerls in this ltter lss inludeX loellinginite @pees2 AD s'orlite @goesAD niolite @xiesAD rmmelsergite @xies2 AD nsenopyrite or mispikel @peesAD oltite @goesAD enrgite @gu3 es4 AD gerdsor(te @xiesAD nd the qurturnry sul(de gluodot @goDpeAesF le QFW shows the typil impurities in rsenopyriteF
WW
Element
Concentration (ppm)
Element
Concentration (ppm)
silver gold olt opper germnium mngnese molydenum
WH V QHDHHH PHH QH QDHHH TH

Table 3.9
nikel led pltinum rhenium selenium vndium zin
< QDHHH
SH HFR SH SH QHH RHH
X ypil impurities in rsenopyriteF
erseni is otined ommerilly y smelting either pees2 or pees t TSHEUHH g in the sene of ir nd ondensing the sulimed element @sub a TIQ gAD @QFIUAF @QFIUA he rseni thus otined is omined with led nd then sulimed @sub a TIR gA whih inds ny sulfur impurities more strongly thn rseniF eny residul rseni tht remins trpped in the iron sul(de is seprted y forming the oxide @es2 y3 A y rosting the sul(de in irF he oxide is sulimed into the )ue system during rosting from where it is olleted nd redued with hrol t UHHEVHH g to give elementl rseniF emiondutor grde rseni @> WWFWWWW7A is formed y zone re(ningF
3.2.3.3 Synthesis and purication of gallium arsenide.
qllium rsenide n e prepred y the diret retion of the elementsD @QFIVAF roweverD while oneptully simple the synthesis of qes is omplited y the di'erent vpor pressures of the regents nd the highly exothermi nture of the retionF purthermoreD sine the synthesis of qes t tmospheri pressure is ompnied y its simultneous deomposes due to the loss y sulimtionD of rseniD the synthesis must e rried out under n overpressure of rseni in order to mintin stoihiometri omposition of the synthesized qesF @QFIVA sn order to overome the prolems ssoited with rseni lossD the retion is usully rried out in seled retion tueF roweverD if stoihiometri quntity of rseni is used in the retion onstnt temperture of IPQV g must e employed in order to mintin the desired rseni overpressure of I tmF rtillyD it is esier to use lrge exess of rseni heted to lower tempertureF sn this sitution the pressure in the tue is pproximtely equl to the equilirium vpor pressure of the voltile omponent @rseniA t the lower tempertureF husD n over pressure of I tm rseni my e mintined if within seled tue elementl rseni is heted to THHETPH g while the qes is mintined t IPRHEIPSH gF pigure QFS shows the seled tue on(gurtion tht is typilly used for the synthesis of qesF he tue is heted within twoEzone furneF he ots holding the retnts re usully mde of qurtzD howeverD grphite is lso used sine the ltter hs loser therml expnsion mth to the qes produtF sf higher purity is required then pyrolyti oron nitride @fxA is usedF yne of the ots is loded with pure gllium the other with rseniF e plug of qurtz wool my e pled etween the ots to t s di'userF he tue is then evuted nd seledF yne rought to the orret retion tempertures @pigure QFSAD the rseni vpor is trnsported to the glliumD nd they ret to form qes in ontrolled mnnerF le QFIH gives the typil impurity onentrtions found in polyrystlline qesF
IHH
Figure 3.5:
Schematic representation of a sealed tube synthesis of GaAs.
Element
Concentration (ppm)
Element
Concentration (ppm)
oron ron nitrogen oxygen )uorine mgnesium luminum
HFI HFU HFI HFS HFP HFHP HFHP
silion phosphorus sulfur hlorine nikel opper zin
HFHP HFI HFHI HFHV HFHR HFHI HFHS
Table 3.10
X smpurity onentrtions found in polyrystlline qesF
olyrystlline qesD formed in from the diret retion of the elements is often used s the strting mteril for single rystl growth via fridgemn or gzohrlski rystl growthF st is lso possile to prepre single rystls of qes diretly from the elements using inEsituD or diretD ompounding within highEpressure liquid enpsulted gzohrlski @rvigA tehniqueF
3.2.4 Bibliography
uF qF frloughD uF qFD in The Chemistry of the Semiconductor IndustryD idsF F tF woss nd eF vedwithD flkie nd onsD qlsgowD otlnd @IWVUAF vF hF grossmn nd tF eF fkerD Semiconductor Silicon 1977D iletrohemF oFD rinetonD xew tersey @IWUUAF wF pleisherD in Economic Geology, 50th Aniv. Vol.D he ionomi qeology ulishing gompnyD vnsterD e @IWSSAF qF rsuD xF ohtgiD nd tF rousemnD AIChE J.D IWVUD 33D UVRF F uF syD F xF plgellD nd pF F hipoloD J. Electrochem. Soc.D IWVPD 129D ISQIF tF uruskopfD tF hF weyerD fF iedemnnD wF ldshmidtD uF fethgeD qF olfD nd F hultzeD Sth gonferene on emiEinsulting sssE wterilsD wlmoD wedenD IWVVD idsF qF qrossmn nd vF vedeoD edmErilgerD xew ork @IWVVAF tF F wgormiD gonfF eF IRth siii hotovoltF peilists gonfFD n hiegoD ge @IWVHAF tF F wgormiD in Semiconductor Silicon 1981D idF rF F ru'D iletrohemil oietyD rinetonD xew tersey @IWVIAF F gF y9wrD idF Handbook of Semiconductor Silicon TechnologyD xoyes uFD xew tersey @IWWHAF
IHI
F qF fnnD Zone MeltingD tohn iley 8 onsD xew orkD @IWTTAF pF himurD Semiconductor Silicon Crystal TechnologyD edemi ress @IWVWAF
3.3 Ceramic Processing of Alumina

3.3.1 Introduction
hile luminum is the most undnt metl in the erth9s rust @ca. V7A nd luminum ompounds suh s lumD uel@y4 A2 FIP@r2 yAD were known throughout the world in nient timesD it ws not until the isoltion of luminum in the lte eighteenth entury y the hnish sientist rF gF ersted tht reserh into the hemistry of the qroup IQ elements egn in ernestF snitillyD metlli luminum ws isolted y the redution of luminum trihloride with potssium or sodiumY howeverD with the dvent of inexpensive eletri power in the lte IVHH9sD it eme eonomilly fesile to extrt the metl via the eletrolyis of lumin @el2 y3 A dissolved in ryoliteD x3 elp6 D @the rllEreroult proessAF odyD lumin is prepred y the fyer proessD in whih the minerl uxite @nmed for ves fuxD prneD where it ws (rst disoveredA is dissolved with queous hydroxidesD nd the solution is (ltered nd treted with gy2 to preipitte luminF ith vilility of oth the minerl nd hep eletri power eing the mjor onsidertions in the eonomil prodution of luminumD it is not surprising tht the leding produers of luminum re the nited ttesD tpnD eustrliD gndD nd the former oviet nionF
3.3.2 Aluminum oxides and hydroxides

he mny forms of luminum oxides nd hydroxides re linked y omplex struturl reltionshipsF fuxite hs the formul elx @yrA3-2x @H < x < IA nd is thus mixture of el2 y3 @EluminAD el@yrA3 @gisiteAD nd ely@yrA @oehmiteAF he ltter is n industrilly importnt ompound whih is used in the form of gel s preEermi in the prodution of (ers nd otingsD nd s (re retrding gent in plstisF reting oehmite nd dispore to RSH g uses dehydrtion to yield forms of lumin whih hve strutures relted to their oxideEhydroxide preursorsF husD oehmite produes the lowEtemperture form EluminD while heting dispore will give Elumin @orundumAF Elumin onverts to the hp struture t IIHH gF e third form of el2 y3 forms on the surfe of the len luminum metlF he thinD toughD trnsprent oxide lyer is the reson for muh of the usefulness of luminumF his oxide skin is rpidly selfErepiring euse its het of formtion is so lrge @r a QQSI ktGmolAF @QFIWA
3.3.2.1 Ternary and mixed-metal oxides
e further onsequene of the stility of lumin is tht most if not ll of the nturlly ourring luminum ompounds re oxidesF sndeedD mny preious gemstones re tully orundum doped with impuritiesF eplement of luminum ions with tre mounts of trnsitionEmetl ions trnsforms the formerly olorless minerl into ruy @redD gr3+ AD spphire @lueD pe2+/3+ D i4+ AD or topz @yellowD pe3+ AF he ddition of stoihiometri mounts of metl ions uses shift from the Eel2 y3 hp struture to the other ommon oxide strutures found in ntureF ixmples inlude the perovskite struture for efy3 type minerls @eFgFD geiy7 or vely3 A nd the spinel struture for ef2 y4 minerls @eFgFD erylD feel2 y4 AF eluminum oxide lso forms ternry nd mixedEmetl oxide phsesF ernry systems suh s mullite @el6 i2 y13 AD yttrium luminum grnet @eqD 3 el5 y12 AD the -lumins @eFgFD xel11 y17 A nd lumintes suh s hionite @gel12 y19 A possessing Elumin or mgnetoplumiteEtype strutures n o'er dvntges over those of the inry luminum oxidesF
3
IHP
epplitions of these mterils re found in res suh s engineering omposite mterilsD otingsD tehnil nd eletroni ermisD nd tlystsF por exmpleD mullite hs exeptionl high temperture shok resistne nd is widely used s n infrredEtrnsprent window for high temperture pplitionsD s sustrte in multilyer eletroni devie pkgingD nd in high temperture struturl pplitionsF rionite nd other hexlumintes with similr strutures re eing evluted s interfil otings for ermi mtrix omposites due to their high therml stility nd unique rystllogrphi struturesF purthermoreD luminum oxides doped with n lkliD lkline erthD rre erthD or trnsition metl re of interest for their enhned hemil nd physil properties in pplitions utilizing their unique optoeletroni propertiesF
3.3.3 Synthesis of aluminum oxide ceramics

sn ommon with the mjority of oxide ermisD two primry syntheti proesses re employed for the prodution of luminum oxide nd mixed metl oxide mterilsX IF he trditionl ermi powder proessF PF he solutionEgeltionD or 4solEgel4 proessF he environmentl impt of lumin nd luminEsed ermis is in generl negligileY howeverD the sme nnot e sid for these methods of preprtionF es prtied ommerillyD oth of the ove proesses n hve signi(nt detrimentl environmentl imptF
3.3.3.1 Traditional ceramic processing
rditionl ermi proessing involves three si steps generlly referred to s powderEproessingD shpeE formingD nd densi(tionD often with (nl mehnil (nishing stepF elthough severl steps my e energy intensiveD the most diret environmentl impt rises from the shpeEforming proess where vrious indersD solventsD nd other potentilly toxi gents re dded to form nd stilize solid @4green4A ody @le QFIIAF
Function Composition Volume (%)
owder olvent he)oulnt finder lstiizer
lumin @el2 y3 A IDIDIEtrihloroethneGethnol menhden oil poly@vinyl utyrolA poly@ethylene glyolAGotyl phthlte
PU SV IFV RFR VFV
Table 3.11
X ypil omposition of lumin green ody
he omponent hemils re mixed to slurryD stD then dried nd (redF sn ddition to ny innte helth risk ssoited with the hemil proessing these gents re susequently removed in gseous form y diret evportion or pyrolysisF he replement of hlorinted solvents suh s IDIDIEtrihloroethylene @giA must e regrded s high priority for limiting environmentl pollutionF he nited ttes invironmentl rotetion egeny @ieA inluded gi on its IWWI list of IU highEpriority toxi hemils trgeted for soure redutionF he plstiizersD indersD nd lohols used in the proess present numer of potentil environmentl impts ssoited with the relese of omustion produts during (ring of the ermisD nd the need to reyle or dishrge lohols whihD in the se of dishrge to wterwysD my exert high iologil oxygen demnds in the reeiving ommunitiesF st would e desirleD thereforeD to e le to use queous proessingY howeverD this hs previously een unsuessful due to prolems ssoited with thingD millingD nd formingF xeverthelessD with suitle hoie of indersD etFD queous proessing is possileF nfortuntelyD in mny stEprts formed y green ody proessing the liquid solvent lone onsists of over SH 7 of the initil volumeD nd while this is not diretly of n environmentl onernD the resultnt shrinkge mkes ner net shpe proessing di0ultF
IHQ
3.3.3.2 Sol-gel
heres the trditionl sintering proess is used primrily for the mnufture of dense prtsD the solutionE geltion @solEgelA proess hs een pplied industrilly primrily for the prodution of porous mterils nd otingsF olEgel involves four stge proessX dispersionD geltionD dryingD nd (ringF e stle liquid dispersion or sol of the olloidl ermi preursor is initilly formed in solvent with pproprite dditivesF fy hnging the onentrtion @gingA or prD the dispersion is 4polymerized4 to form solid dispersion or gelF he exess liquid is removed from this gel y drying nd the (nl ermi is formed y (ring the gel t higher temperturesF he ommon solEgel route to luminum oxides employs luminum hydroxide or hydroxideEsed mteril s the solid olloidD the seond phse eing wter ndGor n orgni solventD howeverD the strong intertions of the freshly preipitted lumin gels with ions from the preursor solutions mkes it di0ult to prepre these gels in pure formF o void this omplitionD lumin gels re lso prepred from the hydrolysis of luminum lkoxidesD el@yA3 F @QFPHA
@QFPIA he ext omposition of the gel in ommeril systems is ordinrily proprietryD howeverD typil omE position will inlude n luminum ompoundD minerl idD nd omplexing gent to inhiit premture preipittion of the gelD eFgFD le QFIPF
Function Composition
foehmite preursor iletrolyte gomplexing gent

Table 3.12
ef luminum sec EutoxideD el@yg4 r9 A3 rxy3 HFHU moleGmole ef glyerol caF IH wtF7
X ypil omposition of n lumin solEgel for slipst ermisF
he prinipl environmentl onsequenes rising from the solEgel proess re those ssoited with the use of strong idsD plstiizersD indersD solventsD nd sec Eutnol formed during the retionF hepending on the (ring onditionsD vrile mounts of orgni mterils suh s inders nd plstiizers my e relesed s omustion produtsF xyx 9s my lso e produed in the o'Egs from residul nitri id or nitrte sltsF woreoverD ids nd solvents must e reyled or disposed ofF inergy onsumption in the proess entils upstrem environmentl emissions ssoited with the prodution of tht energyF
3.3.4 Bibliography
Advances in CeramicsD idsF tF eF wngels nd qF vF wessingD emerin germi oietyD estvilleD yrD IWVRD olF WF edkinsD J. Am. Chem. Soc.D IWPPD 44D PIUSF eF F frronD Comm. Inorg. ChemFD IWWQD 14D IPQF wF uF giniulkD Ceram. Eng. Sci., ProcFD IWWRD 15D UPIF pF eF gotton nd qF ilkinsonD Advanced Inorganic ChemistryD Sth idFD tohn iley nd onsD xew ork @IWVVAF xF xF qreenwood nd eF irnshwD Chemistry of the ElementsD ergmon ressD yxford @IWVRAF F rF rsu nd F pF ftesD Mineral MagFD IWTRD 33D URWF
IHR
F hF uingeryD rF uF fowenD nd hF F hlmnnD Introduction to CeramicsD Pnd idF ileyD xew ork @IWUTAF rF hneiderD uF ykdD nd tF skD Mullite and Mullite CeramicsD iley @IWWRAF F F homsD Systems Analysis and Water Quality ManagementD wqrwErillD xew ork @IWUPAF tF gF illimsD in Treatise on Materials Science and TechnologyD idF pF pF F ngD edemi ressD xew ork @IWUTAF
3.4 Piezoelectric Materials Synthesis

3.4.1 Introduction
his module ws developed s prt of the ie niversity ourse griwERWTX Chemistry of Electronic MaterialsF his module ws prepred with the ssistne of slse F quzmnEtimenezF
iezoeletriity is the genertion of n eletri moment y hnge of stress pplied to solidF he word piezoeletriity literlly mens pressure eletriityY the pre(x piezo is derived from the qreek word piezeinD to pressF he piezoeletri e'et ws disovered in IVVH y the rothers tques nd ierre gurieF xot only did they demonstrte the phenomenonD ut they lso estlished the riteri for its existene in given rystlF yf the thirtyEtwo rystl lssesD twentyEone re nonEentrosymmetri @not hving entre of symmetryAD nd of theseD twenty exhiit diret piezoeletriityF he (rst prtil pplition of the piezoeletri e'et ws developed when ground qurtz rystls were pled etween the pltes of tuning pitor in order to stilize osillting iruits in rdio trnsmitters nd reeiversY howeverD the phenomenon of piezoeletriity ws not well exploited until orld r sD when vngevin used piezoeletrilly exited qurtz pltes to generte sounds wves in wter for use in sumrine detetionF iezoeletriity n lso our in polyrystlline or morphous sustnes whih hve eome nisotropi y externl gentsF yntheti piezoeletri mterils eme ville ner the end of orld r ssD with the identl disovery of the ft tht mterils like rium titnte nd rre erth oxides eome piezoeletri when they re polrized eletrillyF huring the postwr yersD when germnium nd silion were revoluE tionizing the eletronis industryD piezoermis ppered for while to e joining the revolutionD ut the limited vilility of mterils nd omponentsD mde the piezoeletri phenomenon filed to led mture pplitions during the IWSHsF st is only now tht vriety of piezoeletri mterils re eing synthesized nd optimizedF es onsequene piezoeletriEsed devies re undergoing revolutionry developmentD speilly for mediine nd erospe pplitionsF
3.4.2 Piezoelectric ceramics

wost piezoeletri trnsduers re mde up of ermi mterils for rod rnge of eletromehnil onversion tsks s trnsmittersD rnging from uzzers in lrm loks to sonrsD nd s reeiversD rnging from ultr high frequeny @rpA (lters to hydrophonesF wost of the piezoeletri mterils in usge re from the led zironte titnte @A fmilyD euse of their exellent piezoeletri prmetersD therml stilityD nd dieletri propertiesF edditionlly the properties of this fmily n e modi(ed y hnging the zironium to titnium rtio or y ddition of oth metlli nd nonEmetlli elementsF @r1-x iX y3 A ermis nd their solid solutions with severl omplex perovskite oxides hve een studiedY mong the vrious omplex oxide mterilsD niotes hve ttrted speil ttentionF ernry ermi mterilsD led metnioteD s well sD rium nd modi(ed led titntes omplete the list of piezoermi mterilsF
4
IHS eletive prmeters for piezoermi mterils re given in le QFIQD where m is the mehnil qulity ftorD c is the gurie pointD d31 is the the trnsverse hrge oe0ientD nd kp D kt nd k31 re the eletromehnil oupling ftors for plnrD thiknessD nd trnsversl mode respetivelyF
Material property PZT modied Lead metaniobate PSZNT 31/40/29 PZT, x = 0.5 PSNPLT TsTS-421 50/50 PZT, x = 0.48
m c @ gA d31 @xIH gGxA kp kt k31

-12
QSH PWH
RH RTP
PPP
UR QTW
RI ISP EUW
VVU QSS SH RTFS
HFS HFQP HFPI

Table 3.13
TH
HFRPV HFRQV HFPTQ
QHFU E IUFW
X eletive prmeters for illustrtive piezoermi mterilsF
eentlyD solEgel proessing hs een used to prepre ermisD mking possile the preprtion of mteE rils tht re di0ult to otin y onventionl methodsF fothD inorgni nd orgni preursor hve een reportedF edditionllyD new tehniques for the prodution of ermi (ers hve een developedF fetter proessing nd geometril nd miroestruturl ontrol re the min gols in the prodution of (ersF he ltest development in piezoermi (ers is the modi(tion of the visousEsuspensionEspinning proess @A for the prodution of ontinuos piezoeletri ermi (ers for smrt mterils nd tive ontrol deviesD suh s trnsduersD sensorGtutors nd struturlEontrol deviesF he utilizes onventionl synthesized ermi powders nd elluloseD s the fugitive rrierD to produe green ermi (er t resonle ostF pigure QFT shows the shemti representtion of the F
Figure 3.6:
ramic ber.
The viscous-suspension-spinning process (VSSP) for the production of continuous piezoce-
ynthesis of retive preursor powder y the oxlte opreipittion tehnique hs lso een develE opedF he preursor trnsforms to phse pure t or ove VSH g the otined y this tehnique showed gurie temperture of QSS gF he dvntges of the opreipittion tehnique re the lk of moisture sensitive nd speil hndling preursorsF
IHT
elthough new mterils hve een investigted with the purpose of rete replements for ermisD there hs een gret improvement in their properties ndD urrent reserh is foused in the development of new tehniques for oth synthesis nd proessingF
3.4.3 Piezoelectric single crystals.

he reent progress of the eletroni tehnology requires new piezoeletri rystls with high therml stility nd lrge eletromehnil oupling ftorsF ingleErystl mterils hve een onsidered s replements for polyrystlline ermisF sdelly singleErystls of led zironte titnte @A itself would e the min hoie s it is the most previling piezoeletri mterilD ut it is di0ult to grow lrge single rystlsF yn the other hndD the ft tht singleErystls o'er mny dvntges over polyrystlline systems hs een reognizedF wterils suh s lithium niote present essentilly no gingD no mehnil reep nd exellent performne in high temperture onditionsF xew piezoeletri single rystls grown y onventionl pEheting gzohrlski @gA tehnique hve een synthesizedF righ purity strting mterilsD minly oxides powdersD nd er tmosphere re reE quiredF v3 q5 iy14 D v3 x0.5 q5.5 y14 nd v3 0.5 q5.5 y14 single rystls hve een grown y using this methodF roweverD the g tehnique n e pplied only to mterils tht n e synthesized y ordinry solidEstte retion nd n undergo the pulling methodF ffe2 i2 y7 @ryliteA hs een known s mteril with strong piezoeletriityD howeverD it n not e otined y solidEstte retion nd g tehnique therefore is not pplileF es n lterntive for piezoeletri rystls growth hydrotherml synthesis hs een developedF pigure QFU shows the experimentl pprtus for the growth of ryliteF iventhoughD rystls n e otined using this tehniqueD high pressure @SHH E IHHH rA nd solvent for the rw mterils re requiredF
IHU
Figure 3.7: Experimental apparatus for the hydrothermal synthesis of barylite. H = heater, F = furnace, S = specimen vessel, G = growth capsule, P = pressure gauge, and T = thermocouples. Adapted from M. Maeda, T. Uehara, H. Sato and T. Ikeda, Jpn. J. Appl. Phys., 1991, 30, 2240.
hile the piezoermis dominte the single rystl mterils in usgeD single rystls piezoeletris ontinue to mke importnt ontriutions oth in prieEonsious onsumer mrket nd in performneE driven defense pplitionsF eres suh s frequeny stilized osilltorsD surfe ousti wve devies nd (lters with wide pss ndD re still dominted y single rystlsF
3.4.4 Piezoelectric thin lms

eentlyD there hs een gret interest in the deposition of piezoeletri thin (lmsD minly for miroeleE tronil systems @wiwA pplitionsY where the gol is to integrte sensors nd tutors sed on (lms with i semiondutorEsed signl proessingY nd for surfe ousti wve @eA deviesY where the gol is to hieve higher eletromehnil oupling oe0ient nd temperture stilityF iezoeletril mirontileversD mirotutorsD resontors nd e devies using thin (lms hve een reportedF everl methods hve een investigted for thin (lmsF sn the metlloEorgni thin (lm depositionD lkoxides re stirred during long periods of time @up to IV hoursAF efter pyrolisisD morphous (lms re formed nd then lintion etween RHH ! THH g for VH hours leds to rystlliztion @perovskit phseA y onseutive phse trnsformtion proessD whih involves trnsitionl pyrohlore phseF e hyrid metllorgni deomposition @wyhA route hs lso een developed to prepre thin (lmsF ved nd titnium ettes ndD zironium etyletonte re usedF he ferroeletri piezoeletri nd
IHV
dieletri properties indite tht the wyh route provides (lms of good qulity nd omprle to literture vluesF sn ddition to eing simpleD wyh hs severl dvntges whih inludeX homogeneity t moleulr level nd ese omposition ontrolF wetlorgni hemil vpor deposition @wyghA hs een pplied to thin (lms deposition lsoF st hs een proved tht exellent qulity (lms n e grown y using wyghD ut just reently the ontrol of mirostruture the deposition y vrying the tempertureD r to i rtio nd preursors )ow hs een studiedF eent progress in (lms deposition hs led to lower temperture growth nd it is expeted tht y lowering the deposition temperture etter eletril properties n e hievedF edditionllyD novel tehniques suh s urp eximer lser ltion ndD ion nd photoEssisted depositionsD hve lso een used for (lms synthesisF yn the other hndD single proess to deposit thin (lm y hydrotherml method hs een reported reentlyF ine the solEgel methodD sputtering nd hemil vpor deposition tehniques re useful only for mking )t mterilsD the hydrotherml method o'ers the dvntge of mking urved shped mterilsF he hydrotherml method utilizes the hemil retion etween titnium nd ions melted in solutionF e thin (lm hs een suessfully deposited diretly on titnium sustrte nd the optimum ion rtio in the solution is eing investigted to improve the piezoeletri e'etF emong the urrent reported piezoeletri mterilsD the @xi1/3 x2/3 A0.2 r0.4 i0.4 y3 @xxD PGRGRA ferroeletri ermi hs piezoeletri properties tht re out TH nd Q times lrger thn the reported vlues for ny nd F e solEgel tehnique hs een developed for the deposition of novel piezoeletri xx thin (lmF e PEmethoxyethnol sed proess is usedF sn this proess preursors re heted t lower temperture thn the oiling point of the solventD to distill o' wterF hen prior high temperture nnelingD ddition of exess preursor in the preursor solution is required to ompenste the led lossF he pure perovskite phse is then otined t THH o gD fter nnelingF hin (lms of zin oxide @nyAD piezoeletri mteril nd nEtype wideEndgp semiondutorD hve een depositedF ny (lms re urrently used in e devies nd in eletroEopti modultorsF ny thin (lms hve een grown y hemil vpor deposition nd oth dFF nd rFfF sputtering tehniquesF eentlyD optimiztion of ny (lms y rFfF mgnetron sputtering hs een developedF roweverD homogeneity is one of the min prolems when using this tehniqueD sine (lms grown y this optimized methodD showed two regions with di'erent piezoeletri propertiesF hg mgnetron sputtering is other tehnique for piezoeletri thin (lm growthD reently luminum nitrideD promising mteril for use in thinE(lm ulk ousti wve resontors for pplitions in p ndpss (ltersD hs een grown y this methodF he est qulity (lms re otined on i sustrtesF sn order to hieve the highest resontor ouplingD the elx must e grown diretly on the eletrodesF he min prolem in the elx growth is the oxygen ontmintionD whih leds to the formtion of ntive oxide on the el surfeD preventing rystlline growth of elxF
3.4.5 Piezoelectric polymers

he disovery of piezoeletriity in polymeri mterils suh s polyvinylidene di)uoride @pAD ws onE sidered s n indition of renissne in piezoeletriityF sntensive reserh ws foused in the synthesis nd funtionliztion of polymersF e potentil piezoeletri polymer hs to ontin high onentrtion of dipoles nd lso e mehnilly strong nd (lmEformingF he degree of rystllinity nd the morphology of the rystlline mteril hve profound e'ets on the mehnil ehvior of polymersF edditionllyD in order to indue piezoeletri response in morphous systems the polymer is poled y pplition of strong eletri (eld t elevted temperture su0ient to llow moility of the moleulr dipoles in the polymerF eent pprohes hve een foused in the development of ynoEontining polymersD due to the ft tht yno polymers ould hve mny dipoles whih n e ligned in the sme diretionF hse trnsfer tlyzed retion hs een used for piezoeletri polymer preprtion from mlonitrileD however this method leds to low moleulr weightD nd low yield of impure vinylidene ynide units onE tining mterilF he use of solid u2 gy3 nd etonitrile without dded phse trnsfer tlyst shows exellent yields for polyester possessing kone gemEdinitriles nd for polymide synthesisF he polyester
IHW nd polymide otined ontined dinitrile group net dipole whih n e lign in the sme diretion s the ronyl groupsF he pursuit for etter piezoeletri polymers hs led to moleulr modeling whih indites tht one yno sustituent should e lmost s e'etive s two geminl yno sustituentsD opening new re of potentil mterils hving n rylonitrile group s the si uilding lokF roweverD polyrilonitrile itself is not suitle euse it forms helixF hus rylonitrile opolymers hve een investigtedF wost of the piezoeletri polymers ville re still synthesized y onventionl methods suh s polyE ondenstion nd rdil polymeriztionF herefore piezoeletri polymer synthesis hs the sme prolems s the ommeril polymer preprtionD suh s ontrolling the degree of polymeriztion nd rystllinityF e novel tehnique of vpor deposition polymeriztion hs een reported s n lterntive method to opolymeri thin (lmsF eliphti polyure W ws synthesized y evporting monomers of IDWEdiminononno nd IDWEdiisoyntononno onto glss sustrte in vuumF heposition rtes were improved t temperE tures elow H o gF efter poling tretment (lms showed firly lrge piezoeletri tivitiesF edditionllyD ompletely novel pproh to piezoeletri polymers hs een presentedF his pprohD onsists in the synE thesis of ordered piezoeletri polymer networks vi rosslinking of liquidErystlline monomersF he min gol in this pproh is to hieve polymer network whih omines the long term stility of piezoeletri singleErystls with the ese of proessility nd frition of onventionl polymersF pigure QFV shows the shemti representtion of this pprohF
Figure 3.8: Scheme of a ordered piezoelectric networks via a liquid-crystalline monomer strategy. Adapted from D. L. Gin and B. C. Baxter, Polymer Preprints, 1996, 38, 211.
iezoeletri polymers re eoming inresingly importnt ommerilly euse of their esier proessE ilityD lower ostD nd higher impt resistne thn ermisD ut the lk of high temperture stility nd the sene of solid understnding of the moleulr level sis for the eletril properties re limittionsF he requirements for strong piezoeletriity in polymer reX the polymer hin hs lrger resultnt dipole moment norml to the hin xisY polymer rystllizes into polr rystl with the polr xis perpendiulr to the hin xisD hs high rystllinity nd (nlly the polymer polr xis ligns esily in the thikness diretion during polingF
3.4.6 Piezoelectric composites

iezoomposites hve een otined y the omintion of piezoeletri ermis nd polymersD the resulting mteril posses oth the high piezoeletri properties of ermis nd the proessility of polymersF IEQ type piezoomposites hve found wide pplitions s medil nd industril ultrsoni trnsduersF he urrent method for piezoomposite prodution is the dieEndE(ll tehniqueD whih onsists in utting two sets of grooves in lok of piezoermi t right ngles eh otherD then polymer is st into these grooves nd the solid ermi se is ground o'F olishing nd poling re the following steps in order to hieve the (nl thikness nd propertiesF his method is expensiveD time onsuming nd size limitedF
IIH
es n lterntive for the dieEndE(ll tehniqueD ontinuos green (ers otined y the modi(ed visousE suspensionEspinning proessD n e undled into ottonllElike shpeD then urned nd sinteredF he sintered undle impregnted with epoxy resin n e slied into diss nd then polrizedF eent results hve yielded IEQ type omposites with exellent piezoeletri propertiesF yn the other hndD n innovtive proess hs een developed for r2 @x0.5 0.5 A2 y7 Ghp ompositesD in this new frition methodD pproprite mounts of oxides re mixedD pressed nd sinteredF he porous resulting mteril is susequently in(ltrted with hp solution nd then poledF his new method for omposites preprtion is simple nd o'ers ledEfree lterntive smrt mterilF enother kind of piezoomposites n e hieved y spinning (lms of piezoermi onto metl lloysD suh s ixiF he resulting mterils is hyrid omposite tht n utilize the di'erent tive nd dptive properties of the individul ulk mterilsF hue to the shpe memory nture of ixiD possile pplition for this new heterostrutures ould e smrt tive dmping of mehnil virtionsF hg sputtering nd spin oting re the tehniques neessry for the smrt thin (lm ixiGpiezoeletri heterostrutures fritionF roweverD eventhough the (lms hd (ne grin struture nd high mehnil qulitiesD the ferroeletri properties were poor ompred to literture vluesF sn the futureD the properties of piezoomposites will e tiloredD y vrying the ermiD the polymer nd their reltive proportionsF edjustments in the mteril properties will led to ful(llment of the requireE ments for prtiulr devieF le QFIR shows omprison mong piezoeletri ermisD polymers nd omposites prmeters where is the impedneD t 33 is the dieletril onstntD nd is the densityF
Material parameter Piezoceramics Piezopolymers Piezocomposites
kt @7A @IH ylsA

6
RS E SS PH E QH PHH E SHHH
PH E QH IFS E R
TH E US R E PH SH E PSHH
33
G0
IH
IFS E S S E IH IEP
tn @7A m
<I
IH E IHHH
3
<I
P E SH PES
@IH kgGm A
Table 3.14
SFS E V
X rmeter rnges for piezoeletri ermisD polymers nd ompositesF
3.4.7 Piezoelectric coatings.

wny potentil pplitions exist whih require (lm thikness of I to QH mF ome exmples of these mroE sopi devies inlude ultrsoni high frequeny trnsduersD (er opti modultors nd for self ontrolled virtionl dmping systemsF ny nd hve een used for piezoeletri (er opti phse modultors fritionF he piezoeletri mterils hve een sputter deposited using d mgnetron soure nd multimgnetron sputtering systemsF gotings of T m thik of ny nd HFS m of re possile to hieve using these systemsF roweverD thikness vrition of pproximtely IS7 ours etween the enter nd the end of ny otingsD results on 'eted modultion performneF elthough otings hieved y sputtering posses uniformity nd do not exhiit rkingD the is only prtilly rystllized nd it is tully omposite struture onsisting of rystlline nd morphous mterilD diminishing the piezoeletri propertiesF olEgel tehnique for thik (lms hve een developedF st is now possile to frite solEgel (lms of up to TH mF he eletril nd piezoeletril properties of the thik (lms reported re omprle with ermi F iezoeletri polymer otings for highEfrequeny (erEopti modultors hve een lso investigtedF gommeril vinylidene )uoride nd tetr)uoroethylene opolymer hs een usedF he dvntge of using
III polymer otings is tht the polymer jket @otingA n e esily otined y melt extrusion on singleE mode (erF husD uniformity is esily hieved nd surfe roughness is not presentF purthermoreD if nneling of the polymer is mde prior polingD high degree of rystllinity is enhnedD leding to etter piezoeletri propertiesF
3.4.8 Bibliography

F xF uleimnD Mat. Res. Soc. Symp. Proc.D IWWTD 406D PPIF F mmotoD Jpn. J. Appl. Phys.D IWWTD 35D SIHRF F mshitD F rosonoD nd xF shinoseD Jpn. J. Appl. Phys.D IWWUD 36D IIRIF sF ekimov nd qF uF vhukD Inorg. Mater.D IWWUD 33D TQVF vF hel ylmo nd wF vF glzdD J. Non-Cryst. SolidsD IWWHD 121D RPRF F xishiD uF sgrshiD F himizuD uF uoumotoD nd rF ngidD J. Mater. Sci. Lett.D IWVWD 8D VHSF uF F wF oD eF F F oD nd F uomrneniD Mater. Lett.D IWWTD 28D RTQF uF himmurD rF kedD F uohnoD nd F pukudD J. Cryst. GrowthD IWWTD 163D QVVF rF kedD uF himmurD F uohnoD nd F pukudD J. Cryst. GrowthD IWWTD 169D SHQF veeD F stoh nd F ugD Thin Solid FilmsD IWWUD 299D VVF vF tF wthisD hF eF rrishD nd F tedmnD PolymerD IWWRD 35D TSWF qF F poxD xF etterD nd rFqF vimergerD J. Mater. Res.D IWWTD 11D PHSIF vF qin nd fF gF fxterD Polymer PreprintsD IWWTD 38D PIIF
IIP
Chapter 4
Wafer Formation and Processing

4.1 Formation of Silicon and Gallium Arsenide Wafers
4.1.1 Introduction
sntegrted iruits @sgsA nd disrete solid stte devies re mnuftured on semiondutor wfersF ilion sed devies re mde on silion wfersD while sssE @IQEISA semiondutor devies re generlly frited on qes wfersD howeverD for ertin optoeletroni pplitions sn wfers re lso usedF he eletril nd hemil properties of the wfer surfe must e well ontrolled nd therefore the preprtion of strting wfers is ruil portion of sg nd devie mnufturingF sn order to otin high frition yields nd good devie performneD it is very importnt tht the strting wfers e of reproduily high qulityF por exmpleD the front surfe must e smooth nd )t on oth mroE nd mirosleD euse highEresolution ptterns @lithogrphyA re optilly formed on the wferF sn prinipleD utting rystl into thin slies nd polishing one side until ll sw mrks re removed nd the surfe ppers smooth nd glossy ould produe suitle wferF roweverD due in prt to the rittleness of i nd qes rystlsD s well s the inresing requirements of wfer lenliness nd surfe defet redution with ever deresing devie geometriesD very omplex series of proessing steps re required to produe nlytilly lenD )t nd dmgeEfree wfer surfesF he following fouses on the generl priniples nd methods with regrd to wfer formtionF hetiled forE mulsD reipesD nd spei( proess prmeters re not given s they vry onsiderly mong di'erent wfer produersF roweverD in generlD tehniques for frition of i wfers hve generlly eome stndrdized within the semiondutor industryF sn ontrstD qes wfer tehnology is less stndrdizedD possily due to either @A the similrity to silion prties or @A the lower prodution volume of qes wfersF here re two generl lsses of proesses in the methodology of mking wfersX mehnil nd hemilF es oth i nd qes re rittle mterilsD the mehnil proesses for their wfer frition re similrF roweverD the di'erent hemistry of i nd qes require tht the hemil proesses e delt with seprtelyF
1
4.1.2 Wafer formation procedures

ih of the proessing steps in the onversion of semiondutor ingot @formed y gzohrlski or fridgemn growthA into polished wfer redy for devie fritionD results in the removl of mteril from the originl ingotY etween 1 G3 nd 1 G2 of the originl ingot is sri(ed during proessingF wethods for the removl of mteril from rystl ingot re lssi(ed depending on the size of the prtiles eing removed during the proessF sf the removed prtiles re muh lrger thn tomi or moleulr dimensions the proess is desried s eing mroEsleF gonverselyD if the mteril is removed tomEyEtom or moleuleEyEmoleule then the proess is termed miroEsleF e further distintion etween vrious types of proesses is whether
1
IIQ
IIR
CHAPTER 4. WAFER FORMATION AND PROCESSING
the removl ours s result of mehnil or hemil proessesF he formtion of (nished wfer from semiondutor ingot normlly requires six mhining @mehnilA opertionsD two hemil opertionsD nd t lest one polishing @hemilEmehnilA opertionF edditionllyD multiple inspetion nd evlution steps re inluded in the overll proessF e summry of the individul stepsD nd their funtionsD involved in wfer prodution is shown in le RFIF
Process Type Function
ropping grinding orienttion )tting ething wfering het tretment edge ontouring lpping ething polishing lening
Table 4.1
mehnil mehnil mehnil hemil mehnil therml mehnil mehnil hemil mehnoEhemil hemil
removl of onil shped ends nd impure portions otin preise dimeter identi(tion of rystl orienttion nd dopnt type removl of surfe dmge formtion of individul wfers y utting nnihiltion of undesirle eletroni donors provide rdius on the edge of the wfer provides requisite )tness of the wfer removl of surfe dmge provides smooth @speulrA surfe removl of orgnisD hevy metlsD nd prtiultes
X ummry of the proess steps involved in semiondutor wfer produtionF
4.1.3 Crystal shaping

elthough n sEgrown rystl ingot is of high purity @WWFWWWW7A nd rystllinityD it does not hve the su0iently preise shpe required for redy wfer formtionF husD prior to sliing n ingot into individul wfersD severl steps re neededF hese opertions required to prepre the rystl for sliing re referred to s rystl shpingD nd re shown in pigure RFIF
Schematic representation of crystal shaping operations: (a) remove crown and taper, (b) grind to required diameter, (c) grind at, and (d) slice sample for measurements. Shaded area represents material removed.
Figure 4.1:
IIS
4.1.3.1 Cropping
he sEgrown ingots hve onil shped seed @topA nd tng @ottomA ends tht re removed using irulr dimond sw for ese of further mnipultion of the ingot @pigure RFIAF he uttings re su0iently pure tht they re lened nd the reyled in the rystl growth opertionF ortions of the ingot tht fil to meet spei(tions of resistivity re lso removedF sn the se of silion ingots these setions my e sold s metllurgilEgrde silion @wqAF gonverselyD portions of the rystl tht meet desired resistivity spei(tions my e preferentilly seletedF e smple slie is lso ut to enle oxygen nd ron ontent to e determinedY usully this is omplished y pourier trnsform infrred spetrosopi mesurements @pEsAF pinllyD ropping is used to ut rystls to suitle length to (t the sw pityF
4.1.3.2 Grinding
he primry purpose of rystl grinding is to otin wfers of preise dimeter euse the utomti dimeter ontrol systems on rystl growth equipment re not ple of meeting the tight wfer dimeter spei(tionsF sn dditionD rystls re seldom grown perfetly round in ross setionF husD ingots re usully grown with I E P mm llowne nd redued to the proper dimeter y grinding pigure RFIF grystl grinding is strightforwrd proess using n rsive grinding wheelD howeverD it must e well ontrolled in order to void prolems in susequent opertionsF ixit hipping in wfering nd lttie slip in therml proessing re prolems often resulting from improper rystl grindingF wo methods re used for rystl grindingX @A grinding on enter nd @A enterless grindingF pigure RFP shows shemti of the generl setEup for grinding rystl ingot on enterF he rystl is supported t eh end in ltheElike mhineF he rotting utting toolD employing wterEsed oolntD mkes multiple psses down the rotting ingot until the requisite dimeter is otinedF he enter grinder n lso e used for grinding the identi(tion )ts s well s providing uniform ingot dimeterF roweverD grinding the rystl on enters requires tht the opertor lote the rystl xis in order to otin the est yieldF
Figure 4.2:
Schematic representation of grinding on center.
genterless grinding elimintes the prolems ssoited with loting the rystl enterF he enterless method is superior for long rystlsY howeverD enterless grinder is muh lrger thn enter grinder of the
IIT
sme dimeter pityF sn enterless grinding the ingot is supported etween two wheelsD grinding wheel nd drive wheelF e shemti of the enterless grinder is shown in pigure RFQF he xis of the drive wheel is nted with respet to tht of the rystl ingot nd the grinding wheel pushing the rystl ingot pst the sttionry @ut rottingA grinding wheelD see pigure RFQF
Figure 4.3: Schematic representation of centerless grinding viewed (a) along and (b) perpendicular to the crystal axis.
4.1.3.3 Orientation/identication ats
pollowing grinding of the ingot to the desired dimeterD one or two )ts re ground long the length of the ingotF he identi(tion )ts @one or twoA re ground lengthwise long the rystl ording to the orienttion nd the dopnt typeF efter grinding the rystl on enters the rystl is rotted to the proper orienttionD then the wheel is positioned with its xis of rottion perpendiulr to the rystl xis nd moved long the rystl from end to end until the pproprite )t size is otinedF en optil or Ery orienttion (xture my e used in onjuntion with the rystl mounting to filitte the proper orienttion of the rystl on the grinderF he lrgest )t is lled the primry )t @pigure RFIA nd is prllel to one of the rystl plnesD s determined y Ery di'rtionF he primry )t is used for utomted positioning of the wfer during suE sequent proessing stepsD eFgFD lithogrphi ptterning nd diingF yther smller )ts re lled 4seondry )ts4 nd re used to identify the rystl orienttion @<III> versus <IHH>A nd the mteril @nEtype versus pEtypeAF eondry )ts provide quik nd esy mnner y whih unknown wfers n e sortedF he )ts shown shemtilly in pigure RFR re loted ording to emiondutor iquipment nd wterils snstitute @iws A stndrd nd re ground to spei( widthsD depending upon rystls dimeterF xothes re lso used in ple of the seondry )tY howeverD the reltive orienttions of the noth nd primry )t with regrd to rystl orienttion nd dopnt re mintinedF
IIU
Figure 4.4:
SEMI locations for orientation/identication ats.
4.1.3.4 Etching
he ropping nd grinding proesses re performed with reltively orse rsive nd onsequently gret del of susurfe dmge resultsF itsD hipsD nd rks ll ontriute to stress in the ut wfer nd provide nulei for rk propgtion t the edges of the (nished wferF sf regions of stress re removed then rks will no longer propgteD reduing exit hipping nd wfer rekge during susequent frition stepsF he generl method for removing surfe dmge is to eth the rystl in hot solutionF he most ommon ethnts for i re sed on the rxy3 Erp systemD in whih ethnt modi(ers suh s eti id lso ommonly usedF sn the se of qes rglErxy3 is the pproprite systemF hese ethnts seletively ttk the rystl t the dmged regionsF efter ethingD the rystl is trnsferred to the sliing preprtion reF
4.1.4 Wafering
he purpose of wfering is to sw the rystl into thin slies with preise geometri dimensionsF fy frD the most ommon method of wfering semiondutor rystls is the use of n nnulrD or inner dimeter @shAD dimond sw ldeF e shemti digrm of sh sliing tehnology is shown in pigure RFSF
IIV
Figure 4.5:
Schematic diagrams of ID slicing process.
he rystlD when it rrives t the swing reD hs een ground to dimeterD )ttedD nd ethedF sn order to slie itD the rystl must e (rmly mounted in suh wy tht it n e ompletely onverted to wfers with minimum wsteF he rystl is tthed with wx or epoxy to mounting lokD whih is usully ylindril in shpe nd of the sme dimeter s the ingotF elsoD mounting em @or stripA is tthed long the length of the rystl t the rekout point of the sw ldeF his redues exit hipping @rekge tht ours s the lde exits the rystl t the end of utA nd lso provides support for the swn wfer until it is retrievedF qrphite or phenoli resins re ommon mterils for the mounting lok nd emsD lthough some suess hs een otined in mounting ingots using hydruli pressureF he sw lde is thin sheet of stinless steel @QPS mAD with dimond onded to its inner edgeF his lde is mounted on drum tht rottes t caF PHHH rpmF w ldes SV m @PQ inhesA in dimeter with PH m @V inhesA opening re ommonD howeverD s wfer sizes inrese lrger ldes re employedX QH m @IP inhesA wfers re now ommon for iF he lde moves reltive to the sttionry rystl t speed of HFHS mGsD nd the utting proess is wterEooledF husD onsidering tht wfers re slied sequentilly @one t timeAD the overll proess is very slowF e further prolem is tht the kerf loss @loss due to the width of the ldeA results in pproximtely IGQ of the mteril eing lost s sw dustF pinllyD the depth of the drum onto whih the lde is tthed limits the length of the ingot setion tht is essileF sn order to overome this prolemD nother style of sh lde sw ws developed in whih the lde is mounted on n ir ering nd is rotted y elt driveF his llows the entire length of the rystl ingot to e sliedF foth silion nd qes rystls re grown with either the rystllogrphi <IHH> or <III> diretion prllel to the ylindril xis of the rystlF fers my e ut either extly perpendiulr to the rysE tllogrphi xis or deliertely o'Exis y severl degreesF sn order to otin the proper wfer orienttionD the rystl must e properly oriented on the swF ell prodution sliing mhines hve djustments for orienttion of the rystlY howeverD it is usully neessry to hek the orienttion of the (rst slie in order to ssure tht ll susequent slies will e properly orientedF yvious vriles introdued during the wfering proess inludeX utting rteD wheel speedD nd oolnt )ow rteF roweverD the ondition of the mhinesD suh s lignment nd virtionD is the most importnt vrile followed y the ondition of the ldeF e devited lde rim my use tperD owD or wrpF le RFP summrizes the types of deformtions tht n our during wferingD their physil pperne nd their hrteristisF
IIW
Type warp of bow and Surface appearance Lattice curvature Comments
)t urved urved )t urved
)t )t urved urved )t
idel
slips
Table 4.2
X heformed wfers nd their hrteristisF
4.1.5 Heat treatment

esEprodued gzohrlski grown rystls often hve level of oxygen impurity tht my exeed the onenE trtion of dopnt in the semiondutor mteril @iFeFD i or qesAF his oxygen impurity hs deleterious e'et on the semiondutor propertiesD espeilly upon susequent therml proessingD eFgFD therml oxide growth or epitxil (lm growth y metl orgni hemil vpor deposition @wyghAF por exmpleD when silion rystls re heted to out RSH g the oxygen undergoes trnsformtion tht uses it to ehve s n eletron donorD muh like n nEtype dopntF hese oxygen donorsD or 4therml donors4D msk the true resistivity of the semiondutor euse they either dd dditionl rrier eletrons to nEtype rystl or ompenste for the positive holes in pEtype rystlF portuntelyD these therml donors n e 4nnihilted4 y het treting the mterils rie)y in the rnge of SHH E VHH g nd then ooling quikly through the RSH g region efore donors n reformF sn priniple therml donor nnihiltion n e performed on wfers t ny time during their fritionY howeverD it is usully est to perform the het tretment immeditely fter wfering sine suEstndrd wfers my e rejeted efore dditionl proessing steps re undertken nd thus limiting dditionl ostF honor nnihiltion is ulk e'etD nd therefore the therml tretment n e performed in irD sine ny surfe oxide tht my form will e removed in susequent lpping nd polishing stepsF
4.1.6 Lapping or grinding

he sEut wfers vry su0iently in thikness to require n dditionl opertionD the sliing opertion does not onsistently produe the required )tness nd prllelism required for mny wfer spei(tionsD see le RFPF ine onventionl polishing does not orret vritions in )tness or thiknessD mehnil twoEsided lpping opertion is performedF vpping is ple of hieving very preise thikness uniformityD )tness nd prllelismF vpping lso prepres the surfe for polishing y removing the suEsurfe swing dmgeD repling it with more uniform nd smller lpping dmgeF he proess used for lpping semiondutor wfers evolved from the optil lens mnufturing industry using priniples developed over severl hundred yersF roweverD s the lens hs urved surfe nd the wfers re )tD the equipment for lpping wfers is mehnilly simpler thn lens proessing mhinesF he simplest douleEside lpping mhine onsists of two very )t ounterErotting pltesD rriers to hold nd move the wfers etween the pltesD nd devie to feed rsive slurry stedily etween the pltesF he rsive is typilly W m el2 y3 gritF gommeril rsives re suspended in wter or glyerin with proprietry dditives to ssist in suspension nd dispersion of the prtilesD to improve the )ow properties
IPH
of the slurryD nd to prevent orrosion of the lpping mhineF rydrulis or n ir ylinder pplies lpping pressure with low strting pressure for P to S minutesD whih is then inresed through most of the proessF he ompletion of lpping my e determined y elpsed time or y n externl thikness sensing devieF he (nished proess gives wfer with surfe uniform to within P mF epproximtely PH m per side is removed during the lpping proessF elthough lpping would pper to e simple in oneptD the suessful implementtion of prodution lpping opertion requires the development of tehnique nd experiene to hieve eptle qulity with good yieldsF mll djustments to the rottion rtes of the pltes nd rriers will use the pltes to wer onveD onvex or )tF es lpping is messy proessD vrious e'orts hve een mde to void it or to sustitute n lterntive proessF he most likely pproh t present is grindingD in whih the wfer is held on vuum huk nd series of progressively (ner dimond wheels is moved over the wfer while it is rotted on turn tleF qrinding gives lerer surfe thn lppingD howeverD only one side my e ground t time nd the resulting )tness is not s good s tht otined y lppingF
4.1.7 Edge contouring

he rounding of the edge of the wfer to spei( ontour is firly reent development in the tehnology of wfer preprtionF st ws known y the erly seventies tht signi(nt numer of devie yield prolems ould e tred to the physil ondition of the wfer edgeF en ute edge 'ets the strength of the wfer due toX stress onentrtionD nd lowering of its resistne to therml stressD s well s eing the soure of prtile hipD rekgeD nd lttie dmgeF sn dditionD the prtiles originting from the hipped edges nD if present on the wfer surfeD dd to the defet density @h0 A of the sg proess reduing frition yieldF purther prolems ssoited with squre edge inlude the uildEup of photoresist t the wfer edgeF he solution to these proess prolems is to provide ontoured edge with de(ned rdius @rAF ghemil ething of wfers results in degree of edge roundingD ut it is di0ult to ontrolF husD mehnil edge ontouring hs een developed nd the result hs een drmti improvement in yields in downstrem wfer proessingF vosses due to wfer rekge re lso reduedF he edge ontouring proess is usully performed in ssetteEfed high speed equipmentD in whih eh wfer is rotted rpidly ginst shped utting tool @pigure RFTAF
Figure 4.6:
Schematic illustration of edge contouring.
4.1.8 Etching
he mehnil proesses desried ove to shpe the wfer leve the surfe nd edges dmged nd ontmintedF he depth of the work dmge depends on the spei( proessD howeverD IH m is typilF
IPI uh dmge is redily removed y hemil ethingF ithing is used t multiple points during the frition of semiondutor devieF he disussion elow is limited to ethes suitle for wfer fritionD iFeFD nonE seletive ething of the entire wfer surfeF
4.1.8.1 Wet chemical etching
he wet hemil ething of ny mteril n e onsidered to involve three stepsX @A trnsporttion of the retnts to the surfeD @A retion t the surfeD nd @A movement of the retion produts into the ethnt solution @pigure RFUAF ih of these my e the rte limiting step nd thus ontrol the eth rte nd uniformityF his e'et is summrized in le RFQF
Figure 4.7: Schematic representation of the three steps involved in wet chemical etching: (i) diusion of the chemical etch reagents through the boundary layer, (ii) chemical reaction at the surface, and (iii) diusion of the reaction products into the etch solution through the boundary layer.
Rate limiting step
Etching rate
Results
Comments
hi'usion of regent to the surfe etion t semionE dutor surfe hi'usion produts surfe of retion from the
slow fst slow
ething@nisotropiA polishing@isotropiA polishing@isotropiA
enhned surfe roughE ness idel retion produt mins on surfe reE
Table 4.3
X i'ets of rte limiting step in semiondutor ethingF
en ethnt tht is limited y the rte of retion t the surfe will tend to enhne ny surfe fetures nd promote surfe roughness due to preferentil ething t defets @nisotropiAF sn ontrstD if the eth rte is limited y the di'usion of the ethnt regent through stgnnt @dedA oundry lyer ner the surfeD then the eth will result in uniform polishing nd the surfe will eome smooth @isotropiAF sf removl of the retion produts is rte limiting then the eth rte will e slow euse the eth equilirium will e shifted towrds the retntsF sn the se of n individul ethnt retionD the rte determining step my e hnged y rpid stirring to id removl of retion produtsD or y inresing the temperture of the eth solutionD see pigure RFVF he ext ething onditions re hosen depending on the pplitionF por exmpleD dilute high temperture ethes re often employed where the eth dmge must e minimizedD while ooled ethes n e used where preise eth ontrol is requiredF
IPP
Figure 4.8:
Typical etch rate versus temperature plot for a mixture of HF (20%), (45%) and (35%).
rditionlly mixtures of hydro)uori id @rpAD nitri id @rxy3 A nd eti id @wegy2 rA hve een used for silionD ut lkline ethes using potssium hydroxide @uyrA or sodium hydroxide @xyrA solutions re inresingly ommonF imilrlyD gllium rsenide ethes my e either idi or siD howeverD in oth ses the ethes re oxidtive due to the use of hydrogen peroxideF e wide rnge of hemil regents re ommerilly ville in 4trnsistor grde4 purity nd these re employed to minimize ontmintion of the semiondutorF heionized wter is ommonly used s diluent for eh of these regents nd the onentrtion of ommonly used queous regents is given in le RFRF
Reagent Weight % Reagent Weight %
rgl r2 y4 rxy3 wegy2 r xr4 yr

Table 4.4
QU WV UW WW PW
rp r3 y4 rgly4 r2 y2
RW VS UH QH
X eight perent onentrtion of ommonly used onentrted queous regentsF
he equipment used for typil ethnt proess inludes n id @or lklineA resistnt tnkD whih ontins the ethnt solution nd one or more positions for rinsing the wfers with deionized wterF he proess is th in nture involving tens of wfers nd the est equipment provides mens of rotting the wfers during the eth step to mintin uniformityF sn order to ssure the removl of ll surfe dmgeD sustntil overEething is performedF husD the removl of PH m from eh side of the wfer is typilF ith times re usully severl minutes per thF
4.1.8.2 Etching silicon
he most ommonly used ethnts for silion re mixtures of hydro)uori id @rpA nd nitri id @rxy3 A in wter or eti id @wegy2 rAF he ething involves redutionEoxidtion @redoxA retionD followed y
IPQ dissolution of the retion produtsF sn the rpErxy3 system the rxy3 oxidizes the silion nd the rp removes the retion produts from the surfeF he overll retion isX @RFIA he oxidtion retion involves the oxidtion of i0 to i4+ D nd it is utoEtlyti in tht the retion produt promotes the retion itselfF he initil step involves tre impurities of rxy2 in the rxy3 solution @@RFPAAD whih ret to lierte nitrogen dioxide @xy2 AD @RFQAF @RFPA
@RFQA he nitrogen dioxide oxidizes the silion surfe in the presene of wterD resulting in the formtion of i@yrA2 nd the reformtion of rxy2 @@RFRAAF he i@yrA2 deomposes to give iy2 @@RFSAAF ine the retion etween rxy2 nd rxy3 @@RFPAA is rte limitingD n indution period is oservedF roweverD this is overome y the ddition of xy2 - ions in the form of xr4 xy2 F @RFRA
@RFSA he (nl step of the eth proess is the dissolution of the iy2 y rp @@RFTAAF tirring serves to remove the solule produts from the retion surfeF he role of the rp is to t s omplexing regentD nd thus the retion shown in @RFTA is known s omplexing retionF he formtion of wter s retion produt requires tht eti id e used s diluent @solventA to ensure etter ontrolF @RFTA he ething retion is highly dependent on the reltive rtios of the ethnt regentsF husD if n rpErih solution is usedD the retion is limited y the oxidtion step @@RFRAA nd the ething is nisotropiD sine the oxidtion retion is sensitive to dopingD rystl orienttionD nd defetsF sn ontrstD the use of rxy3 Erih solution produes isotropi ething sine the dissolution proess is rte limiting @le RFQAF he retion of rxy3 Erih solutions hs een found to e di'usionEontrolled over the temperture rnge PH E SH g @pigure RFVAD nd is therefore ommonly employed for removing work dmge produed during wfer fritionF he oundry lyer thikness @pigure RFUA nd therefore the dimensionl ontrol over the wfer is ontrolled y the rottion rte of the wfersF e ommon eth formultion is RXIXQ mixture of rxy3 @UW7AD rp @RW7AD nd wegy2 r @WW7AF here re some ethnt formultions tht re sed on lterntive @or dditionlA oxidizing gentsD suh sX fr2 D s2 D nd uwny4 F elkline ething @uyrGr2 y or xyrGr2 yA is y nture nisotropi nd the eth rte depends on the numer of dngling onds whih in turn re dependent on the surfe orienttionF ine ething is retion rte limited no rottion of the wfers is neessry nd exellent uniformity over lrge wfers is otinedF elkline ethnts re used with lrge wfers where dimensionl uniformity is not mintined during lppingF e typil formultion uses uyr in RS7 weight solution in r2 y t WH gF
4.1.8.3 Etching gallium arsenide
elthough wide rnge of ethes hve een investigted for qesD few re truly isotropiF his is euse the surfe tivity of the @IIIA q nd @IIIA es fes re very di'erentF he es rih fe is onsiderly
IPR
more retive thn the q rih feD thus under identil onditions it will eth fsterF es result most ethes give polished surfe on the es feD ut the q fe tends to pper loudy or frosted due to the highlighting of surfe fetures nd rystllogrphi defetsF es with silion the eth systems involve oxidtion nd omplextionF roweverD in the se of qes the gllium is lredy fully oxidized @formlly q3+ AD thusD it is the rseni @formlly the rsenide ionD es3- tht is oxidized y suitle oxidizing gent @eFgFD r2 y2 A to the solule oxideD es2 y3 @@RFUAAF he gllium ions form the oxide q2 y3 vi the hydroxide @@RFVAAF foth oxides re solule in id solutionsD resulting in their removl from the surfeF @RFUA
@RFVA he peroxide sed oxidtive ethes for qes re divided into idi nd si ethesF he omposition nd pplition of some of these systems re summrized in le RFSF he most widely used of these is r2 y4 Gr2 y2 Gr2 y nd is referred to s gro9s idF he high visosity of r2 y4 results in di'usionE limited ething with high id onentrtionsF ithes with low id onentrtions tend to e nisotropiF hosphori id @r3 y4 A or itri id @pigure RFWA my e exhnged for sulfuri id @r2 y4 AF eplement of the id omponent with ses suh s xr4 yr or xyr n result in ner to truly isotropi ethntsD lthough ertin omintions n result in strong nisotropyF
Formulation Volume ratio (100) etch rate (m/min) (110) etch rate (m/min) (111)As etch rate (m/min) (111)Ga etch rate (m/min)
r2 y4 G r2 y2 G r2 y r2 y4 G r2 y2 G r2 y r2 y4 G r2 y2 G r2 y itri idG r2 y2 G r2 y xr4 yrG r2 y2 G r2 y xyrG r2 y2 G r2 y
VXIXI IXVXI QXIXSH IXIXI IXUHH IXHFUT
IFS VFH HFV HFT HFQ HFP
IFS VFH HFV HFT HFQ HFP
IFS IPFH HFV HFT HFQ HFP
HFV QFH HFR HFR HFQ HFP
Table 4.5
X he omposition nd pplition of seleted eth systems for qesF
IPS
Figure 4.9:
Structure of citric acid.
yne of the erliest ething systems for qes is sed on the use of dilute @F HFHS volF7A solution of romine @fr2 A in ethnolF he fr2 ts s the oxidntD resulting in the formtion of solule romidesF he eth rte of this system is di'erent for di'erent rystllogrphi plnesD iFeFD the eth rtes for the @IIIA esD @IHHAD nd @IIIA q fes re in the rtio TXSXID lthough more uniform eth rtes re oserved with high fr2 onentrtions @F IH volF7AF hese higher onentrtion solutions re used for the removl of dmge due to utting with the swF
4.1.9 Polishing
he purpose of polishing is to produe smoothD speulr surfe on whih devie fetures n e de(ned y lithogrphyF sn order to llow for very lrge sle integrtion @vsA or ultr lrge sle integrtion @vsA frition the wfer must hve surfe with high degree of )tnessF ritions less thn S to IH m ross the wfer dimeter re typil )tness spei(tionsF sn dditionD given the preeding stepsD wfer polishing must not leve residul ontmintion or surfe dmgeF he tehniques of wfer polishing re derived from the glss lens industryD with some importnt modi(tions tht hve een developed to meet the speil requirements of the miroeletronis industryF
4.1.9.1 Dierences between polishing and lapping
sf the surfe of wfer tht hs undergone lpping @or grindingA is exmined with n eletron mirosopeD rksD ridges nd vlleys re oservedF he top 4relief lyer4 onsists of peks nd vlleysF felow this lyer is dmged lyer hrterized y mirorksD dislotionsD slip nd stressF pigure RFIH shows shemti representtion of the rded surfeF foth of these lyers must e removed ompletely prior to further fritionF heresing the prtile size of the rsive during lpping only dereses the sle of the dmgeD ut does not eliminte it entirelyF sn ft this surfe dmge is hrteristi of the rittle frture of single rystl i nd qesD nd ours euse during lpping the rsive grins re moved ross the surfe under pressure eyond tht of the frture strength of the wfer mterils @i or qesAF sn ontrst to the mehnil rsion employed in lppingD polishing is mehnoEhemil proess during whih rittle frture does not ourF e polished wfer does not disply ny evidene of relief surfe suh s tht produed y lppingD even t highest resolution eletron mirosopeF
IPT
Figure 4.10:
polishing.
Schematic representation of a cross sectional view of an abraded wafer surface prior to
4.1.9.2 Process of Polishing
idIQQTPSQH shows shemti of the polishing proessF olishing my e onduted on single wfers or s th proess depending on the equipment employedF ingle wfer polishing is preferred for lrger wfers nd llows for etter surfe )tnessF sn oth proessesD wfers re mounted onto (xtureD y either wx or omposite pelxEwountD nd pressed ginst the polishing pdF he polishing pd is usully mde from n rti(il fri suh s polyester feltEpolyurethne lminteF olishing is omplished y mehnoE hemil proess in whih queous polishing slurry is dripped onto the polishing pdD see idIQQTPSQHF he polishing slurry performs oth hemil nd mehnil proessD nd onsists of (ne sili @iy2 A prtiles @IHH dimeterA nd n oxidizing gentF equeous sodium hydroxide @xyrA is used for iD while queous sodium hlorte @xyglA is preferred for qesF uspending gents re usully dded to prevent settling of the sili prtilesF nder the het used y the frition of the wfer on the polishing pd the wfer surfe is oxidizedD whih is the hemil stepD while in the mehnil step the sili prtiles in the slurry rde the oxidized surfe wyF
Figure 4.11:
Schematic representation of the wafer polishing process.
sn order to hieve resonle rte of removl of the relief nd dmged lyers nd still otin the highest qulity surfeD the polishing is done in two stepsD stok removl nd hze removlF he former is
IPU rried out with higher onentrtion slurry nd my proeed for out QH minutes t removl rte of I mGminF rze removl is performed with very dilute slurryD softer pd with retion time of out S to IH minutesD during whih the totl mount of mteril removed is only out I mF hue to the tive hemil retion etween the wfer nd the polishing gentD the wfers must e rinsed in deionized wter immeditely fter polishing to prevent hze or stins from reformingF here re mny vriles tht will in)uene the rte nd qulity of polishingF righ pressure results in higher polishing rteD ut exessive pressure my use nonEuniform polishingD exessive het genertion nd fst pd werF he rte of polishing is inresed with higher tempertures ut this my lso led to hze formtionF righ wheel speeds elerte the polishing rte ut n rise the temperture nd lso results in prolems in mintining uniform )ow of slurry ross the pdF hense slurry onentrtions inrese the polishing rte ut re more ostlyF he pr of the slurry solution n lso 'et the polishing rteD for exmple the polishing rte of i grdully inreses with inresed pr @higher siityA until pr of out IP where drmti derese is oservedF sn generlD the optimum polishing proess for given fility depends lrgely upon the interply of produt spei(tionD yieldsD ostD nd qulity onsidertions nd must e developed uniquelyF he wfer polishing proess does not improve the wfer )tness ndD t estD polishing will not degrde the wfer )tness hieved in the lpping opertionF
4.1.10 Cleaning
huring the proesses desried oveD semiondutor wfers re sujeted to physil hndling tht leds to signi(nt ontmintionF ossile soures of physil ontmintion inludeX F irorne teriD F grese nd wx from utting oils nd physil hndlingD F rsive prtiultes @usullyD siliD silion rideD luminD or dimond dustA from lppingD grinding or swing opertionsD dF plstiizers whih re derived from ontiners nd wrpping in whih the wfers re hndled nd shippedF ghemil ontmintion my lso our s result of improper lening fter eth stepsF vightEmetl @espeE illy sodium nd potssiumA speies my e tred to impurities in ethnt solutions nd re hemisored on to the surfe where they re prtiulrly prolemtil for metl oxide semiondutor @wyA sed deviesD lthough higher levels of suh impurities re tolerle for ipolr deviesF revy metl impurities @eFgFD guD euD peD nd egA re usully used y eletrodeposition from ethnt solutions during fritionF hile wfers re lened prior to shippingD ontmintion umulted during shipping nd storge neessittes tht ll wfers e sujeted to srupulous lening prior to fritionF purthermoreD lening is required t eh step during the frition proessF elthough wfer lening is vitl prt of eh frition stepD it is onvenient to disuss lening within the generl topi of wfer fritionF
4.1.10.1 Cleaning silicon
he (rst step in lening i wfer is removl of ll physil ontminntsF hese ontmintes re removed y rinsing the wfer in hot orgni solvents suh s IDIDIEtrihloroethne @gl3 gr3 A or xylene @g6 r4 we2 AD ompnied y mehnil sruingD ultrsoni gittionD or ompressed gs jetsF emovl of the mE jority of light metl ontminnts is omplished y rinsing in hot deionized wterD howeverD omplete removl requires further more ggressive lening proessF he most widely used lening method in the i semiondutor industry is sed on two stepD two solution sequene known s the ge glening wethodF he (rst solution onsists of r2 yEr2 y2 Exr4 yr in volume rtio of SXIXI to UXPXID whih is used to remove orgni ontminnts nd hevy metlsF he oxidtion of the remining orgni ontminnts y the hydrogen peroxide @r2 y2 A produes wter solule produtsF imilrlyD metl ontminnts suh s dmiumD oltD opperD meruryD nikelD nd silver re soluilized y the xr4 yr through the formtion
IPV of solule mino omplexesD eFgFD @RFWAF
@RFWA he seond solution onsists of r2 yEr2 y2 Ergl in TXIXI to VXPXI volume rtio nd removes the qroup s@IAD ss@PA nd sss@IQA metlsF sn dditionD the seond solution prevents reEdeposition of the metl ontminntsF ih of the wshing steps is rried out for IH E PH minF t US E VS g with rpid gittionF pinllyD the wfers re lown dry under strem of nitrogen gsF
4.1.10.2 Cleaning GaAs
sn priniple qes wfers my e lened in similr mnner to silion wfersF he (rst step involves suessive lening with hot orgni solvents suh s IDIDIEtrihloroethneD etoneD nd methnolD eh for SEIH minutesF qes wfers lened in this mnner my e stored under methnol for short periods of timeF wost lening solutions for qes re tully ethesF e typil solution is similr to the seond ge solution nd onsists of n VHXIHXI rtio of r2 yEr2 y2 ErglF his solution is generlly used t elevted tempertures @UH gA with short dip times sine it hs very fst eth rte @RFH mGminAF
4.1.11 Measurements, inspections and packaging

ulity ontrol mesurements of the semiondutor rystl nd susequent wfer re performed throughout the proess s n essentil prt of the frition of wfersF prom rystl nd wfer shping through the (nl wfer (nishing stepsD qulity ontrol mesurements re used to ensure tht the mterils meets ustomer spei(tionsD nd tht prolems n e orreted efore they rete srp mteril nd thus void further proessing of rejet mterilF ulity ontrol mesurements n e rodly lssi(ed into mehnilD eletrilD struturlD nd hemilF wehnil mesurements re onerned with the physil dimensions of the wferD inludingX thiknessD )tnessD owD tper nd edge ontourF iletril mesurements usully inludeX resistivity nd lterl resistivity grdientD rrier type nd lifetimeF wesurements giving informtion on the perfetion of the semiondutor rystl lttie re lssi(ed in the struturl tegory nd inludeX testing for stking fultsD nd dislotionsF outine hemil mesurements re limited to the mesurement of dissolved oxygen nd ron y pourier trnsform infrred spetrosopy @pEsAF pinished wfers re individully mrked for the purpose of identi(tion nd treilityF kging helps protet the (nished wfers from ontmintion during shipping nd storgeF sndustry stndrds de(ning in detil how qulity ontrol mesurements re to e mde nd determining the eptle rnges for mesured vlues hve een developed y the emerin oiety of esting wterils @ewA nd the emiondutor iquipment nd wterils snstitute @iwsAF
4.1.12 Bibliography
eF gF fonorD Silicon Wafer Process Technology: Slicing, Etching, PolishingD emiondutor ilion IWUUD iletrohemF oFD enningtonD xt @IWUUAF vF hF hyerD in Proceeding of the low-cost solar array wafering workshop 1981D hoiEtvEPIHIPETTD tet ropulsion vFD sden ge @IWVPAF tF gF hyment nd qF eF ozgonyiD J. Electrochem. Soc.D IWUID 118D IQRTF rF qerisher nd F windtD Electrochem. ActaD IWTVD 13D IQPWF F hF qreenD Solid State Electron.D IWUTD 19D VISF gF eF rrper nd F wF ompsonD Electronic Materials & Processing HandbookD wqrw rillD xew orkD Pnd iditionF F sid nd uF stoD J. Electrochem. Soc.D IWUID 118D UTVF F uernD J. Electrochem. Soc.D IWWHD 137D IVVUF F wori nd xF tneD J. Electrochem. Soc.D IWUVD 125D ISIHF
IPW
hF vF rtinD eF qF wilnesD nd vF pF ssmilletD J. Electrochem. Soc.D IWUWD 126D ISVIF hF F hwD J. Electrochem. Soc.D IWTTD 113D WSVF pF nimurD Semiconductor Silicon Crystal TechnologyD edemi ressD xew ork @IWVWAF hF F urnerD J. Electrochem. Soc.D IWTHD 107D VIHF
4.2 Doping
trting with prepredD polished wfer then how do we get n integrted iruitc e will fous on the gwy proessD desried in the lst hpterF vet9s ssume we hve wfer whih ws doped during growth so tht it hs kground onentrtion of eptors in it @iFeF it is pEtypeAF eferring k to gwy vogi3 D you n see tht the (rst thing we need to uild is nEtnk or motF sn order to do thisD we need some wy in whih to introdue dditionl impurities into the semiondutorF here re severl wys to do thisD ut urrent tehnology relies lmost exlusively on tehnique lled ion implantationF e digrm of n ionEimplnter is shown in the (gure in the previous setion4 F en ion implnter uses dopnt soure gsD ionizes itD nd drives the ions into the wferF he dopnt gs is ionized nd the resultnt hrged ions re elerted through mgneti (eldD where they re mssEnlyzedF he vertil mgneti (eld uses the em of ions to spred outD ording to their mssF e thin perture selets the ions of interestD nd lets them pssD loking ll the othersF his mkes sure we re only implnting the ion we wntD nd in ftD even selets for the proper isotope3 he ionized toms re then elerted through severl tens to hundreds of kD nd then de)eted y n eletri (eldD muh like in n osillosope gF sn ftD most of the time the ion em is 4rstered4 ross the surfe of the silion wferF he ions strike the silion wfer nd pss into its interiorF e mesurement of the urrent )ow in the system nd its integrlD is mesure of how muh dopnt ws deposited into the wferF his is usully given in terms of the numer of dopnt atoms to whih cm2 the wfer hs een exposedF efter the toms enter the silionD they intert with the lttieD reting defetsD nd slowing down until (nlly they stopF ypil tomi distriutionsD s funtion of implnt voltge re show in pigure RFIP for implnttion into morphous silionF hen implnttion is done on single rystl mterilD hnnelingD the improved moility of n ion down the 4hllwy4 of given lttie diretionD n skew the impurity distriution signi(ntlyF tust slight hnges of less thn degree n mke ig di'erenes in how the impurity toms re (nlly distriuted in the wferF sullyD the opertor of the implnt mhine purposely tilts the wfer few degrees o' norml to the em in order to rrive t more reproduile resultsF
Figure 4.12:
Implant distribution with acceleration energy
This content is available online at <http://cnx.org/content/m11364/1.2/>. "CMOS Logic", Figure 3 <http://cnx.org/content/m11359/latest/#g46> 4 "Silicon Growth", Figure 1 <http://cnx.org/content/m11363/latest/#g05>
2 3
IQH
es you might expetD shooting IHH k ions t silion wfer proly does quite it of dmge to the rystl strutureF xot only thtD ut just hvingD sy oronD in your wfer does not men you re going to hve holesF por the oron to eome 4eletrilly tive4 E tht is to t s n eptor E it hs to reside on silion lttie siteF iven if the oron tom doesD somehowD end up on n tul lttie site when it stops rshing round in the wferD the mny defets whih hve een reted will t s deep trpsF husD the hole whih is formed will proly e ught t trp site nd will not e le to ontriute to eletril ondutivity in the wfer nywyF row n we (x this situtionc sf we refully het up the wferD we n use the toms in the rystl to shke roundD nd if we do it rightD they ll get k where they elongF xot only thtD ut the newly dded impurities end up on lttie sites s well3 his step is lled annealing nd it does just wht it is supposed toF ypil tempertures nd times for suh n nnel re SHH to IHHH g for IH to QH minutesF omething else ours during the nnel step howeverF e hve just ddedD y our implnttion stepD impurities with firly tight distriution s shown in pigure RFIPF here is n ovious grdient in impurity distriutionD nd if there is grdientD thn things my strt moving round y di'usionD espeilly t elevted temperturesF
4.3 Applications for Silica Thin Films

4.3.1 Introduction
hile the physil properties of sili mke it suitle for use in protetive nd optil oting pplitionsD the iggest pplition of insulting iy2 thin (lms is undoutedly in semiondutor deviesD in whih the insultor performs numer of spei( tsksD inludingX surfe pssivtionD (eld e'et trnsistor @piA gte lyerD isoltion lyersD plnriztion nd pkgingF he term insultor generlly refers to mteril tht exhiits low therml or eletril ondutivityY eletrilly insulting mterils re lso lled dieletrisF st is in regrd to the high resistne to the )ow of n eletri urrent tht iy2 thin (lms re of the gretest ommeril importneF he dieletri onstnt @A is mesure of dieletri mterils ility to store hrgeD nd is hrterized y the eletrostti energy stored per unit volume ross unit potentil grdientF he mgnitude of is n indition of the degree of polriztion or hrge displement within mterilF he dieletri onstnt for ir is ID nd for ioni solids is generlly in the rnge of S E IHF hieletri onstnts re de(ned s the rtio of the mteril9s pitne to tht of irD iFeFD @RFIHAF he dieletri onstnt for silion dioxide rnges from QFW to RFWD for thermlly nd plsm gh grown (lmsD respetivelyF @RFIHA en insulting lyer is (lm or deposited lyer of dieletri mteril seprting or overing ondutive lyersF sdellyD in these pplition n insulting mteril should hve surfe resistivity of greter thn IH13 Gm2 or volume resistivity of greter thn IH11 FmF roweverD for some pplitionsD lower vlues re eptleY n eletril insultor is generlly epted to hve resistivity greter thn IH5 FmF gh iy2 thin (lms hve resistivity of IH6 E IH16 FmD depending on the (lm growth methodF es onsequene of its dieletri properties iy2 D nd relted silisD re used for isolting onduting lyersD to filitte the di'usion of dopnts from doped oxidesD s di'usion nd ion implnttion msksD pping doped (lms to prevent loss of dopntD for gettering impuritiesD for protetion ginst moisture nd oxidtionD nd for eletroni pssivtionF yf the mny methods used for the deposition of thin (lmsD hemil vpor deposition @ghA is most often used for semiondutor proessingF sn order to ppreite the unique prolems ssoited with the gh of insulting iy2 thin (lms it is worth (rst reviewing some of their pplitionsF ummrized elow re three res of gretest importne to the frition of ontemporry semiondutor deviesX isoltion nd gte insultionD pssivtionD nd plnriztionF
5
IQI
4.3.2 Device isolation and gate insulation

e miroiruit my e desried s olletion of devies eh onsisting of 4n ssemly of tive nd pssive omponentsD interonneted within monolithi lok of semionduting mteril4F ih devie is required to e isolted from djent devies in order to llow for mximum e0ieny of the overll iruitF purthermore within devieD ontts must lso e eletrilly isoltedF hile there re numer of methods for isolting individul devies within iruit @reverseEised juntionsD mes isoltionD use of semiEinsulting sustrtesD nd oxide isoltionAD the isoltion of the tive omponents in single devie is lmost exlusively omplished y the deposition of n insultorF sn pigure RFIQ is shown shemti representtion of silion wypi @metlEoxideEsemiondutor (eld e'et trnsistorAF he wypi is the si omponent of silionEgwy @omplimentry metlEoxideE semiondutorA iruits whihD in turnD form the sis for logi iruitsD suh s those used in the g @entrl proessing unitA of modern personl omputerF st n e seen tht the wypi is isolted from djent devies y reverseEised juntion @p+ Ehnnel stopA nd thik oxide lyerF he gteD soure nd drin ontt re eletrilly isolted from eh other y thin insulting oxideF e similr sheme is used for the isoltion of the olletor from oth the se nd the emitter in ipolr trnsistor deviesF
Figure 4.13:
Schematic diagrams of a Si-MOSFET (metal-oxide-semiconductor eld eect transistor).
es trnsistorD wypi hs mny dvntges over lternte designsF he key dvntge is low power dissiption resulting from the high impedne of the devieF his is result of the thin insultion lyer etween the hnnel @region etween soure nd drinA nd the gte onttD see pigure RFIQF he presene of n insulting gte is hrteristi of generl lss of devies lled wspis @metlEinsultorE semiondutor (eld e'et trnsistorAF wypis re suset of wspis where the insultor is spei(lly n oxideD eFgFD in the se of silion wspi devie the insultor is iy2 D hene wypiF st is the frition of wypi iruits tht hs llowed silion tehnology to dominte digitl eletronis @logi iruitsAF roweverD inreses in omputing power nd speed require onstnt redution in devie size nd inresed omplexity in devie rhitetureF
4.3.3 Passivation
ssivtion is often de(ned s proess wherey (lm is grown on the surfe of semiondutor to either @A hemilly protet it from the environmentD or @A provide eletroni stiliztion of the surfeF
IQP
prom the erliest dys of solid stte eletronis it hs een reognized tht the presene or sene of surfe sttes plys deisive role in the usefulness of ny semionduting mterilF yn the surfe of ny solid stte mteril there re sites in whih the oordintion environment of the toms is inompleteF hese sitesD ommonly termed 4dngling onds4D re the use of the eletronilly tive sttes whih llow for the reomintion of holes nd eletronsF his reomintion ours t energies elow the ulk vlueD nd interferes with the inherent properties of the semiondutorF sn order to optimize the properties of semiondutor devie it is desirle to ovlently stisfy ll these surfe ondsD therey shifting the surfe sttes out of the nd gp nd into the vlene or ondution ndsF iletroni pssivtion my therefore e desried s proess whih redues the density of ville eletroni sttes present t the surfe of semiondutorD therey limiting hole nd eletron reomintion possiilitiesF sn the se of silion oth the ntive oxide nd other oxides dmirly ful(ll these requirementsF ghemil pssivtion requires mteril tht inhiits the di'usion of oxygenD wterD or other speies to the surfe of the underlying semiondutorF sn dditionD the mteril is idelly hrd nd resistnt to hemil ttkF e perfet pssivtion mteril would stisfy oth eletroni nd hemil pssivtion requirementsF
4.3.4 Planarization
por the vst mjority of eletroni deviesD the strting point is sustrte onsisting of )t single rystl wfer of semionduting mterilF huring proessingD whih inludes the growth of oth insulting nd onduting (lmsD the surfe eomes inresingly nonEplnrF por exmpleD gte oxide in typil wypi @see pigure RFIQA my e typilly IHH E PSH thikD while the isoltion or (eld oxide my e IHDHHH F sn order for the suessful susequent deposition of onduting lyers @metlliztionA to our without reking metl lines @often due to the di0ulty in mintining step overgeAD the surfe must e )t nd smoothF his proess is lled plnriztionD nd n e rried out y tehnique known s sri(il ethkF he steps for this proess re outlined in pigure RFIRF en rupt step @pigure RFIRA is oted with onforml lyer of low melting dieletriD eFgFD orophosphorosilite glssD fq @pigure RFIRAD nd susequently sri(il orgni resin @pigure RFIRAF he smple is then plsm ethed suh tht the resin nd dieletri re removed t the sme rteF ine the plsm eth follows the ontour of the orgni resinD smooth surfe is left ehind @pigure RFIRdAF he plnriztion proess thus redues step height di'erentils signi(ntlyF sn ddition regions or vlleys etween individul metlliztion elements @visA n e ompletely (lled llowing for route to produing uniformly )t surfesD eFgFD the fq (lm shown in pigure RFIQF
IQQ
Schematic representation of the planarization process. A metallization feature (a) is CVD covered with silicate glass (b), and subsequently coated with an organic resin (c). After etching the resist a smooth silicate surface is produced (d).
Figure 4.14:
he proesses of plnriztion is vitl for the development of multilevel strutures in vs iruitsF o minimize interonnetion resistne nd onserve hip reD multilevel metlliztion shemes re eing developed in whih the interonnets run in QEdimensionsF
4.3.5 Bibliography
tF vF ossen nd F uernD Phys. TodayD IWVHD 33D PTF F uF qhndhiD VLSI Fabrication Principles, Silicon and Gallium ArsenideD ileyD ghihesterD Pnd idF @IWWRAF F wF zeD Physics of Semiconductor DevicesD Pnd iditionD tohn iley 8 onsD xew ork @IWVIAF F iF fedleD tF gF gF siD F hF lummerD Quick Reference Manual for Silicon Integrated Cuircuit TechnologyD ileyD ghihester @IWVSAF eF gF edms nd gF hF gpioD J. Electrochem. Soc.D IWVID 128D PTQHF
IQR

6
4.4 Oxidation of Silicon

note:
Electronic MaterialsF his module ws prepred with the ssistne of endre ueysF
his module ws developed s prt of the ie niversity ourse griwERWTX Chemistry of
4.4.1 Introduction
sn the frition of integrted iruits @sgsAD the oxidtion of silion is essentilD nd the prodution of superior sgs requires n understnding of the oxidtion proess nd the ility to form oxides of high qulityF ilion dioxide hs severl usesX IF PF QF RF SF erves s msk ginst implnt or di'usion of dopnt into silionF rovides surfe pssivtionF ssoltes one devie from nother @dieletri isoltionAF ets s omponent in wy struturesF rovides eletril isoltion of multiElevel metlliztion systemsF
wethods for forming oxide lyers on silion hve een developedD inluding therml oxidtionD wet nodizE tionD hemil vpor deposition @ghAD nd plsm nodiztion or oxidtionF qenerllyD gh is used when putting the oxide lyer on top of metl surfeD nd therml oxidtion is used when lowEhrge density level is required for the interfe etween the oxide nd the silion surfeF
4.4.2 Oxidation of silicon

ilion9s surfe hs high 0nity for oxygen nd thus n oxide lyer rpidly forms upon exposure to the tmosphereF he hemil retions whih desrie this formtion reX @RFIIA
@RFIPA sn the (rst retion dry proess is utilized involving oxygen gs s the oxygen soure nd the seond retion desries wet proess whih uses stemF he dry proess provides 4good4 silion dioxide ut is slow nd mostly used t the eginning of proessingF he wet proedure is prolemti in tht the purity of the wter used nnot e gurnteed to suitle degreeF his prolem n e esily solved using pyrogeni tehnique whih omines hydrogen nd oxygen gses to form wter vpor of very high purityF wintining regents of high qulity is essentil to the mnufturing of integrted iruitsD nd is onern whih plgues eh step of this proessF he formtion of the oxide lyer involves shred vlene eletrons etween silion nd oxygenD whih llows the silion surfe to rid itself of 4dngling4 ondsD suh s lone pirs nd vnt oritlsD pigure RFISF hese vnies rete midEgp sttes etween the vlene nd ondution ndsD whih prevents the desired nd gp of the semiondutorF he iEy ond strength is ovlent @strongAD nd so n e used to hieve the loss of midEgp sttes nd pssivte the surfe of the silionF
6
IQS
Figure 4.15:
Removal of dangling bonds by oxidation of surface.
he oxidtion of silion ours t the silionEoxide interfe nd onsists of four stepsX tep IF hi'usive trnsport of oxygen ross the di'usion lyer in the vpor phse djent to the silion oxideEvpor interfeF tep PF snorportion of oxygen t the outer surfe into the silion oxide (lmF tep QF hi'usive trnsport ross the silion oxide (lm to its interfe with the silion lttieF tep RF etion of oxygen with silion t this inner interfeF es the iEiy2 interfe moves into the silion its volume expndsD nd sed upon the densities nd moleulr weights of i nd iy2 D HFRR i is used to otin IFH iy2 F
4.4.2.1 Pre-oxidation cleaning
he (rst step in oxidizing surfe of silion is the removl of the ntive oxide whih forms due to exposure to open irF his my seem redundnt to remove n oxide only to put on notherD ut this is neessry sine unertinty exists s to the purity of the oxide whih is presentF he ontmintion of the ntive oxide y oth orgni nd inorgni mterils @rising from previous proessing steps nd hndlingA must e removed to prevent the degrdtion of the essentil eletril hrteristis of the devieF e ommon proedure uses r2 yEr2 y2 Exr4 yr mixture whih removes the orgnis presentD s well s some group s nd ss metlsF emovl of hevy metls n e hieved using r2 yEr2 y2 Ergl mixtureD whih omplexes with the ions whih re formedF efter removl of the ntive oxideD the desired oxide n e grownF his growth is useful euse it providesX hemil protetionD onditions suitle for lithogrphyD nd pssivtionF he protetion prevents unwnted retions from ourring nd the pssivtion (lls vnies of onds on the surfe not present within the interior of the rystlF hus the oxidtion of the surfe of silion ful(lls severl funtions in one stepF
4.4.2.2 Thermal oxidation
he growth of oxides on silion surfe n e prtiulrly tedious proessD sine the growth must e uniform nd pureF he thikness wnted usully flls in the rnge SH E SHH D whih n tke long time nd must e done on lrge sleF his is done y stking the silion wfers in horizontl qurtz tue while the oxygen soure )ows over the wfersD whih re situted vertilly in slotted pddle @otAD see pigure RFITF his proedure is performed t I tm pressureD nd the temperture rnges from UHH to IPHH gD eing held to within I g to ensure uniformityF he hoie of oxidtion tehnique depends on the thikness nd oxide properties requiredF yxides tht re reltively thin nd those tht require low hrge t the interfe re typilly grown in dry oxygenF hen thik oxides re required @> HFS mmA re desiredD stem is the soure of hoieF tem n e used t wide rnge of pressures @I tm to PS tmAD nd the higher pressures llow thik oxide growth to e hieved t moderte tempertures in resonle mounts of timeF
IQT
Figure 4.16:
Horizontal diusion tube showing the oxidation of silicon wafers at 1 atm pressure.
he thikness of iy2 lyers on i sustrte is redily determined y the olor of the (lmF le RFT provides guidline for therml grown oxidesF
Film thickness (m) Color Film thickness (m) Color
HFHS HFHU HFIH HFIP HFIS HFIU HFPH HFPP HFPS HFPU HFQH HFQI HFQP
tn rown drk violet to redEviolet royl lue light lue to metlli lue metlli to light yellowE green light gold gold ornge to melon redEviolet lue to violet lue lue lue to lueEgreen
HFTQ HFTV HFUP HFUU HFVH HFVP HFVS HFVT HFVU HFVW HFWP HFWS HFWU
violetEred 4luish4 lueEgreen to gree 4yellowish4 ornge slmon light redEviolet violet lue violet lue lueEgreen yellowEgreen yellow
IQU HFQR HFQS HFQT HFQU HFQW HFRI HFRP HFRR HFRT HFRU HFRV HFRW HFSH HFSP HFSR HFST HFSU HFSV HFTH
Table 4.6
light green green to yellowEgreen yellowEgreen greenEyellow yellow light ornge rntion pink violetEred redEviolet violet lueEviolet lue lue green green yellowEgreen greenEyellow 4yellowish4 light ornge to pink rntion pink
HFWW IFHH IFHP IFHS IFHT IFHU IFIH IFII IFIP IFIV IFIW IFPI IFPR IFPS IFPV IFQP IFRH IFRT IFSH
ornge rntion pink violet red redEviolet violet lueEviolet green yellowEgreen green violet redEviolet violetEred rntion slmon ornge 4yellowish4 sky lue to greenElue ornge lueEviolet lue pink to
X golor hrt for thermlly grown iy2 (lms oserved under dylight )uoresent lightingF
4.4.2.3 High pressure oxidation
righ pressure oxidtion is nother method of oxidizing the silion surfe whih ontrols the rte of oxidtionF his is possile euse the rte is proportionl to the onentrtion of the oxideD whih in turn is proportionl to the prtil pressure of the oxidizing speiesD ording to renry9s lwD @RFIQAD where g is the equilirium onentrtion of the oxideD r is renry9s lw onstntD nd pO is the prtil pressure of the oxidizing speiesF @RFIQA his pproh is fstD with rte of oxidtion rnging from IHH to IHHH mmGhD nd lso ours t reltively low tempertureF st is useful proessD preventing dopnts from eing displed nd lso forms low numer of defetsD whih is most useful t the end of proessingF
4.4.2.4 Plasma oxidation
lsm oxidtion nd nodiztion of silion is redily omplished y the use of tivted oxygen s the oxidizing speiesF he highly retive oxygen is formed within n eletril dishrge or plsmF he oxidtion is rried out in low pressure @HFHS E HFS orrA hmerD nd the the plsm is produed either y hg eletron soure or highEfrequeny dishrgeF sn simple plsm oxidtion the smple @iFeFD the silion wferA is held t ground potentilF sn ontrstD niodiztion systems usully hve hg is etween the smple nd n eletrode with the smple ised positively with respet to the thodeF ltinum eletrodes re ommonly used s the thodesF
IQV
here hve een t lest QR di'erent retions reported to our in n oxygen plsmD howeverD the vst mjority of these re inonsequentil with respet to the formtion of tive speiesF purthermoreD mny of the potentilly tive speies re su0iently short lived tht it is unlikely tht they mke signi(nt ontriutionF he primry tive speies within the oxygen plsm re undoutedly y- nd y2+ F foth eing produed in ner equl quntitiesD lthough only the former is relevnt to plsm niodiztionF hile these speies my e tive with respet to surfe oxidtionD it is more likely tht n eletron trnsfer ours from the semiondutor surfe yields tivted oxygen speiesD whih re the tul retnts in the oxidtion of the silionF he signi(nt dvtge of plsm proesses is tht while the eletron temperture of the ionized oxygen gs is in exess of IHDHHH uD the therml tempertures required re signi(ntly lower thn required for the high pressure methodD iFeFD < THH gF he dvntges of the lower retion tempertures inludeX the minimiztion of dopnt di'usion nd the impediment of the genertion of defetsF hespite these dvntges there re two primry disdvntges of ny plsm sed proessF pirstD the high eletri (elds present during the proesses use dmge to the resultnt oxideD in prtiulrD high density of interfe trps often resultF roweverD post nneling my improve (lm qulityF eondD the growth rtes of plsm oxidtion re lowD typilly IHHH GhF his growth rte is inresed y out ftor of IH for plsm niodiztionD nd further improvements re oserved if I E Q7 hlorine is dded to the oxygen soureF
4.4.2.5 Masking
e seletive msk ginst the di'usion of dopnt toms t high tempertures n e found in silion dioxide lyerD whih n prove to e very useful in integrted iruit proessingF e predeposition of dopnt y ion implnttionD hemil di'usionD or spinEon tehniques typilly results in dopnt soure t or ner the surfe of the oxideF huring the initil highEtemperture stepD di'usion in the oxide must e slow enough with respet to di'usion in the silion tht the dopnts do not di'use through the oxide in the msked region nd reh the silion surfeF he required thikness my e determined y experimentlly mesuringD t prtiulr temperture nd timeD the oxide thikness neessry to prevent the inversion of lightly doped silion sustrte of opposite ondutivityF o this is then dded sfety ftorD with typil totl vlues rnging from HFS to HFU mmF he impurity msking properties result when the oxide is prtilly onverted into sili impurity oxide 4glss4 phseD nd prevents the impurities from rehing the iy2 Ei interfeF
4.4.3 Bibliography
wF wF etllD in Properties of Elemental and Compound SemiconductorsD idF rF qtosD sntersieneX xew ork @IWTHAF F uF qhndhiD VLSI Fabrication Principles, Silicon and Gallium ArsenideD ileyD ghihesterD Pnd idF @IWWRAF F wF zeD Physics of Semiconductor Devices D Pnd iditionD tohn iley 8 onsD xew ork @IWVIAF hF vF vileD Solid State Electron.D IWUVD 21D IIWWF F iF pierD F F ghyeD F F kethD nd gF F uD sF vinduD J. Vac. Sci. Technol.D IWUWD 16D IRPPF F F ro nd F ugnoD IEEE Trans. Electron DevicesD IWVHD ED-27D IRQTF tF F rollnhn nd eF F fellsD Techniques and Applications of Plasma ChemistryD ileyD xew ork @IWURAF F F rF ghng nd eF uF inhD Appl. Phys. LettFD IWUTD 29D STF
4.5 Photolithography
note:
7
his module is sed upon the gonnexions module entitled Photolithography y fill ilsonF
IQW etullyD implnts @espeilly for motsA re usully done t su0iently high energy so tht the dopnt @phosphorusA is lredy pretty fr into the sustrte @often severl mirons or soAD even efore the di'usion strtsF he nnelGdi'usion moves the impurities into the wfer it moreD nd s we shll see lso mkes the nEregion grow lrgerF 4he nEregion43 e hve not sid thing out how we mke our mot in only ertin res of the wferF prom the desription we hve so frD is seems we hve simply uilt n nEtype lyer over the whole surfe of the wferF his would e d3 e need to ome up with some kind of 4window4 to only permit the implnting impurities to enter the silion wfer where we wnt them nd not elsewhereF e will do this y onstruting n implnttion 4rrier4F o do thisD the (rst thing we do is grow lyer of silion dioxide over the entire surfe of the wferF e tlked out oxide growth when we were disussing wypis ut let9s go into little more detilF ou n grow oxide in either dry oxygen tmosphereD or in n tmosphere whih ontins wter vporD or stemF sn pigure RFIUD we show oxide thikness s funtion of time for growth with stemF hry y2 does not ehve too muh di'erentlyD the rte is just somewht slowerF
Figure 4.17:
A plot of oxide thickness as a function of time.
yn top of the oxideD we re now going to deposit yet nother mterilF his is silion nitrideD i3 x4 or just plin 4nitride4 s it is usully lledF ilion nitride is deposited through method lled hemil vpor deposition or 4gh4F he usul tehnique is to ret dihlorosilne nd mmoni in hot wlled low pressure hemil vpor deposition system @vghAF he retion isX @RFIRA ilion nitride is good rrier for impuritiesD oxygen nd other things whih do not wnt to get into the wferF ke look t pigure RFIV nd see wht we hve so frF e word out sle nd dimensionsF he silion wfer is out PSH m thik @out HFHI4A sine it hs to e strong enough not to rek s it is eing hndledF he two deposited lyers re eh out I m thikD so they should tully e drwn s lines thinner thn the other lines in the (gureF his would oviously mke the whole ide of sketh ridiulousD so we will leve things distorted s they reD keeping in mind tht the deposited nd di'used lyers re tully muh thinner thn the rest of wferD whih relly does not do nything exept support the tive iruits up on topF
IRH
Figure 4.18:
Initial wafer conguration.
xow wht we wnt to do is remove prt of the nitrideD so we n mke our nEwellD ut not put in phosE phorous where do not wnt itF e do this with proesses lled photolithography nd etching respetivelyF pirst thing we do is ot the wfer with yet nother lyer of mterilF his is liquid lled photoresist nd it is pplied through proess lled spinEotingF he wfer is put on vuum hukD nd lyer of liquid photoresist is spryed unp of the wferF he huk is then spun rpidlyD getting to severl thousnd w in smll frtion of seondF gentrifugl fore uses the resist to spred out uniformly ross the wfer surfeF he solvent for the photoresist is quite voltile nd so the lyer of photoresist dries while the wfer is still spinningD resulting in thinD uniform oting ross the wfer pigure RFIWF
Figure 4.19:
After the photoresist is spun on.
he nme 4photoresist4 gives some lue s to wht this stu' isF fsillyD photoresist is polymer mixed with some kind of light sensitizing ompoundF sn positive photoresistD wherever light strikes itD the polymer is wekenedD nd it n e more esily removed with solvent during the development proessF gonverselyD negtive photoresist is strengthened when it is illuminted with lightD nd is more resistnt to the solvent thn is the unilluminted photoresistF ositive resist is soElled euse the imge of the developed photoresist on the wfer looks just like the msk tht ws used to rete itF xegtive photoresist mkes n imge whih is the opposite of wht the msk looks likeF e hve to ome up with some wy of seletively illuminting ertin portions of the photoresistF enyone who hs ever seen projetor know how we n do thisF futD sine we wnt to mke smll thingsD not ig onesD we will hnge round our projetor so tht it mkes smller imgeD insted of igger oneF he instrument tht projets the light onto the photoresist on the wfer is lled projetion printer or stepper pigure RFPHF
IRI
Figure 4.20:
A schematic of a stepper conguration.
es shown in pigure RFPHD the stepper onsists of severl prtsF here is light soure @usully merury vpor lmpD lthough ultrEviolet eximer lsers re lso strting to ome into useAD ondenser lens to imge the light soure on the msk or retileF he msk ontins n imge of the pttern we re trying the ple on the wferF he projetion lens then mkes redued @usully SxA imge of the msk on the wferF feuse it would e fr too ostlyD if not just plin impossileD to projet onto the whole wfer ll t oneD only smll seleted re is printed t one timeF hen the wfer is snned or stepped into new positionD nd the imge is printed ginF sf previous ptterns hve lredy een formed on the wferD mersD with rti(il intelligene lgorithms re used to lign the urrent imge with the previously formed feturesF he stepper moves the whole surfe of the wfer under the lensD until the wfer is ompletely overed with the desired ptternF e stepper is one of the most importnt piees of equipment in the whole sg f howeverD sine it determines wht the minimum feture size on the iruit will eF efter exposureD the photoresist is pled in suitle solventD nd 4developed4F uppose for our exmple the struture shown in pigure RFPI is wht results from the photolithogrphi stepF
IRP
Figure 4.21:
After photoresist exposure and development.
he pttern tht ws used in the photolithogrphi @vA step exposed hlf of our re to lightD nd so the photoresist @A in tht region ws removed upon developmentF he wfer is now immersed in hydro)uori id @rpA solutionF rp id ethes silion nitride quite rpidlyD ut does not eth silion dioxide nerly s fstD so fter the eth we hve wht we see in pigure RFPPF
Figure 4.22:
After the nitride etch step.
e now tke our wferD put it in the ion implnter nd sujet it to 4lst4 of phosphorus ions pigure RFPQF
Figure 4.23:
Implanting phospohrus.
IRQ he ions go right through the oxide lyer on the rD ut stik in the resistGnitride lyer on the vr of our strutureF
4.6 Optical Issues in Photolithography

note:
Electronic MaterialsF his module ws prepred with the ssistne of ne fllF
4.6.1 Introduction
hotolithogrphy is one of the most importnt tehnology in the prodution of dvned integrted iruitsF st is through photolithogrphy tht semiondutor surfes re ptterned nd the iruits formedF sn order to mke extremely smll feturesD on the order of the wvelength of the lightD dvned optil tehniques re used to trnsfer pttern from msk onto the surfeF e polymeri (lm or resistD is modi(ed y the light nd reords the informtion in proess not dissimilr to ordinry photogrphyF en illustrtion of the photolithogrphi proess is shown in pigure RFPRF he proess follows the following si stepsX tep IF he wfer is spin oted with resist to form uniform I m thin (lm of resist on the surfeF tep PF he wfer is exposed with ultrviolet light through msk whih ontins the desired ptternF sn the simplest proesses the msk is simply pled over the wferD ut dvned suEmiron tehnologies require the pttern to imged through omplex optil systemF tep QF he photoresist is developed nd the irrdited re is wshed wy @positive resistA or the unirrdited re is wshed wy @negtive resistAF tep RF roessing @ethingD deposition etFA tep SF emining resist is strippedF
8
IRR
Figure 4.24:
Steps in optical printing using photolithography.
sn ddition to eing possily the most importnt semiondutor proess stepD photolithogrphy is lso the most expensive tehnology in semiondutor mnufturingF his expense is the result of two onsidertionsX IF he optis in photolithogrphy tools re expensive where single lens n ost 6I million or more PF ih hip @often referred to s 4dye4A must e exposed individully unlike other semiondutor proesses suh s gh where n entire wfer n e proessed t time or oxidtion proesses where mny wfers n e proessed simultneouslyF his mens tht not only re photolithogrphy mhines the most expensive of semiondutor proessing equipmentD ut more of them re needed in order to mintin throughputF
4.6.2 Optical issues in photolithography

4.6.2.1 The critical dimension and depth of focus
e semiondutor proess tehnology is often desried y hrteristi length known s the ritil dimensionF he ritil dimension @ghA is the smllest feture tht needs to e ptterned on the surfeF he ext de(nition vries from proess to proess ut is often the hnnel length of the smllest trnsistor @typil of memory hipA or the width of the smllest metl interonnetion line @logi hipsAF his ritil dimension is de(ned y the photolithogrphi proess nd is perhps the most importnt (gure of merit in the mnufture of integrted iruitsF wking the ritil dimension smller is the primry fous of improving semiondutor tehnology for the following resonsX IF wking the gh smller drmtilly inreses the numer of devies per unit re nd this inrese goes with the squre of the gh @iFeFD redution in gh y ftor of P genertes R times the numer of deviesAF
IRS PF wking the gh smller of devie lredy in prodution will mke smller hipF his mens tht the numer of hips per wfer inreses drmtillyD nd sine osts generlly sle with the numer of wfers nd not the numer of hips to wferD osts re drmtilly reduedF QF mller devies re fsterF hereforeD improvements in lithogrphy tehnology trnslte diretly into etterD fsterD more omplex irE uits t lower ostF rving estlished the importne of the ritil dimension it is importnt to understnd wht fetures of photolithogrphy system imptF he theory ehind projetion lithogrphy is very well knownD dting from the originl nlysis of the mirosope y eeF st isD in ftD the ee sine ondition tht dittes the ritil dimensionX
@RFISA where the two expressions refer to the limit of purely oherent illuminting soure nd purely inoherent soure respetivelyD nd is the vuum wvelength of the illuminting light soureD n the index of refrtion of the ojetive lensD nd refers to the ngle etween the xis of the lens nd the line from the k fol point to the perture of the entrne of the lensF he quntity in the denomintorD nsin@A is referred to s the numeril perture or xeF es the degree of oherene n e djusted in lithogrphy systemD the ritil dimension is usully written more generlly sX @RFITA prom this equtionD we egin to see wht n e done to redue the ritil dimension of lithogrphy systemX IF ghnge the wvelength of the soureF PF snrese the numeril perture @xeAF QF edue k 1 F fefore we disuss how this is omplishedD we must onsider one other key quntityD the depth of fous or hypF he depth of fous is the length long the xis in whih shrp imge existsF xturlly lrge hyp is desirle for ese of lignmentD sine the entire dye must with lie within this regionF sn relityD howeverD the more meningful onstrint is tht the hyp must e thiker thn the resist lyer so tht the entire volume of resist is exposed nd n e developedF elsoD if the surfe morphology of the devie dittes tht the resist to e exposed is not plnrD then the hyp must e lrge enough so tht ll fetures re properly illumintedF gurrent resists must e I m in thikness in order to hve the neessry eth resistneD so this n e onsidered minimum vlue for n eptle hypF he depth of fous n lso e expressed s funtion of numeril perture nd wvelengthX @RFIUA sf we desire to minimize the ritil dimension simply y mking optis of lrge numeril perture tht we will simultneously redue the depth of fous nd t muh fster rte owing to the dependene on the squre of the numeril pertureF hese two quntitiesD hyp nd ghD provide the diretion in lithogrphy nd semiondutor proessing s wholeF por exmpleD design with n improved surfe plnrity or new resist tht is e'etive t smller thiknesses would llow for smller depth of fous whih would in turn llow for lrger numeril perture implying smller ritil dimensionF he resistD the soure wvelengthD nd the optil delivery system
IRT
ll 'et the ritil dimension nd tht further re(nements require multifeted pproh to improving lithogrphy systemsF ht lso must e relized is thtD s fr s the optil system is onernedD virtully ll tht n e done with onventionl optis hs een done nd tht fundmentl restrints on k 1 hve een rehedF
4.6.2.2 Wavefront engineering
yne wy to get round the fundmentl limittions of n imging system illustrted in @RFISA is through one of vriety of tehniques often termed wavefront engineering. rereD not only is the mplitude mpped from the ojet plne to the imge plneD ut the phse struture of the light going through the msk is mnipulted to improve the ontrst nd llow for e'etive vlues of k 1 lower thn the theoretil minimum for uniform illumintionF he most importnt exmple of these tehniques is the phse shift msk or wF rere the msk onsists of two types of resD those tht llow light to pss through un'eted nd some regions where the mplitude of the light is un'eted ut its phse is shiftedF he resulting eletri (elds will then sum to zero in some ples where use of n ordinry msk would hve resulted in positive intensityF here re mny prolems with the prtil introdution of vrious phse shifting tehniquesF gonstruE tion of msks with phse shifting elements @usully thin lyer of wweA is di0ult nd expensiveF wsk dmgeD lredy key prolem in onventionl prodution tehniquesD eomes n even greter issue s trditionl msk repir tehniques n no longer e usedF elso identifying errors in msk is mde more di0ult y the odd designF
4.6.2.3 Interaction with resists
he ultimte resolution of photolithogrphi proess is not dependent on optis loneD ut lso on the intertion with the resistF yne of the key onernsD prtiulrly s wvelengths of soures eome shorterD is the ility of the soure light to penetrte the resist (lmF wny polymers sor strongly in the whih n limit the intertion to the surfeF sn suh se only thin lyer of the polymer is exposed nd the pttern my not e fully unovered during developingF yne importnt property of resist is the presene of saturable absorptionFF turle sorers re those sorption sites in the polymer tht when exited to higher stte remin there for reltively long periods of time nd do not ontinue to sor into higher sttesF sf only sturle sorption is present in polymer (lmD then ontinued irrdition eventully leds to trnspreny s ll sorption sites will e sturtedF his llows light penetrtion through the resist (lm with full exposure to the sustrte surfeF pull penetrtion of the (lm leds to seond prolemD multiple re)etion interfereneF his ours when light whih hs penetrted the (lm to the sustrte is then re)eted k towrds the surfeF he result is stnding wve interferene pttern whih uses uneven exposure through the (lmF he prolem eomes more severe s optil limits re pprohed where feture size is pproximtely equl to the wvelength of the light soure mening suh stnding wves re the sme size s the irrdited feturesF sn the most dvned lithogrphy tehniques suh s PRV nm lithogrphy with eximer lsersD speil ntiEre)etne oting must e lid down efore the resist is depositedF hevelopment of n e oting tht hs no dverse e'ets during the exposure nd development proess is di0ultF yne ompletely new pproh to photolithogrphy resists re topEsurfeEimged resists or s resistsF hese proesses do not require light penetrtion through the whole volume of resistF sn s resistD silyl mine is seletively inEdi'used from the gs phse into phenoli polymer in response to the lser irrditionF his di'usion proess retes silyl etherD nd development tkes ple in the form of n oxygen plsm ethD sometimes termed 9dry developing9F hepth of fous limittions re thus voided s exposure is neessry only t the surfe of the resist lyerD nd the resolution of the ething proess determines the (nl resist pro(leF uh tehnique hs tremendous dvntgesD prtiulrly s soure wvelengths eome shorter nd trnsprent polymers more rreF uh s resist hs ler optil dvntge s well sine the imge need only e formed t the surfe of the resist lyer reduing the hyp needed to IHH nm or lessD llowing for lrger numeril perture lithogrphy systems with smller ritil dimensionsF
IRU
4.6.2.4 Light sources
gurrent photolithogrphy tehniques in prodution utilize ultrviolet lmps s the light soureF sn the most dvned prodution filitiesD HFQS m merury iEline tehnology is usedF por the next genertion of hips suh s TR wit hew etter performne is neessry nd either iEline tehnology omined with w or new light soure is requiredF gertinly for the PST wit genertion using HFPS m tehnologyD the iEline soure is no longer dequteF he pprent suessor is the PRV nm urp lserD whih entered the most dvned prodution filities in the lte IWWHsF urp tehnology is often referred to in the literture s heep or h lithogrphyF por further shrinkge to HFIV m tehnologyD the erp eximer lser t IWQ nm will likely e used with the trnsition likely to tke ple in the (rst few yers of the next dedeF et ritil dimensions lower thn HFIV E HFI m nd elowD whole host of tehnologil prolems will need to e overome in every stge of mnufturing inluding photolithogrphyF yne likely sheme for future lithogrphy is to use Erys where the wvelength of the light is so muh smller thn the feture size suh tht proximity printing n e usedF his is where the msk is pled lose to the surfe nd n Ery soure is snned ross using no optisF gommon Ery soures for suh tehniques inlude synhrotron rdition nd lser produed plsmsF st hs lso een widely suggested tht the ost of implementing Ery or other postEoptil tehniques together with the inresed ost of every other mnufturing proess step will mke improvements eyond HFI m ost prohiitive where ene(ts in inresed iruit speed nd density will e dwrfed y mssive mnufturing ostF st is noted however tht suh preditions hve een mde in the pst with regrd to other tehnologil rriersF
4.6.3 Bibliography
wF forn nd iF olfD Principles of Optics 6th EditionD ergmon ressD xew ork @IWVHAF wF xkseD IEICE Trans. Electron.D IWWQD E76-CD PTF wF othshildD eF F porteD wF F rornD F F uunzD F gF lmteerD nd tF rF gF edlekD IEEE J. Selected Topics in Quantum ElectronicsD IWWSD 1D WITF
4.7 Composition and Photochemical Mechanisms of Photoresists
note: his module ws developed s prt of the ie niversity ourse griwERWTX Chemistry of Electronic MaterialsF his module ws prepred with the ssistne of engel gindy eiF
4.7.1 Photolithography
sn photolithogrphyD pttern my e trnsferred onto photoresist (lm y exposing the photoresist to light through msk of the ptternF sn the semiondutor industryD the photolithogrphi proedure inludes the following steps s illustrted in pigure RFPSX oting se mteril with photoresistD exposing the resist through msk to lightD developing the resistD ething the exposed res of the seD nd stripping the remining resist o'F
9
IRV
Figure 4.25:
Steps in optical printing using photolithography.
pon exposure to lightD the photoresist my eome more or less solule depending on the hemil properties of the prtiulr resist mterilF he photohemil retions inlude hin sissionD rossElinkingD nd the rerrngement of moleulesF sf the exposed res of the photoresist eome more soluleD then it is positive resistY onverselyD if the exposed resist eomes less soluleD then it is negtive resistF sn developing the photoresistD the more solule mteril is removed leving positive or negtive imge of the msk ptternF
4.7.2 Photoresist
hotoresists were initilly developed for the printing industryF sn the IWPHsD the pplition of photoresists spred to the printed iruit ord industryF hotoresists for semiondutor use were (rst developed in the IWSHsY uodk developed ommeril negtive photoresists nd shortly fterD hipley developed line of positive resistsF everl other ompnies hve entered the mrket sine tht time in hopes of mnufturing resist produts whih meet the inresing demnds of the semiondutor industryX nrrower line widthsD fewer defetsD nd higher prodution rtesF
4.7.2.1 Photoresist composition
everl funtionl requirements must e met for photoresist to e used in the semiondutor industryF hotoresist polymers must e solule for esy deposition onto sustrte y spinEotingF qood photoresistE sustrte dhesion properties re required to minimize underuttingD to mintin edge uityD nd to ontrol the feture sizesF he photoresist must e hemilly resistnt to whihever ethnts re to e usedF enE sitivity of the photoresist to prtiulr light soure is essentil to the funtionlity of photoresistF he speed t whih hemil hnges our in photoresist is its ontrstF he ontrst of resist is dependent
IRW on the moleulr weight distriution of the polymersX rod moleulr weight distriution results in low ontrst resistF righ ontrst resists produe higher resolution imgesF he four si omponents of photoresist re the polymerD the solventD sensitizersD nd other dditivesF he role of the polymer is to either polymerize or photosoluilize when exposed to lightF olvents llow the photoresist to e pplied y spinEotingF he sensitizers ontrol the photohemil retions nd dditives my e used to filitte proessing or to enhne mteril propertiesF hotohemil hnges to polymers re essentil to the funtionlity of photoresistF olymers re omposed primrily of ronD hydrogenD nd oxygenEsed moleules rrnged in repeted ptternF xegtive photoresists re sed on polyisopreme polymersY negtive resist polymers re not hemilly onded to eh otherD ut upon exposure to lightD the polymers rosslinkD or polymerizeF ositive photoresists re formulted from phenolEformldehyde novolk resinsY the positive resist polymers re reltively insoluleD ut upon exposure to lightD the polymers undergo photosoluiliztionF olvents re required to mke the photoresist liquidD whih llows the resist to e spun onto suE strteF he solvents used in negtive photoresists re nonEpolr orgni solvents suh s tolueneD xyleneD nd hlogented liphti hydroronsF sn positive resistsD vriety of orgni solvents suh s ethyl ellosolve etteD ethoxyethyl etteD diglymeD or ylohexnone my e usedF hotosensitizers re used to ontrol or use polymer retions resulting in the photosoluiliztion or rosslinking of the polymerF he sensitizers my lso e used to roden or nrrow the wvelength response of the photoresistF fiszide sensitizers re used in negtive photoresists while positive photoresists utilize dizonphthoquinonesF yne mesure of photosensitizers is their quntum e0ieniesD the frtion of photons whih result in photohemil retionsY the quntum e0ieny of positive dizonphthoquinone photoresist sensitizers hs een mesured to e HFP E HFQ nd the quntum e0ieny of negtive isErylzide sensitizers is in the rnge of HFS E IFHF edditives re lso introdued into photoresists depending on the spei( needs of the pplitionF eddiE tives my e used to inrese photon sorption or to ontrol light within the resist (lmF edhesion promoters suh s hexmethyldisilzne nd dditives to improve sustrte oting re lso ommonly usedF
4.7.2.2 Negative photoresist chemistry
he mtrix resin mteril used in the formultion of these @negtiveA resists is syntheti ruer otined y ieglerExtt polymeriztion of isoprene whih results in the formtion of poly@isEisopreneAF eidE tlyztion of poly@isEisopreneA produes prtilly ylized polymer mterilY the ylized polymer hs higher glss trnsition tempertureD etter struturl propertiesD nd higher densityF yn the vergeD miroeletroni resist polyisoprenes ontin IEQ rings per yli unitD with SEPH7 unreted isoprene units remining9F he resultnt mteril is extremely solule in nonEpolrD orgni solvents inluding tolueneD xyleneD nd hlogented liphti hydroronsF he ondenstion of prEzidoenzldehyde with sustituted ylohexnone produes isErylzide sensitizersF o mximize the sorption of prtiulr light soureD the sorne spetrum of the phoE toresist my e shifted y mking struturl modi(tions to the sensitizersY for exmpleD y using sustiE tuted enzldehydesD the sorption pek my e shifted to longer wvelengthsF e typil iszideEylized polyisoprene photoresist formultion my ontin WU prts ylized polyisoprene to Q prts iszide in @IH wt7A xylene solventF ell negtive photoresists funtion y rossElinking hemilly retive polymer vi photosensitive gent tht initites the hemil rossElinking retionF sn the iszideEylized polyisoprene resistsD the sorption of photons y the photosensitive iszide in the photoresist results in n insolule rosslinked polymerF pon exposure to lightD the iszide sensitizers deompose into nitrogen nd highly retive hemil intermeditesD lled nitrenes @RFIVAF he nitrines ret to produe polymer linkges nd threeEdimensionl rossElinked
ISH
strutures tht re less solule in the developer solutionF
@RFIVA
4.7.2.3 Positive photoresist chemistry
ositive photoresist mterils originlly developed for the printing industry hve found use in the semionE dutor industryF he ommonly used novol resins @phenolEformldehyde opolymerA nd @photosensitiveA dizoquinone oth were produts of the printing industryF he novolk resin is opolymer of phenol nd formldehyde @pigure RFPTAF xovolk resins re solule in ommon orgni solvents @inluding ethyl ellosolve ette nd diglymeA nd queous se solutionsF gommeril resists usully ontin metEresol resins formed y the idEtlyzed ondenstion of metE resol nd formldehydeF
Figure 4.26:
Structure of a novolak resin.
he positive photoresist sensitizers re sustituted dizonphthoquinonesF he hoie of sustituents 'ets the soluility nd the sorption hrteristis of the sensitizersF gommon sustituents re ryl sulfontesF he dizoquinones re formed y retion of dizonphthoquinone sulfonyl hloride with n lohol to form sulfonte esterY the sensitizers re then inorported into the resist vi rrier or onded to the resinF he sensitizer ts s dissolution inhiitor for the novl resin nd is seEinsoluleF he positive photoresist is formulted from novol resinD dizonphthoquinone sensitizerD nd dditives dissolved in PH E RH wt7 orgni solventF sn typil resistD up to RH wt7 of the resist my e the sensitizerF he photohemil retion of quinonedizide is illustrted in @RFIWAF pon sorption of photonD the quinonedizide deomposes through ol' rerrngementD spei(lly us retionD nd produes gseous nitrogen s yEprodutF sn the presene of wterD the deomposition produt forms n indene roxyli idD whih is seEsoluleF roweverD the formtion of id my not e the reson for inresed soluilityY the relese of nitrogen gs produes porous struture through whih the developer my redily di'useD
ISI resulting in inresed soluilityF
@RFIWA
4.7.2.4 Image reversal
fy introduing n dditive to the novol resins with dizonphthquiones sensitizersD the resultnt photoreE sist my e used to form negtive imgeF e smll mount of si dditive suh s monzolineD imidzoleD nd triethylmine is mixed into positive novol resistF pon exposure to lightD the dizonphthquiones sensitizer forms n indene roxyli idF huring the susequent king proessD the se tlyzes therE ml deroxyltionD resulting in sustituted indene tht is insolule in queous seF henD the resist is )ood exposed destroying the dissolution inhiitors remining in the previously unexposed regions of the resistF he development of the photoresist in queous se results in negtive imge of the mskF
4.7.3 Comparison of positive and negative photoresists

snto the IWUHsD negtive photoresist proesses domintedF he poor dhesion nd the high ost of positive photoresists prevented its widespred use t the timeF es devie dimensions grew smllerD the dvntges of positive photoresistsD etter resolution nd pinhole protetionD suited the hnging demnds of the semionE dutor industry nd in the IWVHs the positive photoresists me into promineneF e omprison of negtive nd positive photoresists is given in pigure RFPUF
ISP
Figure 4.27:
A comparison of negative and positive photoresists.
he etter resolution of positive resists over negtive resists my e ttriuted to the swelling nd imge distortion of negtive resists during developmentY this prevents the formtion of shrp vertil wlls of negtive resistF hisdvntges of positive photoresists inlude higher ost nd lower sensitivityF ositive photoresists hve eome the industry hoie over negtive photoresistsF xegtive photoresists hve muh poorer resolution nd the positive photoresists exhiit etter eth resistne nd etter therml stilityF es optil msking proesses re still preferred in the semiondutor industryD e'orts to improve the proesses re ongoingF gurrentlyD reserhers re studying vrious forms of hemil mpli(tion to inrese the photon sorption of photoresistsF
4.7.4 Bibliography
FwF elvinoD Plastics For ElectronicsD wqrwErillD snD xew ork @IWWSAF F F flevinsD F gF hlyD nd F F urnerD in Encyclopedia of Polymer Science and EngineeringD idF tF sF uroehwitzD ileyD xew ork @IWVSAF wF tF fowdenD in Materials for Microlithography: Radiation-Sensitive PolymersD idF vF pF hompE sonD gF qF illsonD nd tF wF tF prehetD emerin ghemil oiety ymposium eries xoF PTTD shingtonD hFgF @IWVRAF F tF woss nd eF vedwithD The Chemistry of the Semiconductor IndustryD flkie 8 on vimitedD qlsgow @IWVUAF iF eihmnisD pF wF roulihnD yF xlmsuD nd F F xeennD in Polymers for MicroelectronicsD idF vF pF hompsonD gF qF illsonD nd F gwD emerin ghemil oiety ymposium eriesD xoF SQUD shingtonD hFgF @IWWRAF F vn ntD Microchip FabricationD Pnd edFD wqrwErill ulishing gompnyD xew ork @IWWHAF
ISQ
gF qrnt illsonD in Introduction to MicrolithographyD Pnd edFD idF vF pF hompsonD gF qF illsonD wF tF fowdenD emerin ghemil oietyD shingtonD hFgF @IWVQAF
4.8 Integrated Circuit Well and Gate Creation

note:
10
Gate Creation y fill ilsonF
his module is sed upon the gonnexions module entitled Integrated Circuit Well and
e then remove the remining resistD nd perform n tivtionGnnelGdi'usion stepD lso sometimes lled the 4driveEin4F he purpose of this step is two foldF e wnt to mke the nEtnk deep enough so tht we n use it for our pEhnnel wyD nd we wnt to uild up n implnt rrier so tht we n implnt into the pEsustrte region onlyF e introdue oxygen into the retor during the tivtionD so tht we grow thiker oxide over the region where we implnted the phosphorusF he nitride lyer over the pEsustrte on the vr protets tht re from ny oxide growthF e then end up with the struture shown in pigure RFPVF
Figure 4.28:
After the anneal/drive-in.
xow we strip the remining nitrideF ine the only wy we n onvert from p to n is to dd donor onentrtion whih is greter thn the kground eptor onentrtionD we hd to keep the doping in the sustrte firly light in order to e le to mke the nEtnkF he lightly doped pEsustrte would hve too low threshold voltge for good nEwy trnsistor opertionD so we will do VT djust implnt through the thin oxide on the vrD with the thik oxide on the r loking the oron from getting into the nEtnkF his is shown in pigure RFPWD where oron is implnted into the pEtype sustrte on the vrD ut is loked y the thik oxide in the region over the nEwellF
10
ISR
Figure 4.29:
VT adjust implant.
xextD we strip o' ll the oxideD grow new thin lyer of oxideD nd then lyer of nitride pigure RFQHF he oxide lyer is grown only euse it is d to grow i3 x4 diretly on top of silionD s the di'erent oe0ients of therml expnsion etween the two mterils uses dmge to the silion rystl strutureF elsoD it turns out to e nerly impossile to remove nitride if it is deposited diretly on to silionF
Figure 4.30:
Strip of the oxide and grow a new nitride layer.
he nitride is ptterned @overed with photoresistD exposedD developedD ethedD nd removl of photoreE sistA to mke two res whih re lled 4tive4 pigure RFQIF he wfer is then sujeted to highEpressure oxidtion step whih grows thik oxide wherever the nitride ws removedF he nitride is good rrier for oxygenD so essentilly no oxide grows underneth itF he thik oxide is used to isolte individul trnsistorsD nd lso to mke for n insulting lyer over whih onduting ptterns n e runF he thik oxide is lled (eld oxide @or py for shortA pigure RFQPF
ISS
Figure 4.31:
Nitride remaining after etching.
Figure 4.32:
After growth of the eld oxide (FOX).
henD the nitrideD nd some of the oxide re ethed o'F he oxide is ethed enough so tht ll of the oxide under the nitride regions is removedD whih will tke little o' the (eld oxide s wellF his is euse we now wnt to grow the gte oxideD whih must e very len nd pure pigure RFQQF he oxide under the nitride is sometimes lled sacricial oxideD euse it is sri(ed in the nme of ultr performneF
IST
Figure 4.33:
Ready to grow gate oxide.
hen the gte oxide is grownD nd immeditely therefterD the whole wfer is overed with polysilion pigure RFQRF
Figure 4.34:
Polysilicon deposition over the gate oxide.
he polysilion is then ptterned to form the two regions whih will e our gtesF he wfer is overed one gin with photoresistF he resist is removed over the region tht will e the nEhnnel devieD ut is left overing the pEhnnel devieF e little re ner the edge of the nEtnk is lso unovered pigure RFQSF his will llow us to dd some dditionl phosphorus into the nEwellD so tht we n mke ontt thereD so tht the nEwell n e onneted to Vdd F
ISU
Figure 4.35:
Preparing for NMOS channel/drain implant.
fk into the implnter we goD this time exposing the wfer to phosphorusF he poly gteD the py nd the photoresist ll lok phosphorus from getting into the wferD so we mke two nEtype regions in the pEtype sustrteD nd we hve mde our nEhnnel wy soureGdrin regionsF e lso dd phosphorous to the Vdd ontt region in the nEwell so s the mke sure we get good ontt performne there pigure RFQTF
Figure 4.36:
Phosphorus S/D implant.
he formtion of the soure nd drin were performed with self-aligning technologyF his mens tht we used the gte struture itself to de(ne where the two inside edges of the soure nd drin would e for the wypiF sf we hd mde the soureGdrin regions efore we de(ned the gteD nd then tried to line the gte up right over the spe etween themD we might hve gotten something tht looks like wht is shown in pigure RFQUF ht9s going to e the prolem with this trnsistorc yviouslyD if the gte does not extend ll the wy to oth the soure nd the drinD then the hnnel will not eitherD nd the trnsistor will never turn on3 e ould try mking the gte widerD to ensure tht it will overlp oth tive resD even if it is slightly mislignedD ut then you get lot of extrneous fringing pitne whih will signi(ntly slow down the speed of opertion of the trnsistor pigure RFQVF his is d3 he development of the selfEligned gte tehnique ws one of the ig rekthroughs whih hs propelled us into the vs nd vs erF
ISV
Figure 4.37:
A representation of a misaligned gate.
Figure 4.38:
A representation of a wide gate.
e pull the wfer out of the implnterD nd strip o' the photoresistF his is sometimes di0ultD euse the t of ion implnttion n 4ke4 the photoresist into very tough (lmF ometimes n rf dishrge in n y2 tmosphere is used to 4sh4 the photoresistD nd literlly urn it o' the wfer3 e now pply some more D nd this time pttern to hve the mot reD nd sustrte ontt exposedD for oron p+ implntF his is shown in pigure RFQWF
ISW
Figure 4.39:
Boron p-channel S/D implant.
e re lmost doneF he next thing we do is remove ll the photoresistD nd grow one more lyer of oxideD whih overs everythingD s shown in pigure RFRHF e put photoresist over the whole wfer ginD nd pttern for ontt holes to go through the oxideF e will put ontts for the two drinsD nd for eh of the souresD mke sure tht the holes re ig enough to lso llow us to onnet the soure ontt to either the pEsustrte or the nEmot s is pproprite pigure RFRIF
Figure 4.40:
Final oxide growth.
ITH
Figure 4.41:
After the contact holes are etched.
4.9 Applying Metallization by Sputtering

note:
11
his module is dpted from the gonnexions module entitled Applying Metal/Sputtering y fill ilsonF e now put the wfer in sputter deposition systemF sn the sputter systemD we ot the entire surfe of the wfer with ondutorF en luminumEsilion lloy is usully usedD lthough other metls re employed s wellF e sputtering system is shown shemtilly in pigure RFRPF e sputtering system is vuum hmerD whih fter it is pumped outD is reE(lled with lowEpressure rgon gsF e high voltge ionizes the gsD nd retes wht is known s the grookes drk spe ner the thodeD whih in our seD onsists of metl trget mde out of the metl we wnt to depositF elmost ll of the potentil of the highEvoltge supply ppers ross the drk speF he glow dishrge onsists of rgon ions nd eletrons whih hve een stripped o' of themF ine there re out equl numer of ions nd eletronsD the net hrge density is out zeroD nd hene y quss9 lwD so is the (eldF
11
ITI
Figure 4.42:
A schematic representation of a sputtering apparatus.
he eletri (eld elertes the rgon toms whih slm into the luminum trgetF here is n exhnge of momentumD nd n luminum tom is ejeted from the trget @pigure RFRQA nd heds to the silion wferD where it stiksD nd uilds up metl (lm pigure RFRRF
Figure 4.43:
The sputtering mechanism.
ITP
Figure 4.44:
Wafer coated with metal.
sf you look t pigure RFRRD you will note tht we hve seemingly done something pretty stupidF e hve wired ll of the elements of our gwy inverter togetherY ut ll is not lostF e n do one more photolithogrphi stepD nd pttern nd eth the luminumD so we only hve it where we need itF his is shown in pigure RFRSF
Figure 4.45:
After interconnect patterning.
Chapter 5
Thin Film Growth

5.1 Molecular Beam Epitaxy
1
note: his module ws developed s prt of the ie niversity ourse griwERWTX Chemistry of Electronic MaterialsF his module ws prepred with the ssistne of rh estottF
5.1.1 Introduction
sn the proess of epitxyD thin lyer of mteril is grown on sustrteF ith respet to rystl growth it pplies to the proess of growing thin rystlline lyers on rystl sustrteF sn epitxil growthD there is preise rystl orienttion of the (lm in reltion to the sustrteF por eletroni deviesD the sustrte is single rystl @usully i or qesA nd therefore so is the epitxil lyer @epilyerAF sn the most si form of moleulr em epitxy @wfiAD the sustrte is pled in ultr high vuum @rA nd the soure mterils for the (lm re evported from elementl souresF he evported moleules or toms )ow s emD striking the sustrteD where they re dsored on the surfeF yne on the surfeD the toms move y surfe di'usion until they reh thermodynmilly fvorle lotion to ond to the sustrteF woleules will dissoite to tomi form during di'usion or t fvorle siteF pigure SFI illustrtes the proesses tht n our on the surfeF feuse the toms require time for surfe di'usionD the qulity of the (lm will e etter with slower growthF ypilly growth rtes of out I monolyer per seond provide su0iently high qulityF
1
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ITR
CHAPTER 5. THIN FILM GROWTH
Figure 5.1: Schematic illustration of processes on growing surface during MBE. Adsorption of atoms on the surface, surface diusion of atoms, formation of crystalline lattice, desorption of particles from the surface.
e typil wfi hmer is shown in pigure SFPF he sustrte is hemilly wshed nd then put into loding hmer where it is further lened using rgon ion omrdment followed y nnelingF his removes the top lyers of the sustrteD whih is usully n undesired oxide whih grew in ir nd ontins impuritiesF he nneling hels ny dmge used y the omrdmentF he sustrte then enters the growth hmer vi the smple exhnge lod lokF st is seured on molydenum holder either mehnilly or with melted indium or gllium whih hold the sustrte y surfe tensionF
Figure 5.2:
The MBE growth chamber.
ih e'usion ell @see pigure SFPA is soure of one element in the (lmF he e'usion ellD lso lled
ITS unudsen ellD ontins the elementl form in very high purity @greter thn WWFWWWWW7 for q nd esAF he ell is heted to enourge evportionF por qes growthD the temperture is typilly ontrolled for vpor pressure of IH-2 to IH-3 orr inside the e'usion ellD whih results in trnsport of out IH15 moleulesGm2 to the sustrte when the shutter for tht ell is openedF he shpe nd size of the opening in the ell is optimized for n even distriution of prtiles on the sustrteF hue to the reltively low onentrtion of moleulesD they typilly do not intert with other moleules in the em during the S E QH m journey to the sustrteF he sustrte is usully rottedD t few rpmD to further even the distriutionF feuse wfi tkes ple in r nd hs reltively low pressure of residul gs t the surfeD nlysis tehniques suh s re)etion high energy di'rtion nd ellipsometry n e used during growthD oth to study nd ontrol the growth proessF he r environment lso llows pre or post growth nlysis tehniques suh s euger spetrosopyF
5.1.2 Elemental and molecular sources

he e'usion ell is used for the mjority of wfi growthF ell mterils used in the ell re refully hosen to e noninterting with the element eing evportedF por exmpleD the ruile is pyroliti oron nitrideF roweverD it hs disdvntgesD suh sX
he evported speies my e moleulrD rther thn monomeriD whih will require further dissotion t the surfeF hen the shutter is openedD the het loss from the ell results in trnsient in the em )ux whih lst for severl minutes nd use vritions of up to SH7F he growth hmer must e opened up to reple the solid souresF
grker ells re used to improve the rtio of monomeri to moleulr @or t lest dimeri to tetrmeriA prtiles from the soureF he rker ellD pled so tht the em psses through it fter the e'usion ellD is mintined t high temperture @nd sometimes high pressureA to enourge dissoitionF he dissoition proess generlly requires tlyst nd the est tlysts for given speies hve een studiedF ome elementsD suh s silionD hve low enough vpor pressure tht more diret heting tehniques suh s eletron omrdment or lser rdition heting re usedF he eletron em is ent using eletromgneti fousing to prevent ny impurities in the eletron soure from ontminting the silion to e used in wfiF feuse the het is onentrted on the surfe to e evportedD intertions with nd ontmintion from the ruile wlls is reduedF sn dditionD this design does not require shutterD so there is no prolem with trnsientsF wodultion of the em n produe very shrp interfes on the sustrteF sn lser rdition hetingD the eletron em is repled y lser emF he dvntges of lolized heting nd rpid modultion re lso mintined without hving to worry out ontmintion from the eletron soure or stry eletronsF ome of the ssEs @IPEITA ompounds hve suh high vpor pressure tht unudson ell nnot e usedF por exmpleD the merury soure must e kept ooler thn the sustrte to keep the vpor pressure low enough to e fesileF he rg soure must lso e seled o' from the growth hmer to llow the hmer to e pumped downF wo other methods of otining the elements for use in epitxy re gsEsoure epitxy nd hemil em epitxy @gfiAF foth of these methods use gs souresD ut they re distinguished y the use of elementl ems in gs soure epitxyD while orgnometlli ems re used in gfiF por the exmple of sssE @IQEISA semiondutorsD in gs epitxyD the group sss mteril my ome from n e'usion ell while the group mteril is the hydrideD suh s esr3 or r3 D whih is rked efore entering the growth hmerF sn gfiD the group mteril is n orgnometlliD suh s triethylgllium q@g2 r5 A3 or trimethylluminum el@gr3 A3 D whih dsors on the surfeD where it dissoitesF he gs soures hve severl dvntgesF qs lines n e run into the hmerD whih llows the supply to e replenished without opening the hmerF hen mking lloysD suh s elx q1-x esD the gses n e premixed for the orret stohiometry or even hve their omposition grdully hnged for mking grded struturesF por rupt struturesD it is neessry to e le to swith the gs lines with speeds of I seond or lessF roweverD the gs lines inrese the omplexity of the proess nd n e hrd on the pumping systemF
ITT
5.1.3 Substrate choice and preparation

wterils n e grown on sustrtes of di'erent strutureD orienttionD nd hemistryF sn deiding whih mterils n e grown on prtiulr sustrteD primry onsidertion ws expeted to e lttie misE mthD iFeFD di'erenes in sping etween tomsF roweverD while lttie mismth n use strin in the grown lyerD onsiderle ommodtion etween mterils of di'erent sizes n tke ple during growthF e greter soure of strin n e di'erenes in therml expnsion hrteristis euse the lyer is grown t high tempertureF yn ooling to room tempertureD dislotion defets n e formed t the interfe or in severe sesD the devie my rekF ghemil onsidertionsD suh s whether the lyer9s elements will dissolve in the sustrte or form ompounds with the sustrteD must lso e onsideredF hi'erent orienttions of the sustrte n lso 'et growthF gloseEpked plnes hve the lowest surfe energyD whih llows toms to desor from the surfeD resulting in slower growth rtesF qrowth is fvored where onds n e mde in severl diretions t the sme timeF hereforeD the sustrte is often ut o'Exis y P E R to provide rougher growth surfeF por ompound semiondutorsD some orienttions result in the numer of loose onds hnging etween lyersF his results in hnges of surfe energy with eh lyerD whih slows growth downF he gretest use of defets in the epitxil lyer is defets on the sustrte9s surfeF sn generlD ny dislotions on the sustrte re replited or even multiplied in the epitxil growthD whih is wht mkes the lening of the sustrte so importntF
5.1.4 Materials grown

wfi is ommerilly used primrily for qes deviesF his is prtly euse the high speed mirowve devies mde from qes required the superior eletril qulity of epitxil lyersF king ple t lower temperture nd under etter ontrolled onditionsD wfi generlly results in lyers of etter qulity thn meltEgrownF prom solid q nd es souresD elementl q nd tetrmeri es4 re evportedF por qes sustrteD the q )ux hs stiking oe0ient very lose to I @lmost ertin to dsorAF he es is muh less likely to dsorD so n exess is usully suppliedF grker ells re often used on the es4 in order to otin es2 instedD whih results in fster growth nd more e0ient utiliztion of the soure emF por nominlly undoped qes grown y wfiD the residul impurities re usully ronD from sustrte ontmintion nd residul gs fter the growth hmer is pumped downD nd sulphurD from the es soureF he most ommon surfe defets re 4ovl4 defetsD whih seem to form when q mnges to form metlli droplets during the growth proessD whih n prtiulrly our if the sustrte ws not lened properlyF hese defets n lso e redued y refully ontrolling the q )uxF huring wfi growthD dopnts n e introdued y hving seprte e'usion ell or gs soure for eh dopntF o hieve desired dopnt onentrtion in the (lmD not only must the rte of dopnts striking the sustrte e ontrolledD ut the hrteristis of how the dopnt ehves on the surfe must e knownF vowEvpor pressure dopnts tend to desor from the surfe nd their ehvior is very temperture dependent nd so re voided when possileF low di'using dopnts dsor to surfe sites nd re eventully overed s more qes is grownF heir inorportion depends linerly on the prtil pressure of the dopnt present in the growth hmerF his is the ehvior exhiited y most nEtype dopnts in qes nd most dopnts of oth types in iF sf the dopntD like most pEtype qes dopntsD is le to di'use through the surfe of the sustrte into the rystl elowD then there will e higher inorportion e0ienyD whih will depend on the squre root of the dopnt prtil pressure for resonle onentrtionsF hue to inresing lttie strinD ll dopnts will sturte t very high onentrtionsF hey my lso tend to form lustersF hopnt ehvior depends on mny ftors nd is tively studiedF he growth of qes epitxil lyers on silion sustrtes hs lso een investigtedF ilion sustrtes re grown in lrger wfersD hve etter therml ondutivity llowing more deviesGhip to e grown on themD nd re heperF roweverD euse i is nonpolr nd qes is polrD the qes tends to form islnds on the surfe with di'erent phse @wht should e q site sed on neighoring domin9s pttern will tully e n es siteAF here is lso firly lrge lttie mismthD leding to my dislotionsF roweverD
ITU pisD vihsD nd lsers hve ll een mde in lortoriesF wny devies require rupt juntions etween lyers of di'erent mterilsF yne groupD studying how to mke high qulityD rupt qes nd eles lyersD found tht rpid movement of the q or el on the surfe ws requiredF his migrtion ws enhned t high temperturesD ut unfortuntelyD di'usion into the sustrte lso inresedF roweverD they lso disovered tht migrtion of q or el inresed if the es supply ws turned o'F fy lternting the q nd es suppliesD the q ws le to reh the sustrte nd migrte to provide more even monolyer overge efore the es toms rrived to retF fesides qesD most other sssE semiondutors hve lso een grown using wfiF trutures involving very thin lyers @only few tomi lyers thikAD often lled superltties or strined superltties if there is lrge lttie mismthD re routinely grownF feuse di'erent mterils hve di'erent energy levels for eletrons nd holesD it is possile to trp rriers in one of these thin lyersD forming quntum wellF his type of on(nement struture is prtiulrly populr for vihs or lsersD inluding lue light lsersF he strined superlttie struture tully shifts nd splits the energy levels of the mterils in some ses mking devies possile for suh pplitions s infrred light detetionD whih requires very smll nd gpsF hin (lms of mny other mterils hve lso een grown using wfi methodsF ilion tehnology hs heper methods of growth nd so i lyers re not very populrF roweverD possile devies mde of iEqe lloys hve een grownF he ssEs ompoundsD hve lso een grownF wgneti mterilsD suh s goEt nd peEt lloysD hve een grown in the hopes of providing etter mgneti storgeF
5.1.5 Analysis techniques

he most populr inEsitu nlysis tehnique for wfiEgrown lyers is re)etion high energy di'rtion @riihAD see pigure SFQF iletrons of energy S E RH ke re direted towrds the smpleF hey re)et from the surfe t very smll ngle @less thn Q A nd re direted onto sreenF hese eletrons intert with only the top few tomi lyers nd thus provide informtion out the surfeF pigure SFR shows typil pttern on the sreen for eletrons re)eted from smooth surfeD in whih onstrutive interferene etween some of the eletrons re)eted from the lttie struture results in linesF sf the surfe is roughD spots will pper on the sreenD lsoF fy looking t the totl intensity of the re)eted eletron ptternD n ide of the numer of monolyers deposited nd how epilyers grow n e otinedF he islndEtype growth shown in this (gure is n re of intense interestF hese osilltions in intensity re grdully dmped s more lyers re grownD euse the overll roughness of the surfe inresesF
Figure 5.3:
Schematic illustrating the formation of a RHEED pattern.
ITV
RHEED diraction pattern of a GaAs surface. Adapted from images by the MBE Laboratory in the Institute of Physics of the ASCR (http://www.fzu.cz/departments/surfaces/mbe/index.html).
Figure 5.4:
hse loked epitxy tkes dvntge of the ptterns of the osilltions to grow very rupt lyersF fy sending the osilltion informtion to omputerD it n deide when to open or lose the shutters of the e'usion ell sed on the lotion in the osilltion yleF his tehnique selfEdjusts for )ututions in em )ux when the shutters re opened nd n grow very rupt lyersF enother nlysis tehnique tht n e used to study surfe smoothness during growth is ellipsometryF olrized lser light is re)eted from the surfe t smll ngleF he polriztion of the light hngesD depending on the roughness of the surfeF smproved growth hrteristis lso require tht the tul )ux from the soures is mesuredF his is typilly done with n ion guge )ux monitorD whih is either used to mesure residul em tht misses the sustrte or is moved into the em pth for lirtion when new soure is usedF feuse of the importne of len sustrte surfes for lowEdefet growthD euger spetrosopy is used following lening y sputteringF euger spetrosopy tkes ple y ionizing n inner shell eletron from n tomF hen n outer shell eletron then deexites to the inner shellD the energy relesed n prompt the emission of nother outer shell eletronF he energy t whih this ours is hrteristi of the tom involved nd the signl n e used to detet impurities s smll s HFI7F
5.1.6 Bibliography
uF tF fhmnnD The Materials Science of MicroelectronicsD gr @IWWSAF F uF qhndhiD VLSI Fabrication Principles: Silicon and Gallium ArsenideD Pnd iditionD ileyE sntersieneD x @IWWRAF wF eF rermn nd rF itterD Molecular Beam Epitaxy: Fundamentals and Current StatusD pringerE erlg @IWVWAF F rorikoshiD wF uwshimD nd rF mguhiD Jpn. J. Appl. Phys.D IWVTD 25D vVTVF tF rF wpeeD fF sF willerD nd uF tF fhmnnD J. Electrochem. Soc.D IWUUD 124D PSWF F kmotoD rF punshiD uF yhtD F xkgwD xF tF uwiD nd F uojimD Jpn. J. Appl. Phys.D IWVRD 23D vTSUF F F sngD J. Crystal GrowthD IWVUD 81D PTIF
ITW
5.2 Atomic Layer Deposition

5.2.1 Introduction
MaterialsF his module ws prepred with the ssistne of tulie eF prnisF
his module ws developed s prt of the ie niversity ourse griwERWTX Chemistry of Electronic
he growth of thin (lms hs hd drmti impt on tehnologil progressF feuse of the vrious properties nd funtions of these (lmsD their pplitions re limitless espeilly in miroeletronisF hese lyers n t s superondutorsD semiondutorsD ondutorsD insultorsD dieletriD or ferroeletrisF sn semiondutor deviesD these lyers n t s tive lyers nd dieletriD ondutingD or ion rrier lyersF hepending on the type of (lm mteril nd its pplitionsD vrious deposition tehniques my e employedF por gsE phse depositionD these inlude vuum evportionD retive sputteringD hemil vpor deposition @ghAD espeilly metl orgni gh @wyghAD nd moleulr em epitxy @wfiAF etomi lyer deposition @evhAD originlly lled tomi lyer epitxy @eviAD ws (rst reported y untol et lF in IWVH for the growth of zin sul(de thin (lms to frite eletroluminesent )t pnel displysF evh refers to the method wherey (lm growth ours y exposing the sustrte to its strting mterils lterntelyF st should e noted tht evi is tully suEset of evhD in whih the grown (lm is epitxil to the sustrteY howeverD the terms re often used interhngelyF elthough oth evh nd gh use hemil @moleulrA preursorsD the di'erene etween the tehniques is tht the former uses self limiting hemil retions to ontrol in very urte wy the thikness nd omposition of the (lm depositedF sn this regrd evh n e onsidered s tking the est of gh @the use of moleulr preursors nd tmospheri or low pressureA nd wfi @tomEyEtom growth nd high ontrol over (lm thiknessA nd omining them in single methodF e seletion of mterils deposited y evh is given in le SFIF
Compound class Examples
ss!s ompounds
nD neD neD n1x ex D gD rD fD r1x ex D gdD gdeD wneD rgeD rg1x gdx eD gd1x wnx e nXw @w a wnD D mAD gXw @w a iuD geD D AD rXw @w a geD D D wnD guA qesD elesD elD snD qD snesD elx q1x esD qx sn1x esD qx sn1x elxD qxD snxD ixx ixD xD 3 x5 D xxD wox el2 y3 D iy2 D ry2 D rfy2 D 2 y5 D x2 y5 D 2 y3 D wgyD gey2 D iy2 D v2 y3 D riy3 D fiy3 sn2 y3 D sn2 y3 XnD ny2 XD nyD sn2 y3 XpD sn2 y3 XrD ny2 D
ss!s sed thinE(lm eletroluminesent @pivA phosphors sss! ompounds emiondutorsGdieletri nitrides wetlli nitrides hieletri oxides rnsprent ondutor oxides
IUH emiondutor oxides uperondutor oxides pluorides

nyXelD q2 y3 D xiyD goyx f2 gu3 y7-x gp2 D rp2 D np2
Table 5.1X ixmples of thin (lm mterils deposited y evh inluding (lms deposited in epitxilD polyrystlline or morphous formF edpted from wF itl nd wF veskelD NanotechnologyD IWWWD 10D IWF
5.2.2 How ALD works

he premise ehind the evh proess is simple oneF he sustrte @morphous or rystllineA is exposed to the (rst gseous preursor moleule @elementl vpor or voltile ompound of the elementA in exess nd the temperture nd gs )ow is djusted so tht only one monolyer of the retnt is hemisored onto the surfe @pigure SFSAF he exess of the retntD whih is in the gs phse or physisored on the surfeD is then purged out of the hmer with n inert gs pulse efore exposing the sustrte to the other retnt @pigure SFSAF he seond retnt then hemisors nd undergoes n exhnge retion with the (rst retnt on the sustrte surfe @pigure SFSAF his results in the formtion of solid moleulr (lm nd gseous side produt tht my then e removed with n inert gs pulse @pigure SFSdAF
Figure 5.5:
Schematic representation of an ALD process.
he deposition my e de(ned s selfElimiting sine oneD nd only oneD monolyer of the retnt speies remins on the surfe fter eh exposureF sn this seD one omplete yle results in the deposition of one monolyer of the ompound on the sustrteF epeting this yle leds to ontrolled lyerEyElyer growthF hus the (lm thikness is ontrolled y the numer of preursor yles rther thn the deposition timeD s is the se for gh proessesF his selfElimiting ehvior is the fundmentl spet of evh nd understnding the underlying mehnism is neessry for the future exploittion of evhF
IUI yne si ondition for suessful evh proess is tht the inding energy of monolyer hemisored on surfe is higher thn the inding energy of susequent lyers on top of the formed lyerY the temperture of the retion ontrols thisF he temperture must e kept low enough to keep the monolyer on the surfe until the retion with the seond retnt oursD ut high enough to reEevporte or rek the hemisorption ondF he ontrol of monolyer n further e in)uened with the input of extr energy suh s irrdition or lser emsF he greter the di'erene etween the ond energy of monolyer nd the ond energies of the susequent lyersD the etter the selfEontrolling hrteristis of the proessF fsillyD the evh tehnique depends on the di'erene etween hemisorption nd physisorptionF hE ysisorption involves the wek vn der l9s foresD wheres hemisorption involves the formtion of relE tively strong hemil onds nd requires some tivtion energyD therefore it my e slow nd not lwys reversileF eove ertin tempertures hemisorption domintes nd it is t this temperture evh opertes estF elsoD hemisorption is the reson tht the proess is selfEontrolling nd insensitive to pressure nd sustrte hnges euse only one tomi or moleulr lyer n dsor t the sme timeF
5.2.3 Equipment for the ALD process

iquipment used in the evh proess my e lssi(ed in terms of their working pressure @vuumD low pressureD tmospheri pressureAD method of pulsing the preursors @moving sustrte or vlve souresA or ording to the types of souresF everl system types re disussedF sn typil moving sustrte evh growth system @pigure SFTA the sustrteD loted in the reess prt of the suseptorD is ontinuously rotted nd uts through strems of the gseous preursorsD in this seD trimethylgllium wqD q@gr3 A3 nd rsine @esr3 AF hese gseous preursors re introdued through seprte lines nd the gses ome in ontt with the sustrte only when it revolves under the inlet tueF his yle is repeted until the required thikness of qes is hievedF he exposure time to eh of the gs strems is out HFQ sF
IUP
A typical moving substrate ALD growth system used to grow GaAs lms. Adapted from M. A. Tischler and S. M. Bedair, Appl. Phys. Lett., 1986, 48, 1681.
Figure 5.6:
evh my e rried out in vuum system using n ultrEhigh vuum with movle sustrte holder nd gseous vlvingF sn this mnner it my e lso equipped with n inEsitu viih system for the diret oservtion of surfe tom on(gurtions nd other systems suh s D D nd ei for surfe nlysisF e lterl )ow system my lso e employed for suessful evi depositionF his uses n inert gs )ow for severl funtionsY it trnsports the retntsD it prevents pump oil from entering the retion zoneD it vlves the soures nd it purges the deposition site etween pulsesF snert gs vlving hs mny dvntges s it n e used t ultr high tempertures where mehnil vlves my fil nd it does not orrode s mehnil vlves would in the presene of hlidesF his method is sed on the ft tht s the inert gs is )owing through the feeding tue from the soure to the retion hmerD it loks the )ow of the souresF elthough in this system the front end of the sustrte reeives higher )ux density thn the downEstrem endD uniform growth rte ours s long s the sturtion lyer of the monoformtion predomintesF his lterl )ow system e'etively utilizes the sturtion mehnism of monolyer formtion otined in eviF hepending on the properties of the preursors usedD nd on the growth tempertureD vrious growth systems my e used for eviF
5.2.4 Requirements for ALD growth

everl prmeters must e tken into ount in order to ssure suessful evh growthF hese inlude the physil nd hemil properties of the soure mterilsD their pulsing into the retorD their intertion with the sustrte nd eh otherD nd the thermodynmis nd voltility of the (lm itselfF oure moleules used in evh n e either elementl or n inorgniD orgniD or orgnometlli omE poundF he hemil nture of the preursor is insigni(nt s long s it possesses the following propertiesF
IUQ st must e gs or must voltilize t resonle temperture produing su0ient vpor pressureF he vpor pressure must e high enough to (ll the sustrte re so tht the monolyer hemisorption n our in resonle length of timeF xote tht prolonged exposure to the sustrte n use the preursor to ondense on the surfe hindering the growthF ghemil intertion etween the two preursors prior to hemisorption on the surfe is lso undesiredF his my e overome y purging the surfe with n inert gs or hydrogen etween the pulsesF he inert gs not only seprtes the retnt pulses ut lso lens out the retion re y removing exess moleulesF elsoD the soure moleules should not deompose on the sustrte insted of hemisoringF he deomposition of the preursor leds to unontrolled growth of the (lm nd this defets the purpose of evh s it no longer is selfEontrolledD lyerEyElyer growth nd the qulity of the (lm plummetsF sn generlD temperture remins the most importnt prmeter in the evh proessF here exists proE essing window for idel growth of monolyersF he temperture ehvior of the rte of growth in monolyer units per yle gives (rst indition of the limiting mehnisms of n evh proessF sf the temperture flls too lowD the retnt my ondense or the energy of tivtion required for the surfe retion my not e ttinedF sf the temperture is too highD then the preursor my deompose or the monolyer my evporte resulting in poor evh growthF sn the pproprite temperture windowD full monolyer sturtion ours mening tht ll onding sites re oupied nd growth rte of one lttie unit per yle is oservedF sf the sturtion density is elow oneD severl ftors my ontriute to thisF hese inlude n oversized retnt moleuleD surfe reonstrutionD or the ond strength of n dsored surfe tom is higher when the neighoring sites re unoupiedF hen the lower sturtion density my e thermodynmilly fvoredF sf the sturtion density is ove oneD then the undeomposed preursor moleules form the monolyerF qenerllyD idel growth ours when the temperture is set where the sturtion density is oneF
5.2.5 Advantages of ALD

etomi lyer deposition provides n esy wy to produe uniformD rystllineD high qulity thin (lmsF st hs primrily een direted towrds epitxil growth of sssE @IQEISA nd ssE @IPEITA ompoundsD espeilly to lyered strutures suh s superltties nd superlloysF his pplition is due to the gretest dvntge of this methodD it is ontrollle to n ury of single tomi lyer euse of sturted surfe retionsF xot only thtD ut it produes epitxil lyers tht re uniform over lrge resD even on nonEplnr surfesD t tempertures lower thn those used in onventionl epitxil growthF enother dvntge to this method tht my e most importnt for future pplitionsD is the verstility ssoited with the proessF st is possile to grow di'erent thin (lms y hoosing suitle strting mterils mong the thousnds of ville hemil ompoundsF rovided tht the thermodynmis re fvorleD the djustment of the retion onditions is reltively esy tsk euse the proess is insensitive to smll hnges in temperture nd pressure due to its reltively lrge proessing windowF here re lso no limits in priniple to the size nd shpe of the sustrtesF yne dvntge tht is resultnt from the selfElimiting growth mehnism is tht the (nl thikness of the (lm is dependent only upon the numer of deposition yles nd the lttie onstnt of the mterilD nd n e reprodued nd ontrolledF he thikness is independent of the prtil pressures of the preursors nd growth tempertureF nder idel onditionsD the uniformity nd the reproduiility of the (lms re exellentF evi lso hs the potentil to grow very rupt heterostrutures nd very thin lyers nd these properties re in demnd for some pplitions suh s superltties nd quntum wellsF
5.2.6 Bibliography

hF gF frdleyD Chem. RevFD IWVWD 89D IQIUF wF itl nd wF veskelD NanotechnologyD IWWWD 10D IWF wF essD F ruttunenD nd wF eF rermnD J. Appl. PhysFD IWVQD 54D THRUF F untol nd tF entsonD Method for producing compound thin lmsD FF tent RDHSVDRQH @IWUUAF wF eF ishler nd F wF fedirD Appl. Phys. LettFD IWVTD 48D ITVIF
IUR

3
5.3 Chemical Vapor Deposition

note:
Electronic MaterialsF his module ws prepred with the ssistne of ott tokesF
5.3.1 Introduction
ghemil vpor deposition @ghA is deposition proess where hemil preursors re trnsported in the vpor phse to deompose on heted sustrte to form (lmF he (lms my e epitxilD polyrystlline or morphous depending on the mterils nd retor onditionsF gh hs eome the mjor method of (lm deposition for the semiondutor industry due to its high throughputD high purityD nd low ost of opertionF gh is lso ommonly used in optoeletronis pplitionsD optil otingsD nd otings of wer resistnt prtsF gh hs mny dvntges over physil vpor deposition @hA proesses suh s moleulr em evportion nd sputteringF pirstlyD the pressures used in gh llow oting of three dimensionl strutures with lrge spet rtiosF ine evportion proesses re very diretionlD h proesses re typilly line of sight depositions tht my not give omplete overge due to shdowing from tll struturesF eondlyD high preursor )ow rtes in gh give deposition rtes severl times higher thn hF elsoD the gh retor is reltively simple nd n e sled to (t severl sustrtesF ltrEhigh vuum is not needed for gh nd hnges or dditions of preursors is n esy tskF purthermoreD vrying evportion rtes mke stoihiometry hrd to ontrol in physil depositionF hile for gh stoihiometry is more esily ontrolled y monitoring )ow rtes of preursorsF yther dvntges of gh inlude growth of high purity (lms nd the ility to frite rupt juntionsF here reD howeverD some disdvntges of gh tht mke h more ttrtive for some pplitionsF righ deposition tempertures for some gh proesses @often greter thn THH gA re often unsuitle for strutures lredy frited on sustrtesF elthough with some mterilsD use of plsmEenhned gh or metlEorgni preursors my redue deposition temperturesF enother disdvntge is tht gh preursors re often hzrdous or toxi nd the yEproduts of these preursors my lso e toxiF herefore extr steps hve to e tken in the hndling of the preursors nd in the tretment of the retor exhustF elsoD mny preursors for ghD espeilly the metlEorgnisD re reltively expensiveF pinllyD the gh proess ontins lrge numer of prmeters tht must e urtely nd reproduily optimized to produe good (lmsF
5.3.2 Kinetics of CVD

e norml gh proess involves omplex )ow dynmis sine gses re )owing into the retorD retingD nd then yEproduts re exhusted out of the retorF he sequene of events during gh retion re shown in pigure SFU nd s followsX IA reursor gses input into the hmer y pressurized gs linesF PA wss trnsport of preursors from the min )ow region to the sustrte through the oundry lyer @pigure SFUAY QA edsorption of preursors on the sustrte @normlly hetedA @pigure SFUAF RA ghemil retion on the surfe @pigure SFUA SA etoms di'use on the surfe to growth sitesF TA hesorption of yEproduts of the retions @pigure SFUdAF UA wss trnsport of yEproduts to the min )ow region @pigure SFUeAF
3
IUS
Sequence of events during CVD: (a) diusion of reactants through boundary layer, (b) adsorption of reactants on substrate, (c) chemical reaction takes place, (d) desorption of adsorbed species, and (e) diusion out of by-products through boundary layer. Adapted from H. O. Pierson, Handbook of Chemical Vapor Deposition, Noyes Publications, Park Ridge (1992).
Figure 5.7:
5.3.2.1 The boundary layer
qs )ow in gh retor is generlly lminrD lthough in some ses heting of the hmer wlls will rete onvetion urrentsF he omplete prolem of gs )ow through the system is too omplex to e desried hereY howeverD ssuming we hve lminr )ow @often sfe ssumptionA the gs veloity t the hmer wlls will e zeroF fetween the wll @zero veloityA nd the ulk gs veloity there is oundry lyerF he oundry lyer thikness inreses with lowered gs veloity nd the distne from the tue inlet @pigure SFVAF etnt gses )owing in the ulk must di'use through the oundry lyer to reh the sustrte surfeF yftenD the suseptor is tilted to prtilly ompenste for the inresing oundryElyer thikness nd onentrtion pro(leF
Figure 5.8:
Organometallic Vapor-Phase Epitaxy: Theory and Practice
Development of boundary layer in a horizontal reactor. Adapted from G. B. Stringfellow, , Academic Press, New York (1994).
IUT
5.3.2.2 Rate limiting steps
huring gh the growth rte of the (lm is limited y either surfe retion kinetisD mss trnsport @di'uE sionA of preursors to the sustrteD or the feed rte of the preursorsF urfe retion ontrols the rte when growth ours t low tempertures @where the retion ours slowlyA nd lso domintes t low pressures @where the oundry lyer is thin nd retnts esily di'use to the surfeAD see pigure SFWF ine retnts esily di'use through the oundry lyerD the mount of retnt t the surfe is independent of retor pressureF hereforeD it is the retions nd motions of the preursors dsored on the surfe whih will determine the overll growth rte of the (lmF e sign of surfe retion limited growth would e dependene of the growth rte on sustrte orienttionD sine the orienttion would ertinly not 'et the thermodynmis or mss trnsport of the systemF
Figure 5.9:
ical Vapor Deposition
Surface reaction limited growth in CVD. Adapted from H. O. Pierson, , Noyes Publications, Park Ridge (1992).
Handbook of Chem-
e deposition limited y mss trnsport is ontrolled y the di'usion of retnts through the oundry lyer nd di'usion of yEproduts out of the oundry lyerF wss trnsport limits retions when the temperture nd pressure re highF hese onditions inreses the thikness of the oundry lyer nd mke it hrder for gses to di'use through @pigure SFIHAF sn dditionD deomposition of the retnts is typilly quiker sine the sustrte is t higher tempertureF hen mss trnsport limits the growthD either inresing the gs veloity or rotting the sustrte during growth will derese the oundry lyer nd inrese the growth rteF
IUU
Figure 5.10:
Chemical Vapor Deposition
Mass transport limited growth in CVD. Adapted from H. O. Pierson, , Noyes Publications, Park Ridge (1992).
Handbook of
peed rte limits the deposition when nerly ll the retnt is onsumed in the hmerF he feed rte is more importnt for hot wll retor sine the heted wlls will deompose lrge mount of the preursorF gold wll retors tend to hve higher deposition rtes sine the retnts re not depleted y the wllsF e plot of growth rte versus tempertureD known s n errhenius plotD n e used to determine the rte limiting step of retion @pigure SFIIAF wss trnsport limits retions t high tempertures suh tht growth rte inreses with prtil pressures of retntsD ut is onstnt with tempertureF urfe retion kinetis domintes t low tempertures where the growth rte inreses with tempertureD ut is onstnt with pressures of retntsF peed rte limited retions re independent of tempertureD sine it is the rte of gs delivery tht is limiting the retionF he errhenius plot will show where the trnsition etween the mss trnsport limited nd the surfe kinetis limited growth ours in the temperture regimeF
Figure 5.11:
Film Processes II
Dependence of CVD deposition rate on temperature. Adapted from J. G. Eden, in , Eds. J. L. Vossen and W. Kern, Academic Press, New York (1991).
Thin
snreses in retnt onentrtions will to point inrese the deposition rteF roweverD t very high retnt onentrtionsD gs phse nuletion will our nd the growth rte will drop @pigure SFIPAF low deposition in gh retor n often e ttriuted to either gs phse nuletionD preursor depletion due to hot wllsD thik oundry lyer formtionD low tempertureD or low preursor vpor pressureF
IUV
Figure 5.12: Demonstration of deposition rate on reactant concentration for CVD deposition. Adapted from J. G. Eden, in Thin Film Processes II, Eds. J. L. Vossen and W. Kern, Academic Press, New York (1991).
5.3.3 CVD systems

5.3.3.1 Precursor delivery
plow of retnts into the retor must e losely monitored to ontrol stoihiometry nd growth rteF reursor delivery is very importnt sine in mny ses the )ow rte n limit the depositionF por low vpor pressure solidsD rrier gs is pssed over or through ed of the heted solid to trnsport the vpor into the retorF qs )ow lines re usully heted to redue ondenstion of the vpor in the )ow linesF sn the se of gs preursorsD mss )owmeters esily guge nd ontrol the )ow rtesF viquid preursors re normlly heted in uler to hieve desired vpor pressure @pigure SFIQAF
Figure 5.13:
Schematic representation of a bubbler for liquid precursors.
en inert gs suh s hydrogen is uled through the liquid nd y lulting the vpor pressure of the retnt nd monitoring the )ow rte of the hydrogenD the )ow rte of the preursor is ontrolled y using @SFIAD where MO is the )ow rte of the metlEorgni preursorD H2 is the )ow rte of hydrogen through the ulerD MO is the vpor pressure of the metlEorgni t the uler tempertureD nd B is
IUW the pressure of the ulerF @SFIA enother method of introduing liquid preursors involves )sh vporiztion where the liquid is pssed into )sk heted ove the oiling point of the liquidF he gs vpor is then pssed through heted lines to the gh hmerF yftenD rrier gs is dded to provide (xed )ow rte into the retorF his method of preursor introdution is useful when the preursor will deompose if heted over timeF e similr tehnique lled spry pyrolysis introdues the preursors in the form of erosol dropletsF he droplets evporte in the hmer from the heted gs ove the sustrte or heted hmer wlls @pigure SFIRAF hen the retion proeeds s norml gh proessF
Schematic representation of a typical aerosol delivery system for CVD precursors. Adapted from T. T. Kodas and M. J. Hamton-Smith, The Chemistry of Metal CVD, VCH, New York (1994).
Figure 5.14:
5.3.3.2 Thermal CVD reactors
sn therml gh tempertures s high s PHHH g my e needed to thermlly deompose the preursorsF reting is normlly omplished y use of resistive hetingD rdio frequeny @rfA indution hetingD or rdint hetingF here re two si types of retors for therml ghX the hot wll retor nd the old wll retorF e hot wll retor is n isotherml furne into whih the sustrtes re pledF rot wll retors re typilly very lrge nd depositions re done on severl sustrtes t oneF ine the whole hmer is hetedD preise temperture ontrol n e hieved with orret furne designF e disdvntge of the hot wll on(gurtion is tht deposition ours on the wlls of the hmer s well s on the sustrteF es onsequeneD hot wll retors must e frequently lened to redue )king of prtiles from the wlls whih my ontminte the sustrtesF purthermoreD retions in the heted gs nd t the wlls deplete the retnts nd n result in feed rte limited growthF pigure SFIS shows typil low pressure hot wll gh retorF
IVH
Figure 5.15: Schematic of a typical low pressure hot wall CVD reactor used in coating silicon substrates. Adapted from H. O. Pierson, Handbook of Chemical Vapor Deposition, Noyes Publications, Park Ridge (1992).
sn old wll retor only the sustrte is hetedD usully y indution or rdint hetingF ine most gh retions re endothermiD deposition is preferentilly on the re of highest tempertureF es resultD deposition is only on the sustrte nd the ooler retor wlls sty lenF gold wll gh hs two min dvntges over the hot wll on(gurtionF pirstD prtiulte ontmintion is redued sine there re no deposits formed on the wlls of the retorF eondD sine deomposition only ours on the sustrte there is no depletion of soure gses due to retion on the wllsF roweverD hot wll retors tend to hve higher throughput sine the designs more esily ommodte multiple wfer on(gurtionsF he (nl issue in design of therml gh retor is the operting pressureF he pressure of the retor hs lrge e'et on the rte limiting step of the depositionF etmospheri pressure retors hve lrge oundry lyer @pigure SFIHA nd nonEuniform di'usion of retnts through the oundry lyer often results in nonEuniform (lm ompositions ross the wferF gonverselyD low pressure retors hve nerly nonEexistent oundry lter nd retnts esily di'use to the sustrte @pigure SFWAF roweverD the di0ulty in mintining uniform temperture pro(le ross the wfer n result in thikness nonEuniformities sine the deposition rte in low pressure retors is strongly temperture dependentF greful studies of the )ow dynmis nd temperture pro(les of gh retors re lwys rried out in order to hieve uniform mteril depositionsF
5.3.3.3 Plasma-enhanced CVD
lsms re generted for vriety of thin (lm proesses inluding sputteringD ethingD shingD nd plsmE enhned ghF lsmEenhned gh @ighAD sometimes lled plsmEssisted @eghAD hs the dvntge tht plsm tivted retions our t muh lower tempertures ompred to those in therml ghF por exmpleD the therml gh of silion nitride ours etween UHH E WHH gD the equivlent igh proess is omplished etween PSH E QSH gF e plsm is prtilly ionized gs onsisting of eletrons nd ionsF ypil ioniztion frtions of IH-5 to -1 IH re enountered in proess retorsF lsms re eletrilly ondutive with the primry hrge rriers eing the eletronsF he light mss of the eletron llows it to respond muh more quikly to hnges in the (eld thn the hevier ionsF wost plsms used for igh re generted using rf eletri (eldF sn the high frequeny eletri (eldD the light eletrons re quikly elerted y the (eld ut do not inrese the temperture of the plsm euse of their low mssF he hevy ions nnot respond to the quik hnges
IVI in diretion nd therefore their temperture stys lowF iletron energies in the plsm hve wxwellin distriution in the HFI ! PH e rngeF hese energies re su0iently high to exite moleules or rek hemil onds in ollisions etween eletrons nd gs moleulesF he high energy eletrons inelstilly ollide with gs moleules resulting in exittion or ioniztionF he retive speies generted y the ollisions do not hve the energy rriers to retions tht the prent preursors doF hereforeD the retive ions re le to form (lms t tempertures muh lower thn those required for therml ghF he generl retion sequene for igh is shown in pigure SFITF sn ddition to the proesses tht our in therml ghD retive speies resulting from eletron dissoition of prent moleules lso di'use to the surfeF he retive speies hve lower tivtion energies for hemil retions nd usully hve higher stiking oe0ients to the sustrteF hereforeD the igh retion is dominted y the retive speies on the surfe nd not ny of the the prent preursor moleules tht lso di'use to the surfeF
Figure 5.16:
Techniques
Reaction sequence in PECVD. Adapted from M. Konuma, , Springer-Verlag, New York (1992).
Film Deposition by Plasma
e si igh retor is shown in pigure SFIUF he wfer huk ts s the lower eletrode nd is normlly pled t ground potentilF qses re either introdued rdilly t the edges of the retor nd pumped out from the enterD or gses n e introdued from the enter nd pumped t the edges s shown in pigure SFIUF he mgneti drive llows rottion of the wfers during proessing to rndomize sustrte positionF ome newer retors introdue the gses through holes drilled in the upper eletrodeF his method of gs introdution gives more uniform plsm distriutionF
IVP
Figure 5.17:
Handbook of Chemical Vapor Deposition
Schematic representation of a radial ow PECVD reactor. Adapted from H. O. Pierson, , Noyes Publications, Park Ridge (1992).
lsm gh hs numerous dvntges over therml ghF yviously the redued deposition temperture is onus for the semiondutor industry whih must worry out dopnt di'usion nd metl interonnets melting t the tempertures required for therml ghF elsoD the low pressures @etween HFI E IH orrA required for sustining plsm result in surfe kinetis ontrolling the retion nd therefore greter (lm uniformityF e disdvntge of plsm gh is tht it is often di0ult to ontrol stoihiometry due to vritions in ond strengths of vrious preursorsF por exmpleD igh (lms of silion nitride tend to e silion rih euse of the reltive ond strength of x2 reltive to the iEr ondF edditionllyD some (lms my e esily dmged y ion omrdment from the plsmF
5.3.3.4 Photochemical CVD
hotohemil gh uses the energy of photons to initite the hemil retionsF hotodissoition of the hemil preursor involves the sorption of one or more photons resulting in the reking of hemil ondF he most ommon preursors for photoEssisted deposition re the hydridesD ronylsD nd the lkylsF he dissoition of dimethylzin y @SFPAD photon retes zin rdil nd methyl rdil @. gr3 A tht will ret with hydrogen in the retor to produe methneF @SFPA vike severl metlEorgnisD dimethylzin is dissoited y the sorption of only one photonF roweverD some preursors require sorption of more thn one photon to ompletely dissoiteF here re two si on(gurtions for photohemil ghF he (rst method uses lser primrily s lolized het soureF he seond method uses high energy photons to deompose the retnts on or ner the growth surfeF sn therml lser ghD sometimes referred to s lser pyrolysisD the lser is used to het sustrte tht sors the lser photonsF vser heting of sustrtes is very lolized proess nd deposition ours
IVQ seletively on the illuminted portions of the sustrtesF ixept for the method of hetingD lser gh is identil to therml ghF he lser gh method hs the potentil to e used for diret writing of fetures with reltively high resolutionF he lterl extent of (lm growth when the sustrte is illuminted y lser is determined not only y the spot size of the lserD ut y the therml ondutivity of the sustrteF e vrition of lser pyrolysis uses lser to het the gs moleules suh tht they re frgmented y therml proessesF hotohemil e'ets n e indued y lser if the preursor moleules sor t the lser wvelengthF photons hve su0ient energy to rek the onds in the preursor hemilsF vserEssisted gh @veghA uses lserD usully n eximer lserD to provide the high energy photons needed to rek the onds in the preursor moleulesF pigure SFIV shows two geometries for veghF por the perpendiulr illumintion the photohemil e'ets generlly our in the dsored dlyer on the sustrteF erpendiulr irrdition is often done using lmp insted of lser so tht unwnted sustrte heting is not produed y the light soureF he prllel illumintion on(gurtion hs the ene(t tht retion yEproduts re produed further from the growth surfe nd hve less hne of eing inorported into the growing (lmF he min ene(t of vegh is tht nerly no het is required for deposition of high qulity (lmsF
Figure 5.18:
Thin Film Processes II
Parallel (a) and perpendicular (b) irradiation in laser CVD. Adapted from J. G. Eden, in , Eds. J. L. Vossen and W. Kern, Academic Press, New York (1991).
IVR
en pplition of lser photolysis is photonuletionF hotonuletion is the proess y whih hemisored dlyer of metl preursors is photolyzed y the lser to rete nuletion site for further growthF hotonuletion is useful in promoting growth on sustrtes tht hve smll stiking oe0ients for gs phse metl tomsF fy eginning the nuletion proess with photonuletion the nturl rrier to surfe nuletion on the sustrte is overomeF
5.3.4 Bibliography
tF qF idenD in Thin Film Processes IID idsF tF vF ossen nd F uernD edemi ressD xew ork @IWWIAF F F uods nd wF tF rmtonEmithD The Chemistry of Metal CVDD grD xew ork @IWWRAF wF uonumD Film Deposition by Plasma TechniquesD pringerEerlgD xew ork @IWWPAF rF yF iersonD Handbook of Chemical Vapor DepositionD xoyes ulitionsD rk idge @IWWPAF F eif nd F uernD in Thin Film Processes IID idsF tF vF ossen nd F uernD edemi ressD xew ork @IWWIAF qF fF tringfellowD Organometallic Vapor-Phase Epitaxy: Theory and PracticeD edemi ressD xew ork @IWWRAF
5.4 Liquid Phase Deposition

5.4.1 Introduction
ilion dioxide @siliD iy2 A hs een the most reserhed hemil ompound prt from wterF ili hs een used throughout historyD for exmpleD )intD whih when shrpened formed one of humnities (rst toolsF grystlline siliD or sndD ws melted into glss s erly s SHHH fFgFD irthing tehnology tht hs gined sophistition in modern timesF ilion is the seond most plentiful element in the irth9s rustD the most plentiful eing oxygenF st is thus surprising tht it ws not until IVHH tht sili ws nmed ompound y ir rumphry hvyF reD howeverD filed to isolte its omponents vi eletrolysisD nd it is tons to ferzelius who is thus redited with disovering sili in IVPRF re heted potssium )uorosilite with potssium metl ndD fter purifying the produt of this retion with wterD produed morphous sili powderF he most ommon forms of sili employed in industry inlude EqurtzD vitreous siliD sili gelD fumed sili nd ditomeous erthF yntheti qurtz is hydrothermlly grown from seed rystlD with queous xyr nd vitreous iy2 D t RHH g nd IFU krF feuse it is piezoeletri mterilD it is used in rystl osilltorsD trnsduersD pikups nd (lters for frequeny ontrol nd modultionF itreous sili is super ooled liquid sili used in lortory glsswreD protetive tuing sheths nd vpor grown (lmsF ili gel is formed from the retion of queous sodium silite with idD fter whih it is wshed nd dehydrtedF ili gel is n exeptionlly porous mteril with numerous pplitions inluding use s dessintD hromtogrphi supportD tlyst sustrte nd insultorF yrogeni or fumed sili is produed y the high temperture hydrolysisD in n oxyhydrogen )meD of igl4 F sts pplitions inlude use s thikening gent nd reinforing (ller in polymersF hitomeous erthD the etoEskeletons of tiny uniellulr mrine lge lled ditomsD is mined from vst deposits in iurope nd xorth emeriF sts primry use is in (ltrtionF edditionl pplitions inlude use s n rsiveD insultorD (ller nd lightweight ggregteF wethods of olloidl growth nd thin (lm deposition of morphous sili hve een investigted sine IWPSF he two most ommon nd wellEinvestigted methods of forming iy2 in sol or s (lm or oting re ondenstion of lkoxysilnes @known s the toer methodA nd hydrolysis of metl lkoxides @the sler or dense sili h proessAF
4
IVS
5.4.2 Liquid phase deposition (LPD)

vh is method for the nonEeletrohemil prodution of polyrystlline ermi (lms t low temperE turesF vhD long with other queous solution methods hemil th deposition @gfhAD suessive ion lyer dsorption nd retion @sveA nd eletroless deposition @ihA with tlyst hs developed s potentil sustitute for vporEphse nd hemilEpreursor systemsF equeous solution methods re not dependent on vuum systems or glove oxesD nd the use of esily quired regents redues reline on exE pensive or sensitive orgnometlli preursorsF husD vh holds potentil for redued prodution osts nd environmentl imptF pilms my e deposited on sustrtes tht might not e hemilly or mehnilly stle t higher temperturesF sn dditionD the use of liquid s deposition medium llows oting of nonE plnr sustrtesD expnding the rnge of sustrtes tht re ple of eing otedF equeous deposition tehniques hve not rehed the level of mturtion tht vporEphse tehniques hve in respet to high level of ontrol over ompositionD mirostruture nd growth rtes of the resulting (lmsD ut their prospet mkes them ttrtive for reserhF vh generlly refers to the formtion of oxide thin (lmsD the most ommon eing iy2 D from n queous solution of metlE)uoro omplex wpn m-n D whih is slowly hydrolyzed using wterD ori id or luminum metlF eddition of wter drives preipittion of the oxideF fori id nd luminum work s )uoride svengersD rpidly wekening the )uoro omplex nd preipitting the oxideF hese retnts re dded either drop wise or outrightD oth methods llowing for high ontrol of the hydrolysis retion nd of the solution9s supersturtionF pilm formtion is omplished from highly idi solutionsD in ontrst to the si or wekly idi solutions used in hemil th depositionF e generi desription of the vh retion is shown in @SFQAD where m is the hrge on the metl tionF sf the onentrtion of wter is inresed or the onentrtion of hydro)uori id @rpA is deresedD the equilirium will e shifted towrd the oxideF se of ori id or luminum metl will omplish the ltterD see @SFRA nd @SFSAF he most populr of these methods for omplishing oxide formtion hs een through the ddition of ori idF @SFQA
@SFRA
@SFSA he (rst ptent using liquid phse deposition @vhA of silion dioxide vi )uorosilii id solutions @r2 ip6 A ws grnted to the dio gorportion of emeri @geA in IWSHF ge used vh s method for oting ntiEre)etive (lms on glssD ut the ptent promised further pplitionsF ine this initil ptent there hve een mny further ptents nd ppers utilizing this methodD in vrile formsD to ot sustrtesD usully silionD with silion dioxideF he impetus ehind this work is to rete n lterntive to the growth of insultor otings y therml oxidtion or hemil vpor deposition @ghA for plnr silion hip tehnologyF herml oxidtion nd gh re performed t elevted temperturesD requiring higher output of energy nd more omplited instrumenttion thn tht of vhF he most simple nd elegnt of the vh methods uses only wter to tlyze sili thin (lm growth on silion from solution of )uorosilii id supersturted with silion dioxideD @SFTAF @SFTA he mount of wter reted with the supersturted )uorosilii id solution ontrols oth the growth rte nd inorportion of )uorine into the resulting sili mtrixF foth growth rte nd )uorine ontent inrese with inresed ddition of wterF ltimtely this dilution 'ets the optil properties of the resulting sili (lmY n inresed mount of )uorine dereses its dieletri onstnt @nd thus its refrtive indexAF
IVT
o ensure uniform (lm growth with vhD the preprtion of the surfe to e oted is of utmost importneF uitle tretments my involve the formtion of surfe hydroxidesD the preEdeposition or selfE ssemly of n pproprite seed lyerF he most e0ient overge is seen with silion surfes funtionlized with hydroxy @EyrA groups prior to immersion in the growth solutionF his n e hieved through pproprite ething of the silion surfeF st is proposed tht the silnol @iEyrA groups t to seed the growth of the sili (lm through ondenstion retions with the silii id formed in the growth solutionF vee nd oEworkers nd romm seprtely propose tht intermediteD hydrolyzed speiesD ipn @yrA4-n @n < RAD re formed y the retion shown in @SFUAF eording to veeD these speies then ret with the sustrte surfe to form (lmF romm proposes tht )uorineEontining siloxnes re susequently formedD whih dsor onto the surfe where ondenstion nd onding ours etween the oligomers nd surfe hydroxyl groupsF he former mehnism implies moleulr growth mehnismD wheres the ltter implies homogeneous nuletion with susequent depositionF @SFUA sn onentrted )uorosilii id solutions sili n e dissolved to well eyond its soluilityD forming )uorosilion omplexes suh s ip6 Fip4 2- D @SFVAF he ridged )uorosilion omplex hs eletron de(ient silion euse of the high eletronegtivity of the onded )uorinesD reting wek iEp ondsF hese onds re then prone to nuleophili ttk y wterF he )uorine ion @p- A omines with the proton in this retion to form hydro)uori id @rpAF he produt of this retion n then ret further with wter to yield ip4 @yrA2 2- D ip4 nd rpF he high idity of the solution then llows protons to ret with ip4 @yrA2 2- to form tetr)uorosilite @ip4 A nd wterD @SFWAF rydrolysis of the ip4 will then yield the hex)uorosilite nionD protons nd silii idD @SFIHAF @SFVA
@SFWA
@SFIHA ilii id is dsored onto the surfe of the sustrte tht hs een introdued into the growth solutionF woleulr growth of sili on the sustrte surfe is initilized in n id tlyzed dehydrtion etween the silii id nd the silnol groups on the sustrte surfeF iEyEi onds re formedD resulting in n initil sili oting of the surfeF pollowing retions etween the initil sili oting nd the monosilii id in solution result in further sili deposition nd growthF feuse of the presene of rp in the solutionD the surfe nd growing sili mtrix is sujet to ttk ording to the retion in @SFIIAF his explins the inorportion of quntity of )uorine into the sili (lmF edditionllyD it revels tht ertin mount of sili ething ours long with growthF feuse of the prevlene of the silii id in the solutionD howeverD deposition is predominntF @SFIIA his proposed mehnismD whih is more in depth thn those proposed y vee nd rommD eluidtes wht is experimentlly provenF he deposition rte of the sili inreses with ddition of r2 y euse the nuleophili ttk of the )uorosilion omplex is then ugmentedD inresing the onentrtion of silii id in the growth solutionF he r2 y ddition inreses the retion rte nd thus the onentrtion of rp in the growth solutionD resulting in greter inorportion of )uorine into the sili mtrix euse of rp ttk of the deposited (lmF edditionllyD eh9s mehnism supports moleulr growth modelD iFeFD heterogeneous growthD whih represents onsensus of the ody of reserh performed thus frF sn solution with dissolved ermi preursorsD nuletion nd growth will our either in solution @homogenous nuletionA or on the surfes of introdued solid phses @heterogeneous nuletionAF uessful
IVU (lm formtion relies on the promotion of heterogeneous nuletionF oluility generlly depends on the solution pr nd the onentrtion of the speies in solutionF es the solution rosses over from solvted stte to stte of supersturtionD (lm formtion n ourF st is vitl to ssure tht the stte of supersturtion is one tht promotes (lm growth nd not homogeneous nuletion nd preipittionF his onept is illustrted in pigure SFIWF
Idealized solubility diagram for lm forming species in water. Adapted from B. C. Bunker, P. C. Rieke, B. J. Tarasevich, A. A. Campbell, G. E. Fryxall, G. L. Gra, L. Song, J. Liu, J. W. Virden, and G. L. McVay, Science, 1994, 264, 48.
Figure 5.19:
ili n e dissolved in )uorosilii id to well ove its soluility in wterD whih is pproximtely PPH ppm @mgGvAF hepending on the onentrtion of the )uorosilii id solutionD it n ontin up to PH7 more sili thn is implied y the formul r2 ip6 F efter sturtion of the solution with iy2 D the solvted speies is mixture of )uorosilitesD whih rets s explined erlierF st must e emphsized tht ddition of wter in this retion is not simply dilutionD ut is the ddition of retntD whih ples the solution in metstle stte @the lue re in pigure SFIWA in preprtion for the introdution of suitle surfe to seed the growth of siliF enother importnt ftor in solution growth methods is interfil energyF hen sustrte with lower interfil energy thn tht of growing homogeneous nuleus is introdued into growth solutionD heterogeneous growth is fvoredF husD seeded growth mehnism y de(nition introdues sustrte of lower interfil energy into supersturted solutionD filitting heterogeneous growthF vower interfil energies n e produt of surfe modi(tionD s well s property of the mterils9 nturl stteF
5.4.2.1 Comparing LPD to sol-gel
en lterntive method to vh for forming sili thin (lms is the solEgel methodF e sol is olloidl dispersion of prtiles in liquidF e gel is mteril tht ontins ontinuous solid mtrix enlosing ontinuous liquid phseF he liquid inhiits the solid from ollpsing nd the solid impedes relese of the liquidF e forml de(nition of solEgel proessing is the growth of olloidl prtiles nd their linking together to form
IVV
gelF his method desries oth the hydrolysis nd ondenstion of silion lkoxides nd the hydrolysis nd ondenstion of queous silites @the h proessAF sn the hydrolysis of silion lkoxidesD n lkoxide group is repled with hydroxyl groupD @SFIPAF purther ondenstion retions etween lkoxyl groups or hydroxyl groups produe siloxne ondsD see @SFIQA nd @SFIRAF @SFIPA
@SFIQA
@SFIRA etrmethoxysilne i@yweA4 D wy nd tetrethylorthoxysilne i@yitA4 D iy re the most omE monly used preursors in sili solEgel proessingF he lkoxides re hydrolyzed in their prent loholsD with minerl id or se tlystD produing silite gels tht n e deposited s otingsF he toer methodD whih utilizes this hemistryD relies on homogeneous nuletion to produe monodisperse solsF sler9s h method of sili (lm formtion ws originlly ptented s pigment oting to inrese disE persiility of titni prtiles for use in the pint industryF he h method is sed on the queous hemistry of sili nd tkes dvntge of the speies present in solution t vrying prF felow pr U threeEdimensionl gel networks re formedF eove pr U sili surfes re quite negtively hrged @@SFISAAD so tht prtile growth ours without ggregtionF he isoeletri point of sili is pr PF etions ove nd elow pr P re thought to our through imoleulr nuleophili ondenstion mehnismsF eove pr P n nioni speies ttks neutrl speies @@SFITAA nd elow pr P ondenstion involves protonted silnol @@SFIUAAF he h proess hs een utilized extensively in solEgel oting tehnology nd s growth method for monodisperse nd polydisperse solsF @SFISA
@SFITA
@SFIUA
5.4.3 Bibliography
fF gF funkerD F gF iekeD fF tF rsevihD eF eF gmpellD qF iF pryxllD qF vF qr'D vF ongD tF viuD tF F irdenD nd qF vF wyD ScienceD IWWRD 264D RVF FErF ghngD gFEF rungD nd tFEF hieD J. Electrochem. Soc.D IWWUD 144D IIRRF tFEF ghou nd FEgF veeD J. Electrochem. Soc.D IWWRD 141D QPIRF F rommD F utohD F mdD nd F wuroD J. Electrochem. Soc.D IWWQD 140D PRIHF F uF slerD The Chemistry of Silica Solubility, Polymerization, Colloid and Surface Properties, and BiochemistryD tohn iley 8 ons @IWUWAF rF F tfryD iF eF hitsittD nd eF F frronD J. Mater. SciFD PHHUD 42D UQVIF F xiesen nd wF F he quireD J. ElectroceramicsD PHHID 6D ITWF xF yzwD F uumzwD nd F oD Thin Solid FilmsD PHHPD 418D IHPF F toerD eF pinkD nd iF fohnD J. Colloid Interface Sci.D IWTVD 26D TPF hF hitehouseD Glass of the Roman EmpireD gorning @IWVVAF
IVW
iF eF hitsitt nd eF F frronD Nano LettFD PHHQD 3D UUSF iF eF hitsitt nd eF F frronD Chem. CommunFD PHHQD IHRPF iF eF hitsitt nd eF F frronD J. Colloid Interface SciFD PHHSD 287D QIVF gFEpF ehD gFEvF ghenD nd qFErF vinD J. Electrochem. Soc.D IWWRD 141D QIUUF
IWH
Chapter 6
Chemical Vapor Deposition

6.1 Selecting a Molecular Precursor for Chemical Vapor Deposition
6.1.1 Introduction
he proven utility of hemil vpor deposition @ghA in wide rnge of eletroni mterils systems @semiondutorsD ondutorsD nd insultorsA hs driven reserh e'orts to investigte the potentil for thin (lm growth of other mterilsD inludingX high temperture superonduting metl oxidesD piezoeletri mterilD etF woreoverD gh potentilly is well suited for the preprtion of thin (lms on wide rnge of sustrtesD inluding those of nonplnr geometriesF gh o'ers the dvntges of mild proess onditions @iFeFD low temperturesAD ontrol over mirostruture nd ompositionD high deposition rtesD nd possile lrge sle proessingF es with ny gh proessD howeverD the ritil ftor in the deposition proess hs een the seletion of preursors with suitle trnsport propertiesF
1
6.1.2 Factors in selecting a CVD precursor molecule

he following properties re mong those tht must e onsidered when seleting suitle ndidtes for gh preursorX IF he preursor should e either liquid or solidD with su0ient vpor pressure nd mss trnsport t the desired tempertureD preferly elow PHH gF viquids re preferred over solidsD due to the di0ulty of mintining onstnt )ux of soure vpors over nonEequilirium peroltion @solidA proessF uh nonEuling proesses re funtion of surfe reD nonEonstnt vrile with respet oth to time nd prtile sizeF he upper temperture limit is not ditted y hemil ftorsY rtherD it is limittion imposed y the stility of the mss )ow ontrollers nd pneumti vlves utilized in ommeril deposition equipmentF st must e stressed tht while the hievement of n optimum vpor pressure for e0ient utiliztion s n industrilly prtile soure providing high (lm growth rtes @>IH orr t PS gA is worthy golD the usle pressure regimes re those in whih evlution n e rried out on ompounds whih exhiit vpor pressures exeeding I orr t IHH gF PF he preursor must e hemilly nd thermlly stle in the region ordered y the evportion nd trnsport temperturesD even fter prolonged useF irly workers were plgued y irreproduile (lm growth results used y premture deomposition of soure ompounds in the ulerD in trnsfer linesD ndD silly everywhere except on the sustrteF uh experienes re to e voided3 QF fy its very ntureD gh demnds deomposle preursorF his generlly is omplished thermllyY howeverD the plsmEenhned growth regime hs seen muh improvementF sn dditionD photolyti proesses hve tremendous potentilF xeverthelessD the preursor must e thermlly roust until deposition conditions are employedF
1
IWI
IWP
CHAPTER 6. CHEMICAL VAPOR DEPOSITION
RF he preursor should e reltively esy to synthesizeD ensuring su0ient vilility of mteril for testing nd fritionF st lso is importnt tht the synthesis of the ompound e reproduileF st should e simple to prepre nd purify to reltively high level of purityF st should e nonEtoxi nd environmentally friendly @iFeFD s low toxiity s n e ttinedD given the fundmentl toxiity of prtiulr elements suh s meruryD thlliumD riumD etFAF st should e routine to reprodue nd sleEup the preprtion for further developmentl studiesF st should utilize redily ville strting regentsD nd proeed y minimum numer of hemil trnsformtions in order to minimize the ostF SF hue to hndling onsidertionsD the soure should e oxidtivelyD hydrolytillyD thermlly nd phoE tohemilly stle under norml storge onditionsD in ddition the preusor should resist oligomerE iztion @in the solidD liquidD or gseous sttesAF st is worth noting tht prtitioners of metl orgni gh @wyghAD espeilly for IQEIS mterils hve of neessity eome expert in the hndling of very toxiD highly ir sensitive mterilsF ristorillyD reserhers were limited in their hoies of preursors to those tht were redily known nd ommerilly villeF st must e emphsized tht none of these previously known ompounds hd een designed spei(lly to serve s vpor phse trnsport moleules for the ssoited elementF husD the sope ws often limited to wht ws ommerilly villeF roweverD s new ompounds hve now een mde with the spei( gol of providing idel gh preursors the hoie to demi nd industry hs inresedF
6.1.3 Bibliography
qF fF tringfellowD Organometallic Vapor Phase Epitaxy: Theory and PracticeD edemi ressD xew ork @IWVWAF
6.2 Determination of Sublimation Enthalpy and Vapor Pressure for Inorganic and Metal-Organic Compounds by Thermogravimetric Analysis
2
6.2.1 Introduction
wetl ompounds nd omplexes re invlule preursors for the hemil vpor deposition @ghA of metl nd nonEmetl thin (lmsF sn generlD the preursor ompounds re hosen on the sis of their reltive voltility nd their ility to deompose to the desired mteril under suitle temperture regimeF nfortuntelyD mny redily otinle @ommerilly villeA ompounds re not of su0ient voltility to mke them suitle for gh pplitionsF husD prediction of the voltility of metlEorgni ompounds s funtion of its lignd identity nd moleulr struture would e desirle in order to determine the suitility of suh ompounds s gh preursorsF iqully importnt would e method to determine the vpor pressure of potentil gh preursor s well s its optimum temperture of sulimtionF st hs een oserved tht for orgni ompounds it ws determined tht rough proportionlity exists etween ompound9s melting point nd sulimtion enthlpyY howeverD signi(nt devition is oserved for inorgni ompoundsF inthlpies of sulimtion for metlEorgni ompounds hve een previously determined through vriE ety of methodsD most ommonly from vpor pressure mesurements using omplex experimentl systems suh s unudsen e'usionD temperture drop mirolorimetry ndD more reentlyD di'erentil snning lorimeE try @hgAF roweverD the mesured vlues re highly dependent on the experimentl proedure utilizedF por exmpleD the reported sulimtion enthlpy of el@A3 @pigure TFID where w a elD n a QA vries from RUFQ to IPT ktGmolF
2
IWQ
Structure of a typical metal -diketonate complex. (a) acetylacetonate (acac); (b) triuoro acetylacetonate (tfac), and (c) hexauoroacetylacetonate (hfac).
Figure 6.1:
hermogrvimetri nlysis o'ers simple nd reproduile method for the determintion of the vpor pressure of potentil gh preursor s well s its enthlpy of sulimtionF
6.2.2 Determination of sublimation enthalpy

he enthlpy of sulimtion is quntittive mesure of the voltility of prtiulr solidF his informtion is useful when onsidering the fesiility of prtiulr preursor for gh pplitionsF en idel sulimtion proess involves no ompound deomposition nd only results in solidEgs phse hngeD iFeFD @TFIAF @TFIA ine phse hnges re thermodynmi proesses following zeroEorder kinetisD the evportion rte or rte of mss loss y sulimtion @msub AD t onstnt temperture @AD is onstnt t given tempertureD @TFPAF hereforeD the msub vlues my e diretly determined from the liner mss loss of the qe dt in isotherml regionsF @TFPA he thermogrvimetri nd di'erentil therml nlysis of the ompound under study is performed to determine the temperture of sulimtion nd therml events suh s meltingF pigure TFP shows typil qGhe plot for gllium hlogenide une ompound @pigure TFQAF
IWR
6.2: A typical thermogravimetric/dierential thermal analysis (TG/DTA) analysis of [(EtMe2 C)GaSe]4 , whose structure is shown in Figure 6.3. Adapted from E. G. Gillan, S. G. Bott, and A. R. Barron, Chem. Mater., 1997, 9, 3, 796. Figure
Figure 6.3: Structure of gallium chalcogenide cubane compound, where E = S, Se, and R = CMe3 , CMe2 Et, CEt2 Me, CEt3 .
6.2.2.1 Data collection
sn typil experiment S E IH mg of smple is used with heting rte of F S gGmin up to under either PHHEQHH mvGmin inert @x2 or erA gs )ow or dynmi vuum @caF HFP orr if using typil vuum pumpAF he rgon )ow rte ws set to WHFH mvGmin nd ws refully monitored to ensure stedy )ow rte during runs nd n identil )ow rte from one set of dt to the nextF yne the temperture rnge is de(nedD the qe is run with preprogrmmed temperture pro(le @pigure TFRAF st hs een found tht su0ient dt n e otined if eh isotherml mss loss is monitored over period @etween U nd IH minutes is found to e su0ientA efore moving to the next temperture plteuF sn ll ses it is importnt to on(rm tht the mss loss t given temperture is linerF sf it is
IWS notD this n e due to either @A temperture stiliztion hd not ourred nd so longer times should e spent t eh isothermD or @A deomposition is ourring long with sulimtionD nd lower temperture rnges must e usedF he slope of eh mss drop is mesured nd used to lulte sulimtion enthlpies s disussed elowF
Figure 6.4:
A typical temperature prole for determination of isothermal mass loss rate.
es n illustrtive exmpleD pigure TFS displys the dt for the mss loss of gr@A3 @pigure TFID where w a grD n a QA t three isotherml regions under onstnt rgon )owF ih isotherml dt set should exhiit liner reltionF es expeted for n endotherml phse hngeD the liner slopeD equl to msub D inreses with inresing tempertureF
IWT
Figure 6.5: Plot of TGA results for Cr(acac)3 performed at dierent isothermal regions. Adapted from B. D. Fahlman and A. R. Barron, Adv. Mater. Optics Electron., 2000, 10, 223.
mples of iron etyletonte @pigure TFID where w a peD n a QA my e used s lirtion stndrd through rsub determintions efore eh dy of useF sf the mesured vlue of the sulimtion enthlpy for pe@A3 is found to di'er from the literture vlue y more thn S7D the smple is reEnlyzed nd the )ow rtes re optimized until n pproprite vlue is otinedF ynly fter suh lirtion is optimized should other omplexes e nlyzedF st is importnt to note tht while smll mounts @< IH7A of involtile impurities will not interfere with the rsub nlysisD ompetitively voltile impurities will produe higher pprent sulimtion rtesF
note:
st is importnt to disuss t this point the vrious ftors tht must e ontrolled in order to otin meningful @usefulA msub dt from qe dtF IF he sulimtion rte is independent of the mount of mteril used ut my exhiit some dependene on the )ow rte of n inert rrier gsD sine this will 'et the equilirium onentrtion of the une in the vpor phseF hile little vrition ws oserved we deided tht for onsisteny msub vlues should e derived from vuum experiments onlyF PF he surfe re of the solid in given experiment should remin pproximtely onstntY otherwise the sulimtion rte @iFeFD mssGtimeA t di'erent tempertures nnot e ompredD sine s the reltive surfe re of given rystllite dereses during the experiment the pprent sulimtion rte will lso dereseF o minimize this prolemD dt ws tken over smll temperture rnges @caF QH gAD nd overll sulimtion ws kept low @caF PS7 mss loss representing surfe re hnge of less thn IS7AF sn experiments where signi(nt surfe re hnges ourred the vlues of msub devited signi(ntly from linerity on log@msub A versus IG plotF QF he ompound eing nlyzed must not deompose to ny signi(nt degreeD euse the mss hnges due to deomposition will use redution in the pprent msub vlueD produing erroneous resultsF ith simultneous qGhe system it is possile to oserve exothermi events if deomposition oursD however the lerest indition is shown y the mss loss versus time urves whih re no longer liner ut exhiit exponentil deys hrteristi of (rst or seond order deomposition proessesF
IWU
6.2.2.2 Data analysis
he sis of nlyzing isotherml qe dt involves using the glusiusEglpeyron reltion etween vpor pressure @pA nd temperture @AD @TFQAD where rsub is the enthlpy of sulimtion nd is the gs onstnt @VFQIR tGuFmolAF @TFQA ine msu dt re otined from qe dtD it is neessry to utilize the vngmuir equtionD @TFRAD tht reltes the vpor pressure of solid with its sulimtion rteF @TFRA efter integrting @TFQA in log formD sustituting in @TFRAD nd onsolidting the onstntsD one otins the useful equlityD @TFSAF @TFSA reneD the liner slope of log@msub A versus IG plot yields rsub F en exmple of typil plot nd the orresponding rsub vlue is shown in pigure TFTF sn dditionD the y interept of suh plot provides vlue for sub D the lulted sulimtion temperture t tmospheri pressureF
1/2
1/2 Figure 6.6: Plot of log(msub T ) versus 1/T and the determination of the Hsub (112.6 kJ/mol) for Fe(acac)3 (R2 = 0.9989). Adapted from B. D. Fahlman and A. R. Barron, Adv. Mater. Optics Electron., 2000, 10, 223.
le TFI lists the typil results using the qe method for vriety of metl EdiketontesD while le TFP lists similr vlues otined for gllium hlogenide une ompoundsF
IWV
Compound

Hsub (kJ/mol) Ssub
Tsub calc. ( C) Calculated vapor pressure @ 150 C (Torr)
(J/K.mol)
el@A3 el@tfA3 el@hfA3 gr@A3 gr@tfA3 gr@hfA3 pe@A3 pe@tfA3 pe@hfA3 go@A3 go@tfA3 go@hfA3
WQ UR SP WI UI RT IIP WT TH IQV IIW UQ
PPH IWP ISP PIT IVT IQR PSW PRQ ITW QII PWS PHH
ISH III UH IRV IHW TW ITI IPI VI IUH IQI WH
QFPTI WFUIS PWFIPH QFQPV WFWIH PWFSII PFUVI VFQRH PSFHPI IFHSW QFQIW WFIQP
Table 6.1X eleted thermodynmi dt for metl Ediketonte ompounds determined from thermogrvimetri nlysisF ht from fF hF phlmn nd eF F frronD Adv. Mater. Optics ElectronFD PHHHD 10D PPQF
Compound
Hsub (kJ/mol)
Ssub
mol)
(J/K.
Tsub calc. ( C)
Calculated vapor pressure @ 150 C (Torr)
@we3 gAq4 @itwe2 gAq4 @it2 wegAq4 @it3 gAq4 @we3 gAqeA4 @itwe2 gAqe4 @it2 wegAqe4 @it3 gAqe4
IIH IPR IQU IRW IIW IQU IRU IST
QHH QQH QQW QQQ QHS QRR QSW QQW
WR IHP IQI IUS IIT IPR IQT IVW
PPFUS IVFVW IFIUQ HFHIV QFTTV PFSTP HFVIS HFHHS
Table 6.2X eleted thermodynmi dt for gllium hlogenide une ompounds determined from thermogrvimetri nlysisF ht from iF qF qillnD F qF fottD nd eF F frronD Chem. Mater., IWWUD 9D QD UWTF
e ommon method used to enhne preursor voltility nd orresponding e0y for gh pplitions is to inorporte prtilly @pigure TFIA or fully @pigure TFIA )uorinted ligndsF es my e seen from le TFI this sustitution does results in signi(nt derese in the rsub D nd thus inresed voltilityF he oserved enhnement in voltility my e rtionlized either y n inresed mount of intermoleulr repulsion due to the dditionl lone pirs or tht the redued polrizility of )uorine @reltive to hydrogenA uses )uorinted lignds to hve less intermoleulr ttrtive intertionsF
IWW
6.2.3 Determination of sublimation entropy

he entropy of sulimtion is redily lulted from the rsub nd the lulted sub dtD @TFTAF @TFTA le TFI nd le TFP show typil vlues for metl Ediketonte ompounds nd gllium hlogenide une ompoundsD respetivelyF he rnge oserved for gllium hlogenide une ompounds @sub a QQH PH tGuFmolA is slightly lrger thn vlues reported for the metl Ediketontes ompounds @sub a IQH E QQH tGuFmolA nd orgni ompounds @IHH E PHH tGuFmolAD s would e expeted for trnsformtion giving trnsltionl nd internl degrees of freedomF por ny prtiulr hlogenideD iFeFD @Aq4 D the lowest sub re oserved for the we3 g derivtivesD nd the lrgest sub for the it2 weg derivtivesD see le TFPF his is in line with the reltive inrese in the modes of freedom for the lkyl groups in the sene of rystl pking foresF
6.2.4 Determination of vapor pressure

hile the sulimtion temperture is n importnt prmeter to determine the suitility of potentil preursor ompounds for ghD it is often preferle to express ompound9s voltility in terms of its vpor pressureF roweverD while it is reltively strightforwrd to determine the vpor pressure of liquid or gsD mesurements of solids re di0ult @eFgFD use of the isotenisopi methodA nd few lortories re equipped to perform suh experimentsF qiven tht qe pprtus re inresingly essileD it would therefore e desirle to hve simple method for vpor pressure determintion tht n e omplished on qeF ustitution of @TFPA into @TFRA llows for the lultion of the vpor pressure @pA s funtion of temperture @AF por exmpleD pigure TFU shows the lulted temperture dependene of the vpor pressure for @we3 gAq4 F he lulted vpor pressures t ISH g for metl Ediketontes ompounds nd gllium hlogenide une ompounds re given in le TFI nd le TFPF
Figure 6.7: A plot of calculated vapor pressure (Torr) against temperature (K) for [(Me3 C)GaS]4 . Adapted from E. G. Gillan, S. G. Bott, and A. R. Barron, Chem. Mater., 1997, 9, 3, 796.
PHH
he qe pproh to show resonle greement with previous mesurementsF por exmpleD while the vlue lulted for pe@A3 @PFUV orr d IIQ gA is slightly higher thn tht mesured diretly y the isotenisopi method @HFSQ orr d IIQ gAY howeverD it should e noted tht mesurements using the sulimtion ul method otined vlues muh lower @V x IH-3 orr d IIQ gAF he qe method o'ers suitle lterntive to onventionl @diretA mesurements of vpor pressureF
6.2.5 Bibliography

F F etkinsD Physical Chemistry, Sth edFD F rF preemnD xew ork @IWWRAF qF feeh nd F wF vintononD Thermochim. Acta, IWUID 3D WUF fF hF phlmn nd eF F frronD Adv. Mater. Optics ElectronFD PHHHD 10D PPQF iF qF qillnD F qF fottD nd eF F frronD Chem. Mater., IWWUD 9D QD UWTF tF yF rill nd tF F wurryD Rev. Inorg. Chem., IWWQD 13D IPSF tF F wurryD uF tF gvell nd tF yF rillD Thermochim. Acta, IWVHD 36D WUF wF eF F ieiro d ilv nd wF vF gF gF rF perroD J. Chem. Thermodyn., IWWRD 26D QISF F hD hF etD F feldiD Thermochim. Acta, IWWRD 247D IWQF vF eF orresEqomezD qF frreiroEodriquezD nd eF qlrzEwondrgonD Thermochim. Acta, IWVVD 124D PPWF
6.3 13-15 (III-V) Semiconductor Chemical Vapor Deposition

6.3.1 Phosphine and Arsine
3
feuse of their use in metl orgni hemil vpor deposition @wyghA of IQEIS @sssEA semiondutor ompounds phosphine @r3 A nd rsine @esr3 A re prepred on n industril sleF
6.3.1.1 Synthesis
hosphine @r3 A is prepred y the retion of elementl phosphorus @4 A with wterD @TFUAF ltr pure phosphine tht is used y the eletronis industry is prepred y the therml disproportiontion of phosE phorous idD @TFVAF @TFUA
@TFVA ersine n e prepred y the redution of the hlorideD @TFWA or @TFIHAF he orresponding syntheses n lso e used for stiine nd ismuthineF @TFWA
@TFIHA he hydrolysis of lium phosphide or rsenide n lso generte the trihydridesF

3
PHI
6.3.1.2 Structure
he phosphorus in phosphine dopts sp3 hyridiztionD nd thus phosphine hs n umrell struture @pigE ure TFVA due to the stereohemilly tive lone pirF he rrier to inversion of the umrell @ia a ISS ktGmolA is muh higher thn tht in mmoni @ia a PR ktGmolAF utting this di'erene in ontextD mmoE ni9s inversion rte is IH11 while tht of phosphine is IH3 F es onsequene it is possile to isolte hirl orgnophosphines @94AF ersine dopts the nlogous struture @pigure TFVAF
Figure 6.8:
The structures of (a) phosphine and (b) arsine.
6.3.1.3 Reactions
hosphine is only slightly solule in wter @QIFP mgGIHH mvA ut it is redily solule in nonEpolr solventsF hosphine ts s neither n id nor se in wterY howeverD proton exhnge proeeds vi the phosphoE nium ion @r4 + A in idi solutions nd vi r2 - t high prD with equilirium onstnts ub a R x IH-28 nd ua a RIFT x IH-29 D respetivelyF ersine hs similr soluility in wter to tht of phosphine @iFeFD UH mgGIHH mvAD nd esr3 is generlly onsidered nonEsiD ut it n e protonted y superids to give isolle slts of esr4 + F ersine is redily oxidized in irD @TFIIAF @TFIIA ersine will ret violently in presene of strong oxidizing gentsD suh s potssium permngnteD sodium hypohlorite or nitri idF ersine deomposes the its onstituent elements upon heting to PSH E QHH gF
6.3.1.3.1 Gutzeit test
he qutzeit test is the hrteristi test for rseni nd involves the retion of rsine with eg+ F ersine is generted y redution of queous rseni ompoundsD typilly rsenitesD with n in the presene of r2 y4 F he evolved gseous esr3 is then exposed to silver nitrte either s powder or s solutionF ith solid egxy3 D esr3 rets to produe yellow eg3 esxy3 D while with solution of egxy3 lk eg3 es is formedF
6.3.1.4 Hazards
ure phosphine is odorlessD ut tehnil grde phosphine hs highly unplesnt odor like grli or rotting (shD due to the presene of sustituted phosphine nd diphosphine @2 r4 AF he presene of 2 r4 lso uses spontneous omustion in irF hosphine is highly toxiY symptoms inlude pin in the hestD senstion of oldnessD vertigoD shortness of rethD nd t higher onentrtions lung dmgeD onvulsions nd dethF he reommended limit @vA is HFQ ppmF
PHP
ersine is olorless odorless gs tht is highly toxi y inhltionF ywing to oxidtion y ir it is possile to smell slightD grliElike sent when rsine is present t out HFS ppmF ersine ttks hemogloin in the red lood ellsD using them to e destroyed y the odyF purther dmge is used to the kidney nd liverF ixposure to rsine onentrtions of PSH ppm is rpidly ftlX onentrtions of PS ! QH ppm re ftl for QH min exposureD nd onentrtions of IH ppm n e ftl t longer exposure timesF ymptoms of poisoning pper fter exposure to onentrtions of HFS ppm nd the reommended limit @vA is s low s HFHS ppmF
6.3.1.5 Bibliography
F winkwitzD eF uornthD F wodnyD nd rF rrtnerD Z. Anorg. Allg. Chem.D IWWRD 620D USQF
6.3.2 Mechanism of the Metal Organic Chemical Vapor Deposition of Gallium Arsenide
4
6.3.2.1 Introduction
reprtion of epitxil thin (lms of sssE @IQEISA ompound semiondutors @notly qesA for pplitions in dvned eletroni devies eme relisti tehnology through the development of metl orgni hemil vpor deposition @wyghA proesses nd tehniquesF he proesses minly involves the therml deomposition of metl lkyls ndGor metl hydridesF sn IWTV wnsevit t the okwell gorportion ws the (rst to pulish on wygh for the epitxil growth of qesF his followed his pioneering work in IWTQ with the epitxil growth of silion on spphireF he (rst pulition used triethylgllium q@gr2 gr3 A3 nd rsine @esr3 A in n open tue with hydrogen s the rrier gsF wnsevit tully oined the phrse wygh nd sine this seminl work there hve een numerous ttempts to improve nd expnd wygh for the frition of qesF everl proessesD prtly in seriesD prtly in prllel tke ple during the growth y ghF hey re presented shemtilly in pigure TFWF he reltive importne of eh of them depends on the hemil nture of the speies involved nd the design of the retor usedF he tul growth rte is determined y the slowest proess in the series of events needed to ome to depositionF
4
PHQ
Schematic representation of the fundamental transport and reaction steps underlying MOCVD. Adapted from K. F. Jensen and W. Kern, in Thin Film Processes II, Eds. J. L. Vossen and W. Kern, Academic Press, New York (1991).
Figure 6.9:
gonventionllyD the metl orgni hemil vpor deposition @wyghA growth of qes involves the pyrolysis of vpor phse mixture of rsine ndD most ommonlyD trimethylgllium q@gr3 A3 D wq nd triethylgllium q@gr2 gr3 A3 D iqF rditionllyD growth is rried out in oldEwll qurtz retor in )owing r2 t tmospheri or low pressureF he sustrte is heted to tempertures RHH E VHH gD typilly y p heting of grphite suseptorF rnsport of the metlEorgnis to the growth zone is hieved y uling rrier gs @eFgFD r2 A through the liquid soures tht re in held tempertureEontrolled ulersF
6.3.2.2 Reaction mechanism
hile the overll retion @where a gr3 or gr2 gr3 A n e desried y @TFIPAF @TFIPA he nture of the retion is muh more omplexF prom erly studies it ws thought tht free q toms re formed y pyrolysis of wq nd es4 moleules re formed y pyrolysis of esr3 nd these speies reomine on the sustrte surfe in n irreversile retion to form qesF elthough vewis idEse omplex formed etween wq nd esr3 is possileD it is now known tht if there is ny intermedite retion etween the wq nd esr3 D the produt is unstleF roweverD erly work indited tht free qes moleules resulted from the deomposition of wqFesr3 intermedite nd tht the heted surfe ontriuted to the retionF st ws susequently suggested tht the retion ours y seprte pyrolysis of the retnts nd omintion of individul q nd es toms t the surfe or just ove itF pinllyD evidene hs lso een found for wq pyrolysis followed y di'usion through oundry lyer nd for esr3 pyrolysis tlyzed y the qes surfeF here re severl di'erent kinds of potentil retions ouring in the gh retion hmerD nmelyD lignd dissoitionD lignd ssoitionD D redutive elimintionD oxidtive dditionD Ehydride elimintionD etF ome of them re listed in the following equtionsX @TFIQA
PHR
@TFIRA
@TFISA
@TFITA
@TFIUA
@TFIVA
6.3.2.2.1 Using ALE studies as insight for MOCVD
qiven the stepwise nd presumly simpli(ed mehnism for tomi lyer epitxy @eviA growth of qesD numer of mehnisti studies hve een undertken of evi using wq nd esr3 to provide insight into the omprle wygh retionsF xishizw nd uuryshi proposed tht gr3 Eterminted qes surfe inhiits further heterogeneous deomposition of wq nd selfElimits the growth rte to one monolyerGyleF hileD Ery photoeletron spetrosopy @A studies showed tht no ron ws oserved on qes surE fe reted with wqF purthermoreD the sme selfElimiting growth ws seen in in evi using metlorgni moleulr em epitxy @wywfiA with wq nd esr3 F st ws reported tht trnsient surfe reonE strution is oservle y re)etion highEenergy eletron di'rtion @riihA during the evi of qes in wywfiF st ws suggested tht this struture is used y gr3 Etermintion nd the selfElimittion of the growth rte is ttriuted to this strutureF roweverD mesurement of the desorption of gr3 y mens of omintion of pulsed moleulr ems nd timeEresolved mss spetrometryD indites tht gr3 desorption is too fst to ttriute the selfElimittion to the gr3 Eterminted surfeF usequentlyD investigtions of the pyrolysis of wq on @IHHAqes surfe y the surfe photoEsorption method @eA llowed for the diret oservtion of gr3 desorption from qes surfe reted with wqF prom the mesured gr3 desorption kinetisD it ws shown tht the gr3 Eterminted surfes uses the selfElimittion of the growth rte in evi euse the exess wq nnot dsorF ell this reserh helped people to visulize the rel retion mehnism in the formtion of qes y wygh methodsD in whih the deompositionD di'usion nd surfe retion intert with eh other nd result in muh more omplited retion mehnismF
6.3.2.2.2 Gas phase reaction: pyrolysis of TMG and AsH3
sn the wqGr2 systemD there is lmost no retions t temperture elow RSH gD wheres the retion of wq with r2 lmost ompletely hnged into gr4 nd q t temperture ove THH gD @TFIWAF @TFIWA es for the esr3 deompositionD without ny deposition of q or qes in the retorD the pyrolysis of esr3 proeeded rely t temperture elow THH gD howeverD it proeeded nerly ompletely t temperture ove USH gF sn the esr3 Gr2 system with the wq introdued previouslyD the deomposition of esr3 ws lrgely enhned even t temperture elow THH gF he deomposition of esr3 seems to e 'eted
PHS sensitively y the deposited qes or qF his phenomenon my e onluded to e used y the tlyti tion y qes or qF he retion t temperture elow THH g n e desried s shown in @TFPHAD ut t temperture ove THH gD pyrolysis of esr3 n our even without qes or qD @TFPIAF @TFPHA
@TFPIA
6.3.2.2.3 Adsorption and surface reactions
prom the temperture dependent mesurements of the desorption spetrum from surfe on whih wq ws suppliedD it ws estimted tht the surfeEdsored speies ws q t the high temperture region of sub > SHH gD qgr3 t the rnge of QSH g < sub < SHH gD nd q@gr3 A2 nd q@gr3 A3 t the rnge of sub < QSH gF he retionsD where @dA mens the dsored stte of the moleulesD reX @TFPPA
@TFPQA
@TFPRA
@TFPSA hen esr3 is suppliedD the retions with these dsortes reX @TFPTA
@TFPUA
@TFPVA
@TFPWA st ws oserved tht there is no growth in the rnge of sub < QSH gD iFeFD q@gr3 A2 . (ad) nd q@gr3 A3(ad) do not ret with esr3 in the wqEesr3 systemF wonomoleulr lyer growth is limited y the formtion of qgr3 nd its retion with esr3 F
PHT
6.3.2.2.4 Overall reaction pathway
et lower temperture @QSH E SHH gAD equivlently low energyD wq deompose in the gs phse to q@gr3 A2 nd methyl rdilD @TFQHAF @TFQHA efter the (rst lignd dissoitionD there re two di'erent pthwysD in the (rstD the q@gr3 A2 keeps deE omposing into qgr3 nd nother methyl group when it is t the gsEsustrte interfeD @TFQIAD nd then further deomposes into free gllium toms on the sustrte surfeD @TFQPAF sn the seond retionD the q@gr3 A2 deomposes diretly into q nd gr3 Egr3 y redutive elimintionD @TFQQAF @TFQIA
@TFQPA
@TFQQA et high temperture @> SHH gAD the wq deomposes into q@gr3 A nd two methyl groups insted of the stepEwise deomposition t lower tempertureD @TFQRAD nd the q@gr3 A further deomposes into free q toms t the sustrte surfeD @TFQSAF
@TFQRA
@TFQSA he deomposition of esr3 forms n rseni loud in the retion hmerF he deomposition is lso stepEwiseX @TFQTA
@TFQUA
@TFQVA he methyl groups in the surfe q@gr3 A moleules re removed y the formtion of methne with tomi hydrogen from the deomposition of esr3 D @TFQWAF @TFQWA
PHU
6.3.2.2.5 Kinetics for other systems
snvestigtions hve een reported for the mehnism of the growth of qes using triethylgllium q@gr2 gr3 A3 D iq nd wq with trimethylrsene es@gr3 A3 D weD triethylrsene es@gr2 gr3 A3 D ieD tertEutylrsine {@gr3 A3 gesr2 D fe}D nd phenylrsine @g6 r5 Aesr2 F he experiments were onduted in wygh retor equipped with reording mirolne for inEsitu growth rte mesureE mentsF por exmpleD the kinetis of the growth of qes were investigted y mesuring growth rte s funtion of temperture using the mirolne retor while holding the prtil pressure of gllium preurE sor @eFgFD wqA nd rseni preursor eFgFD es@gr3 A3 onstnt t HFHI nd HFHS orrD respetivelyF hree di'erent )ow rtes were used to determine the in)uene of the gs residene timeF he growth rte of qes with wq nd es@gr2 gr3 A3 is higher s ompred with the growth from wq nd es@gr3 A3 euse of the lower therml stility of es@gr2 gr3 A3 thn es@gr3 A3 F foth of the two growth rtes showed strong dependene on the residene timeF imilrlyD the kineti ehviors of the wqGfe nd iqGfe system were investigted under the sme onditions s the we nd ie studiesF here re two distint regions of growthF por wqGfeD the deposition rte is independent t low temperture nd in the intermedite temperture @round THH gA the dependene of the growth rte on the totl )ow rte is signi(ntF his mens tht the growth t the lower temperture is ontrolled y surfe retionsF he iqGfe system showed similr ehvior exept tht the mximum growth rte ours round RSH g while it is round USH g for wqGfe systemF elsoD the growth of wqG@g6 r5 Aesr2 ws studied on the sme onditions s for the we3 qGt fuesr2 systemF st ws reported tht the di'erene in the growth rte t vrious )ow rtes ws relted to omintion of prsiti retions nd depletion e'ets from depositionF prom the omprison of the dtD it is dedued tht the e'et of prsiti retions is slightly smller for @g6 r5 Aesr2 thn for feF wo possile mehnisms for the dependene of growth rte on )ow rte were proposedF he (rstD mssEtrnsfer limittion ws thought to e unlikely euse of the high di'usivity of the gllium preursors t I orr @F QSH m2 GsAF he seondD lso the more likely explntion for the oserved growthErte dependene on )ow rtes is gsEphse depletion use y the prsiti retionsF ine the growth e0ieny is high @RI7 t UHH gAD the loss of preursor from the gs phse will diretly 'et the growth rteF st ws evidened y the di'erenes in the growth rtes etween split nd omined feed stremsF he growth rte is lower when the regents re omined upstrem of the retor thn when they re omined inside the retor @split stremAF st s suggested tht the experimentl oservtions n e explined y model sed on the reversile formtion of n ddut nd the deomposition of this ddut to useless polymeri mteril ompeting with the growth of qesF st n e written in the form shown in @TFRHA where kf nd kr re the forwrd nd reverse rte onstnts for ddut formtionD respetivelyD kd is the rte onstnt for the irreversile deomposition of the ddut to polymerD nd ks is the surfe retion rte onstnt for the growth of qesF st is ovious tht eh step involves severl elementry retionsD ut there were insu0ient dt to provide ny more detilF @TFRHA
F rF ghiuD Appl. Phys. Lett.D IWVWD 55D IPRRF rF sshiiD rF yhnoD uF wtsuzki nd rF rsegwD J. Crys. GrowthD IWVWD 95D IQPF uF pF tensen nd F uernD in hin pilm roesses ssD idsF tF vF ossen nd F uernD edemi ressD xew ork @IWWIAF xF uoyshiD F muhiD nd F rorikoshiD J. Crys. GrowthD IWWID 115D QSQF uF uodmD wF yzekiD uF wohizukiD nd xF yhtsukD Appl. Phys. Lett.D IWVWD 54D TSTF wF F veys nd rF eenvlietD J. Crys. GrowthD IWVID 55D IRSF F wemmert nd wF vF uD Appl. Phys. Lett.D IWWHD 56DIVVQF
PHV

tF xishizw nd F uuryshiD J. Crys. GrowthF IWVVD 93D IQPF F F ymsted nd uF pF tensenD Chem. Mater.D IWWHD 2D QWF hF tF hyer nd wF eF ingD J. Electrochem. SocFD IWUUD 124D STWF tneD F ssuD wF rtD F umijohD nd F utymD Japan. J. Appl. PhysFD IWVWD 28D vIHVHF F hngD hF feuermnnD nd wF tukeD Appl. Phys. BD IWVWD 48D WUF F hngD F wF gleverD wF tukeD nd eF F frronD Appl. Phys. AD IWWPD 55D PTIF
6.4 Oxide Chemical Vapor Deposition

6.4.1 Chemical Vapor Deposition of Silica Thin Films
6.4.1.1 General considerations
5
fefore desriing individul hemil vpor deposition @ghA systems for the deposition of sili thin (lmsD it is worth outlining generl onsidertions to e tken into ount with regrd to the growth y gh of ny insulting (lmX the type of gh methodD deposition vrilesD nd limittions of the preursorF
6.4.1.1.1 Deposition methods
sn regrd to the gh of insulting (lms in generlD nd sili (lms in prtiulrD three generl retors re presently usedX tmospheri pressure gh @eghAD low nd medium temperture low pressure gh @vghAD nd plsmEenhned gh @ighAF vgh is often further divided into low nd high temE perturesF egh systems llow for high throughput nd even ontinuous opertionD while vgh provides for superior onforml step overge nd etter (lm homogeneityF igh hs een trditionlly used where low tempertures re requiredD howeverD (lm qulity is often poorF es ompred to ighD photoEssisted gh hs the dditionl dvntge of highly seletive depositionD lthough it hs een little used in ommeril systemsF le TFQ summrizes the dvntges nd disdvntges of eh type of gh system ommerilly used for iy2 (lmsF
Atmospheric pressure CVD Low temperature LPCVD Medium temperature LPCVD Plasma enhanced CVD
emperture @ gA hroughput tep overge pilm properties ses
QHH E SHH high poor good pssivtionD insuE ltion
QHH E SHH high poor good pssivtionD insuE ltion
SHH E WHH high onforml exellent insultion
IHH E QSH low poor poor pssivtionD insuE ltion
Table 6.3
X gomprison of di'erent deposition methods for iy2 thin (lmsF
6.4.1.1.2 Deposition variables
he requirements of gh (lms for eletroni devie pplitions hve eome inresingly more stringent s devie sizes re ontinully reduedF pilm thikness must e uniform ross n entire wferD iFeFD etter
5
PHW thn I7F he struture of the (lm nd its omposition must e ontrolled nd reproduileD oth on single wferD s well s etween wfer smplesF st is lso desirle tht the proess is sfeD inexpensiveD nd esily utomtedF e numer of vriles determine the qulity nd rte of (lm growth for ny mterilF sn generlD the deposition rte inreses with inresed temperture nd follows the errhenius equtionD @TFRIAD where is the deposition rteD ia is the tivtion energyD is the temperture @uAD e is the frequeny ftorD nd k is foltzmnn9s onstnt @IFQVI x IH-23 tGuAF @TFRIA et the high tempertures the rte of deposition eomes mss trnsport limitedF weningD the rte of surfe retion is fster thn the rte t whih preursors re trnsported to the surfeF sn multiple soure systemsD the (lm growth rte is dependent on the vpor phse onentrtion @or prtil pressureA of eh of the retntsD ut in ertin ses the rtio of retnts is lso importntD eFgFD the ir4 Gy2 growth of iy2 F urfe tlyzed retions n lso lter the deposition rteF uh s the nonEliner dependene of the deposition rte of iy2 on the prtil pressure of i@yitA4 F qs depletion my lso e signi(nt requiring either therml rmp in the hmer ndGor speil retor designsF he neessry inorportion of dopnts usully lowers deposition rtesD due to ompetitive surfe indingF por the pplitions of insulting mterils s isoltion lyersD n importnt onsidertion is step overgeX whether oting is uniform with respet to the surfeF pigure TFIH shows shemti of ompletely uniform or onforml step overge of trenh @suh s ours etween isolted deviesA where the (lm thikness long the wlls is the sme s the (lm thikness t the ottom of the stepF niform step overge results when retnts or retive intermedites re le to migrte rpidly long the surfe efore retingF hen the retnts dsor nd ret without signi(nt surfe migrtionD deposition is dependent on the men free pth of the gsF pigure TFIH shows n exmple of miniml surfe migrtion nd short men free pthF por iy2 (lm growth vgh hs highly uniform overge @pigure TFIHA nd igh poor step overge @pigure TFIHAF
Figure 6.10: Step coverage of deposited lms with (a) uniform coverage resulting from rapid surface migration and (b) nonconformal step coverage due to no surface migration.
6.4.1.1.3 Precursor considerations
he generl requirements for ny gh preursor hve een dequtely reviewed elsewhereD nd will not e overed hereF roweverD mny of the gses nd orgnometllis used to deposit dieletri (lms re hzrdousF he sfety prolems re more severe for vgh euse the proess often uses no diluent gs suh s rgon or nitrogenF le TFR lists the oiling point nd hzrds of ommon inorgni nd orgnometlli preursor
PIH
soures for gh of iy2 nd doped siliF wny of the preursors ret with ir to form solid produtsD thus leks n use prtiles to form in the hmer nd gs linesF
Gas Formula Bpt ( C) Hazard
mmoni rgon rsine diorne dihlorosilne hydrogen nitrogen nitrous oxide oxygen phosphine silne
Table 6.4
xr3 er esr3 f2 r6 igl2 r2 r2 x2 x2 y y2 r3 ir4
EQQFQS EIVSFU ESS EWPFS VFQ EPSPFV EPHWFVT EVVFS EIVPFWTP EVUFU EIIIFV
toxiD orrosive inert toxi toxiD )mmle toxiD )mmle )mmle inert oxidizer oxidizer toxiD 2 r4 impuritiesD )mmle )mmleD toxi
X hysil nd hzrd properties of ommon gseous soures for gh of dieletri mterilsF
sn prinipleD the deposition of iy2 D or siliD thin (lm y gh requires two hemil souresX the element @or elementsA in questionD nd n oxygen soureF hile dioxygen @y2 A is suitle for mny ppliE tionsD its retions my e too fst or too slow for optimum (lm growthD requiring tht lterntive oxygen soures e usedD eFgFD nitrous oxide @x2 yA nd ozone @y3 AF e ommon nonEoxidizing oxygen soure is wterF e more dvntgeous pproh is to inorporte oxygen into the lignd environment of the preursorD nd endevor to preserve suh n intertion intt from the soure moleule into the ultimte (lmY suh soure is often termed 4singleEsoure4 preursorF
6.4.1.2 CVD silica (SiO2 )
he proessing sequene for silion dioxide @iy2 A used depends on its spei( useF gh proesses for iy2 (lms n e hrterized y either the hemil retion typeD the growth pressureD or the deposition tempertureF he hoie of route is often ditted y requirements of the therml stility of the sustrte or the onformlityF le TFS summrizes seleted properties of iy2 grown y vrious gh methodsD in omprison to tht of thermlly grown siliF sn generlD sili grown t high tempertures resemle thermlly grown ntive iy2 F roweverD the use of luminum metlliztion requires low temperture deposition of siliF
Deposition Plasma
SiH4 + O2
Si(OEt)4
SiCl2 H2 + N2 O
Thermal
emperture @ gA gomposition tep overge herml stility efrtive idex hieletri onstnt
Table 6.5
PHH iy1.9 @rA nonEonforml loses r IFRU RFW
RSH iy2 @rA nonEonforml densi(es IFRR RFQ
UHH iy2 onforml stle IFRT RFH
WHH iy2 @glA onforml loses gl IFRT RFH
IHHH iy2 onforml stle IFRT QFW
X gomprison of physil properties of iy2 grown y ommeril gh methodsF
PII
6.4.1.2.1 CVD from hydrides
he most widely used method for iy2 thin (lm gh is the oxidtion of silne @ir4 AD (rst developed in IWTU for eghF xonethelessD vgh systems hve sine eome inresingly employedD nd exeptionlly high growth rtes @QHDHHH GminA hve een otined y the use of rpid therml ghF he hemil retion for iy2 deposition from ir4 isX @TFRPA et high oxygen prtil pressures n lterntive retion oursD resulting in the formtion of wterF @TFRQA hile these retions ppers simpleD the detiled mehnism involves omplex rnhingEhin sequene of retionsF he pprent tivtion energy is low @< RI ktGmolA s onsequene of its heterogeneous ntureD nd involves oth surfe dsorption nd surfe tlysisF xitrous oxide @x2 yA n e used s n lterntive oxygen soure to y2 D ording to the overll retionD @TFRRAF @TFRRA e simple kineti sheme hs een developed to explin mny of the oserved spets of ir4 Ex2 y growthF st ws suggested tht the retion is initited y deomposition of x2 yD @TFRSAD generting n oxygen rdil whih n strt hydrogen from silne forming hydroxyl rdilD @TFRTAD tht n ret further with silneD @TFRUAF @TFRSA
@TFRTA
@TFRUA ividene for the retion of the yr rdil to form wter is the formtion of smll quntity of wter oserved during the oxidtion of ir4 F ilyl rdils re oxidized y x2 y to form siloxy rdilsD @TFRVAD whih provide suitle propgtion stepD @TFRWAF @TFRVA
@TFRWA st hs een proposed tht the silnol @ir3 yrA is the penultimte (lm preursorF he ir4 Ey2 nd ir4 Ex2 y routes to iy2 thin (lms re perhps the most widely studied photohemil gh system of ll dieletrisF hotoEgh of iy2 provides suitle route to deposition t low sustrte temperturesD therey voiding potentil therml e'ets of wfer wrpge nd deleterious dopnt redistriE utionF sn dditionD unlike other low temperture methods suh s egh nd ighD photoEgh often provides good purity of (lmsF e summry of ommon silne gh systems is given in le TFTF
PIP
Oxygen source Carrier (diluent) gas

CVD method Deposition temp. ( C) Growth (/min) rate
y2 y2 y2 y2 x2 y x2 y x2 y x2 y
Table 6.6
x2 er erGx2 er x2 x2 x2 er
egh vgh vgh igh egh vgh vgh igh
QSH E RUS IHH E SSH PS E SHH PS E PHH RWH E TWH UHH E VTH PS E QSH IHH E PHH
IHH E IRDHHH IHH E QHDHHH IH E RSH PHH E WHH PHH E IDPHH
caF SH
U E IVH VH E VHH
X reursors nd deposition onditions for iy2 gh using silne @ir4 AF
6.4.1.2.2 CVD from halides
he most widely used proess of the high temperture growth of iy2 y vgh involves the x2 y oxidtion of dihlorosilneD igl2 r2 D @TFSHAF @TFSHA heposition t WHH E WIS g llows for growth of iy2 (lms t caF IPH GminY howeverD these (lms re ontminted with glF eddition of smll mounts of y2 is neessry to remove the hlorineF hile igh hs een employed utility hlide preursorsD the ility of smll quntities of )uorine to improve the eletril properties of iy2 hs prompted investigtion of the use of ip4 s suitle soureF
6.4.1.2.3 CVD from tetraethoxylsilane (TEOS)
he (rst gh proess to e introdued into semiondutor tehnology in IWTI ws tht involving the pyrolE ysis of tetrethoxysilneD i@yitA4 @ommonly lled iy from tetrethylorthosiliteAF heposition ours t n optimum temperture round USH gF roweverD under vgh onditionsD the growth temperture n e signi(ntly lowered @> THH gAF he high temperture growth of iy2 from iy involves no externl oxygen soureF hissoitive dsorption studies indite tht deomposition of the iyEderived surfe ound diE nd triEethoxysiloxnes is the diret soure of the ethyleneF igh signi(ntly lowers deposition tempertures using iyD ut requires the ddition of y2 to remove ron ontmintionD vi the formtion of gseous gy nd gy2 D whih re susequently not inorE ported within the (lmF elthough deposition s low s IHH g my e otinedD the (lm resistivity inreses y three orders of mgnitude y depositing t PHH gY eing IH16 FmD with rekdown strength of U x IH6 GmF eddition of y2 for egh growth does not derese the deposition tempertureD howeverD if ozone @y3 A is used s the oxidtion soureD deposition tempertures s low s QHH g my e otined for uniform rkEfree (lmsF st hs een postulted tht the ozone trps the iy moleule on the surfe s it rets with the ethoxy sustituentD providing lower energy pthwy @iyEy3 d SS ktGmol versus iyEy2 d PQH ktGmol nd iy only d IWH ktGmolAF here re signi(nt dvntges of the iyGy3 systemD for exmple the superior step overge it providesF purthermoreD (lms hve low stress nd low prtile ontmintionF yn this sis the iyGy3 system hs eome widely used for siliD s well s silite glssesF
PIQ
6.4.1.2.4 CVD from other organosilicon precursors
e wide rnge of lterntive silion soures hs een investigtedD espeilly with regrd to either lower temperture deposition ndGor preursors with greter mient stilityF hiethylsilne @it2 ir2 AD IDREdislutne @hfD r3 igr2 gr2 ir3 AD PDRDTDVEtetrmethylylotetrsiloxne @wgD pigure TFIID where a gr3 AD nd PDRDTDVEtetrethylylotetrsiloxne @igD pigure TFIID where a g2 r5 AD hve een used in onjuntion with y2 over deposition tempertures of IHH E THH gD depending on the preursorF hietoxydiEtertEutyl silne @hehfD pigure TFIIA hs een used without dditionl oxidtion souresF righ qulity silion oxide hs een grown t QHH g y egh using the mido preursorD i@xwe2 A4 @pigure TFIIAF
Alternative organometallic silicon sources that have been investigated for the growth of silica thin lms.
Figure 6.11:
en interesting onept hs een to preform the EiEyEiE frmework in the preursorF sn this regrdD the novel preursor 8 Ehydridospherosiloxne @r8 i8 y12 D pigure TFIIdA gives smooth morphous stoihiometri iy2 t RSH E SPS g y vghF he deomposition mehnism in the presene of dded oxygen involves the loss of wterD @TFSIAF s studies indite tht the iEyEi onds re preserved during depositionF hile (lms re of high qulityD the present synthesis of r8 i8 y12 is of low yield @caF PI7AD mking it urrently imprtil for lrge sle proessingF @TFSIA
PIR
6.4.1.3 CVD silicate glasses
forosilite glsses @fqAD phosphosilite glsses @qA nd orophosphosilite glsses @fqA re freE quently used s insulting lyers seprting onduting lyersF hese glsses hve lower intrinsi stressD lower melting tempertures nd etter dieletri properties thn iy2 itselfF q nd fq hve the dded property of gettering nd immoilizing dopntsF rtiulrly importnt is the gettering of sodium ionsD whih re soure of interfe trpsF he low temperture molten properties of fqD qD nd fq glsses llow for the smoothing of the devie topogrphy y visous therml fusion to onvert rupt steps to more grdully tpered steps @pigure TFIPA s well s plnriztion of omplex topologies @pigure TFIPAD enling deposition of ontinuous metl lyersF his proess is ommonly lled Eglss )owF he oron nd phosphorous ontents of the silite glsses vryD depending on the pplitionD typilly eing from P to V weight per entF
Schematic cross section of BPSG as deposited (a) and after annealing (b), showing the ow causing a decrease in the angle of the BPSG going over the step.
Figure 6.12:
he dvntge of fq over q is tht )ow ours over the temperture rnge of USH E WSH gD depending on the reltive nd f ontent @s opposed to WSH E IIIH g for qAF vowering of the )ow temperture is required to minimize dopnt migrtion in vs deviesF gonverselyD the disdvntges of fq versus q inlude the formtion of ules of voltile phosphorous oxides nd rystllites of oronE rih phsesF sfD howeverD the dopnt onentrtion is ontrolledD these e'ets n e minimizedF ersenosilites @esqA were employed originlly in silion devie tehnology s n rseni dopnt soure for plnr sustrtes prior to the dvent of lrge sle ion implnttion whih hs lrgely removed the need for esq in doping pplitionsF roweverD with vs silion iruit fritionD the requirement for doping of deep trenhes @inessile to ion implnttionA hs witnessed the reEemergene of interest in esq (lmsF he gh growth of silite glsses follows tht of iy2 D with ir4 nd iy eing the most ommonly employed silion preursorsF e summry of ommon gh preursor systems for silite glsses is given in le TFUF
PIS
Precursors
CVD method
Deposition temp. ( C)
Applications
ir4 Gf2 r6 ir4 Gf2 r6 ir4 Gr3 ir4 Gr3 ir4 Gf2 r6 Gr3 ir4 Gf2 r6 Gr3 ir4 Gesr3 iyGf@yweA3 iyGf@yweA3 iyGf@yitA3 iyGf@yitA3 iyGr3 iyGya@yweA3 iyG@yweA3 iyGya@yweA3 iyGf@yweA3 Gr3 iyGf@yweA3 G@yweA3 iyGf@yweA3 Gya@yweA3 iyGesgl3 iyGes@yitA3 iyGyaes@yitA3
Table 6.7
egh vgh egh vgh egh vgh egh egh vgh egh vgh vgh egh vgh vgh vgh vgh vgh egh vgh vgh
QHH E RSH QSH E RHH QHH E RSH QSH E RHH QHH E RSH QSH E RHH SHH E UHH TSH E UQH SHH E USH RUS E VHH SHH E USH TSH QHH E VHH SHH E USH SHH E VHH TPH E VHH TUS E USH TVH SHH E UHH UHH E UQH UHH E UQH
good step overge E E )ow glss E E E di'usion soure trenh (lling di'usion soure di'usion soure )ow glss )ow glss di'usion soure )ow glss trenh (lling )ow glss )ow glss di'usion soure trenh doping trenh doping
X reursors nd deposition onditions for gh of orosilite glss @fqAD phososilite glss @qAD orophosphosilite glss @fqA nd rsenosilites @esqA thin (lmsF
6.4.1.3.1 CVD from hydrides
pilms of fqD qD nd fq my ll e grown from ir4 D y2 nd f2 r6 ndGor r3 D t QHH E TSH gF por eghD the retnts re diluted with n inert gs suh s nitrogenD nd the y2 Ghydride molr rtio is refully ontrolled to mximize growth rte nd dopnt onentrtion @vlues of I to IHH re used depending on the pplitionAF yrdinrilyD the dopnt onentrtion for oth fq nd q dereses with inresed tempertureF roweverD some reports indite n inrese in oron ontent with inresed tempertureF pilm growth of fq ws found to our in two temperture regionsF heposition t low temperture @PUH E QTH gA ourred vi surfe retion rte limiting growth @ia a QW klGmolAD while t higher temperture @QSH E RSH gAD mssEtrnsport rte limited retion region is oserved @ia a UFT klGmolAF vgh of fq nd q is onduted t RSH E SSH g with n y2 Xhydride rtio of IXIFSF gonverselyD n y2 Xhydride rtio of IFSXI provides the optimum growth onditions for fq over the sme temperture rngeF he phosphorous in q (lms ws found to exist s mixture of 2 y5 nd 2 y3 D howeverD the ltter n e minimized under the orret deposition onditionsF ome di0ulties hve een reported for the use of f2 r6 due to its therml instilityF ustitution of f2 r6 with fgl3 ovites this prolemD lthough the resulting (lms re invrily ontminted with I weight per ent hlorideF
PIT
ersenosilite glss @esqA thin (lms re generlly grown y egh using rsine @esrQAY the use of whih is eing limited due to its high toxiityF roweverD rsine inhiits the gs phse retions etween ir4 nd y2 D suh tht (lm grown from ir4 Gesr3 Gy2 show improved step overge t high deposition rtesF
6.4.1.3.2 CVD from metal organic precursors
es with iy2 depositionD see oveD there hs een trend towrds the replement of ir4 with iy on ount of its ility to produe highly onforml otingsF his is prtiulrly ttrtive with respet to trenh (llingF purthermoreD (lms of doped iy2 glsses hve een otined using oth egh nd vgh @typilly elow Q orrAD with wide vriety of dopnt elements inludingX oronD phosphorousD nd rseniD inluding ntimonyD tinD nd zinF foronEontining glsses re generlly grown using either trimethylorteD f@yweA3 D or triethylorteD f@yitA3 D lthough the multiEelement soureD tris @trimethylsilylAorteD f@yiwe3 A3 D hs een employed for oth silion nd oron in fq thin (lm growthF imilrlyD wheres r3 my e used s the phosphoE rous soureD trimethylphosphiteD @yweA3 D nd trimethylphosphteD ya@yweA3 D re preferredF vikewiseD triethoxyrsineD es@yitA3 D nd triethylrsenteD yaes@yitA3 D hve een employed for esq growthF he oEretion of iy with orgnooron nd orgnophosphorous ompounds llows for deposition t lower tempertures @SHH E TSH gA thn for hydride growth of omprle rtesF roweverD vghD using n ll orgnometlli pprohD requires @yweA3 euse the low retivity of ya@yweA3 prevents signi(nt phosphorus inorportionF elthough premture deomposition of @yweA3 ours t THH g @leding to nonEuniform growthAD deposition t SSH g results in high (lm uniformity t resonle deposition rtesF
F uern nd F F fnD in Thin Film ProcessesD idsF tF vF ossenD F uernD edemi ressD xew ork @IWUVAF wF vF rmmodD Sold State Technol.D IWVHD 23D IHRF eF F frron nd F F eesD trFD Adv. Mater. Optics Electron.D IWWQD 2D PUIF xF qoldsmith nd F uernD RCA Rev., IWTUD 28D ISQF gF velesuD tF F wittieD gF ghngD uF gF rswtD nd tF F veongD Thin Solid FilmsD IWWPD 217D TVF tF hF ghppleEokolD gF tF qiuntD nd F qF qordonD J. Electrochem. SocFD IWVUD 136D PWWQF F qonzlezD hF pernndezD tF ouD iF qrD tF errD fF venD nd wF rezEemorD Thin Solid FilmsD IWWPD 218D IUHF iF vF tordnD J. Electrochem. SocFD IWTID 108D RUVF uF pujinoD F xishimotoD xF okumsuD nd uF wedD J. Electrochem. Soc.D IWWHD 137D PVVQF F eF vevy nd uF xssuD J. Electrochem. Soc.D IWVTD 133D IRIUF vF uF hiteD tF wF hwD F eF uuryloD nd xF wiszkowskiD J. Electrochem. Soc.D IWWHD 137D ISHIF
6.4.2 Chemical Vapor Deposition of Alumina

6.4.2.1 Alumina
eluminD el2 y3 D exists s multiple rystlline formsD howeverD the two most importnt re the nd formsF Eel2 y3 @orundumA is stle t high tempertures nd its struture onsists of hexgonl loseEpked rry of oxide @y2- A ions with the el3+ ions oupying othedrl interstiesF sn ontrstD Eel2 y3 hs defet spinel strutureD redily tkes up wter nd dissolves in idF hespite the potentil disdvntges of Eel2 y3 there is preferene for its deposition on silion sustrtes euse of the two di'erent lttieE mthing reltionships of Eel2 y3 @IHHA on i@IHHAF hese re shown s shemti digrms in pigure TFIQF e summry of gh preursor systems for el2 y3 is given in le TFVF
6
PIU
Figure 6.13:
Schematic diagram of the crystallographic relations of -Al2 O3 on Si(100): (a) -Al2 O3 (100)||Si(100), and (b) -Al2 O3 (100)||Si(110). Adapted from A. R. Barron, CVD of Non-Metals, W. S. Rees, Jr., Ed. VCH, New York (1996).
Aluminum precursor
Oxygen source
Carrier gas
CVD method
Deposition temp. ( C)
Comments
elgl3
gy2 Gr2
r2 or x2
egh
UHH E WHH
morphous @UHHAD rysE tlline @VSH E WHHA depF rte highly deE pendent on gsEphse onF el nd y2
elwe3
y2
x2 or re
egh
QSH E QVH
PIV elwe3 y2 x2

vgh QUS plsmE enhnedD IH lower qulity thn with y2 good pssivE tion properties of i wy deE vies plsmE enhnedD
elwe3 elwe3
x2 y x2 y
x2 or re x2
egh vgh
IHH E TTH WSH E IHSH
elwe3 el@yi rA3 el@y rA3 el@y rA3 el@A3 el@A3 el@A3
i i
x2 y y2 y2 x2 y ir y2 nd r2 y
re x2 x2 er x2 x2 er
igh egh vgh vgh egh egh vgh
IPH E QHH RPH E THH PSH E RSH PHH E USH RPH E RSH PSH E THH PQH E SSH
epitxil on i high g ontent signi(nt ontent g
growth rte inE depF of r2 y ut (lm qulE ity depF on r2 y
Table 6.8
X reursors nd deposition onditions for el2 y3 ghF
6.4.2.1.1 CVD from halides
he initil use of gy2 Gr2 s hydrolysis soure for the gh of iy2 from igl4 D led to the nlogous deposition of el2 y3 from elgl3 D iFeFD @TFSPA heposition in the temperture rnge UHH E WHH g ws found to yield (lms with optimum dieletri propertiesD ut (lms deposited elow UHH g ontined signi(nt hloride impuritiesF st hs een determined tht r2 y vporD formed from r2 nd gy2 D ts s the oxygen donorD nd not the gy2 F he rystl form of the ghE grown lumin (lms ws found to depend on the deposition tempertureY (lms grown elow WHH g were Eel2 y3 D while those grown t IPHH g were Eel2 y3 D in ord with the known phse digrm for this mterilF
6.4.2.1.2 CVD from trimethylaluminum (TMA)
elthough trimethylluminumD elwe3 @weAD rets rpidly with wter to yield el2 y3 D the retion is highly exothermi @EIPRQ ktGmolA nd thus di0ult to ontrolF he oxygen gettering properties of luminum metlD howeverD n e employed in the ontrolled wygh growth of el2 y3 F he ommon deposition onditions employed for gh of el2 y3 from elwe3 re similr to those used for luminumEmetl ghD ut with the ddition of n oxygen soureD either y2 or x2 yF pilms grown y egh using x2 y re of inferior qulity to those employing y2 D due to their exhiiting some optil sorption in the visile wvelength regionF he growth of high qulity (lms using either
PIW oxygen soure is highly dependent on the gs phse onentrtions of luminum nd oxygenF purther improvements in (lm qulity re oserved with the use of temperture grdient in the hmers deposition zoneF ettempts to lower the deposition temperture employing igh hve een generlly suessfulF rowE everD detiled spetrosopi study showed tht the use of x2 y s the oxygen soure resulted in signi(nt ron nd hydrogen inorportion t low tempertures @IPH E QHH gAF he ron nd hydrogen ontmiE ntion re lowered t high deposition tempertureD nd ompletely removed y postEdeposition tretment under y2 F st ws proposed tht the ron inorported in the (lms is in the hemil form of elEgr3 or elEg@yAyrD while hydrogen exists s elEyr moieties within the (lmF hotoEssisted gh of el2 y3 from elwe3 hs een reported to provide very high growth rtes @PHHH GminA nd give (lms with eletril properties omprle to (lms deposited using therml or plsm tehniquesF srrdition with PRV nm @urpA lser soure llowed for uniform deposition ross Q4 wferF roweverD use of IWQ nm @erpA irrdition required dilution of the elwe3 onentrtion to void nonEuniform (lm growthF
6.4.2.1.3 CVD from alkoxides and
-diketonates
he pyrophori nture of elwe3 urged investigtions into lterntive preursorsD in prtiulr those whih lredy ontin oxygenF elterntive preursors might lso provide possile routes to eliminte ron onE tmintionF qiven the suessful use of iy in iy2 thin (lm growthD n nlogous lkoxide preursor pproh is logilF he (rst report of el2 y3 (lms grown y gh used n luminum lkoxide preursorsF eluminum trisEiso EpropoxideD el@yi rA3 D is ommerilly ville inexpensive lkoxide preursor omE poundF heposition my e rriedEout y either egh or vghD using oxygen s n dditionl oxidtion soure to ensure low ron ontmintionF st is dventitious to use vgh @IH orrA growth to inhiit gs phse homogeneous retionsD using formtion of powdery depositF he use of lower hmer pressures @Q orrA nd x2 y s the oxide soure provided su0ient improvement in (lm qulity to llow for devie fritionF he deposition of el2 y3 (lms from the pyrolysis of luminum etyletonteD el@A3 @pigure TFIRAD hs een widely investigted using oth egh nd vghF he pereived dvntge of el@A3 over other luminum preursors inludes loweredEtoxiityD good stility t room tempertureD esy hndlingD high voltility t elevted temperturesD nd low ostF roweverD the qulity of (lms ws originlly poorY ron eing the min ontminnt resulting from the thermolysis nd inorportion of etone nd ron dioxide formed upon therml deomposition @pigure TFISAF
Figure 6.14:
Aluminum -diketonate precursors.
PPH
Figure 6.15: Gaseous decomposition products from the pyrolysis of Al(acac)3 as a function of pyrolysis temperature (Data from J. Von Hoene, R. G. Charles, and W. M. Hickam, J. Phys. Chem., 1958, 62, 1098).
snomplete oxidtion of the (lm my e redily solved y the ddition of wter vpor to the rrier gs stremY pure ronEfree (lms eing grown t tempertures s low s PQH gF sn ftD wter vpor plys n importnt role in the (lm growth kinetisD (lm purityD nd the surfe morphology of the grown (lmsF hile the growth rte is un'eted y the ddition of wter vporD its in)uene on the surfe morphology is signi(ntF pilms grown without wter vpor on the el2 y3 surfe is rough with prtiultesF sn ontrstD (lms grown with wter vpor re mirror smoothF e systemti study of the kinetis of vporiztion of el@A3 long with )uorinted luminum E diketonte omplexesD el@tfA3 @pigure TFIRA nd el@hfA3 @pigure TFIRAD hs een reportedD nd the sturtion vpor pressures determined t US E IUS gF
6.4.2.2 Aluminum silicates
he high dieletri onstntD hemil stility nd refrtory hrter of luminosilitesD @el2 y3 Ax @iy2 Ay D mkes them useful s pkging mterils in sg hip mnuftureF wullite @Qel2 y3 FPiy2 A prepred y solE gel tehniquesD is often used s n enpsulnt for tive devies nd thinE(lm omponentsF emorphous luminEsili (lms hve lso een proposed s insultors in multilevel interonnetionsD sine they do not su'er the temperture instility of lumin (lms retin the desirle insulting hrteristisF nder ertin onditions of growth nd fritionD sili my rystllizeD therey llowing di'usion of oxygen nd impurities long grin oundries to the silion sustrte undernethF uh unwnted retions re tstrophi to the eletroni properties of the devieF he retention of morphous struture over lrger temperture rnge of silion rih luminEsili (lms o'ers possile solution to this deleterious di'usionF hin (lms of mixed metl oxides re usully otined from mixture of two di'erent kinds of lkoxide preursorsF roweverD this method su'ers from prolems with stoihiometry ontrol sine extensive e'orts must e mde to ontrol the vpor phse onentrtion of two preursors with often dissimilr vpor presE suresF elso of import here is the ner impossile tsk of mthing rtes of hydrolysisGoxidtion to give 4pure4D nonEphse segregted (lmsD iFeFD those hving homogeneous omposition nd strutureF sn n e'ort
PPI to solve these prolemsD reserh e'ort hs een imed t singleEsoure preursorsD iFeFD those ontining oth luminum nd silionF he (rst study of singleEsoure preursors for @el2 y3 Ax @iy2 Ay (lms employed the monoEsiloxide omplex el@yi rA2 @yiwe3 A @pigure TFITAF roweverD it ws found tht exept for deposition t very high temperE tures @> WHH gA the deposited (lms this monoEsiloxide ompound were luminumErih @elGi a IFQ E PFIA nd thus showed therml instility in the insulting properties used y rystlliztion in the (lmsF st would pper tht in order for silionErih luminEsili (lms to e grown more siloxne sustituents re requiredD eFgFD the tris Esiloxy luminum omplex el@yiit3 A3 2 @pigure TFITAF
Figure 6.16:
Precursors for aluminum silicate thin lms.
he elGi rtio of thin (lms growth y egh using el@yiit3 A3 2 t RPH E SSH gD ws found to e dependent on the deposition temperture nd the rrier gs omposition @y2 GerAF his temperture nd oxygenEdependent vrition in the (lm omposition suggests tht two ompeting preursor deomposition pthwys re presentF IF heposition in the sene of y2 D is similr to tht oserved for the deomposition of el@yi rA2 @yiwe3 A under x2 D nd would imply tht the (lm omposition is determined y the tempertureEdependent tendenies of the elEyEi onds to leveF PF he tempertureEindependent oxidtive deomposition of the preursorF hile it is possile to prepre (lms riher in i using el@yiit3 A3 2 rther thn el@yi rA2 @yiwe3 AD the elXi rtio is unfortuntely not esily ontrolled simply y the numer of siloxy lignds per luminum in the preursorF pilms grown from the singleEsoure preursor el@yi rA2 @yiwe3 A rystllize to kyniteD el2 iy5 D wheres those grown from el@yiit3 A3 2 remined morphous even fter nnelingF
eF F eplettD vF uF ghethmD nd eF F frronD J. Mater. Chem.D IWWID 1 DIRQF uF wF qustin nd F qF qordonD J. Electronic Mater.D IWVVD 17D SHWF gF vndryD vF uF ghethmD eF xF wsnnesD nd eF F frronD Adv. Mater. Optics Electron.D IWWPD 1D QF F xkido nd F oyoshimD J. Electrochem. Soc.D IWTVD 115D IHWRF F wruym nd F xkiD Appl. Phys. Lett.D IWWID 58D PHUWF uF wdD wF sshidD F xkmurD nd xF yhtkeD Appl. Phys. Lett.D IWVVD 52D ITUQF tF on roeneD F qF ghrlesD nd F wF rikmD J. Phys. Chem.D IWSVD 62D IHWVF
PPP
6.5 Nitride Chemical Vapor Deposition

6.5.1 Introduction to Nitride Chemical Vapor Deposition
7
he refrtory nture nd high dieletri properties of mny nitrides mke them ttrtive for hemil nd eletroni pssivtionF es onsequene silion nitride hs eome the stndrd within the semiondutor industryD s oth n enpsultion lyer nd s n eth mskF sn similr mnner to oxide growth y hemil vpor deposition @ghAD two soures re generlly required for inry nitride ghX the element of hoie nd nitrogen soureF roweverD unlike the gh of oxidesD elementl nitrogen @x2 A is not retiveD even t elevted temperturesD therey requiring plsm enhnementF iven with plsm enhned gh @ighAD x2 does not yield high qulity (lmsF es sustitute for x2 D mmoni @xr3 A hs found generl eptne s suitle nitrogen soureF st is gsD redily puri(ed nd hepD howeverD it is of low retivity t low temperturesF igh hs therefore found fvor for low temperture xr3 Esed preursor systemsF eent ttempts to lower deposition tempertures hve inluded the use of more retive soures @eFgFD r2 xxr2 A nd preursors ontining nitrogen s oordinted ligndF roly the most importnt disovery with respet to nitride deposition is the use of trnsmintion retion etween mido ompounds nd mmoni @@TFSQAAF
@TFSQA
hF wF ro'mnD PolyhedronD IWWRD 13D IITWF
6.5.2 Chemical Vapor Deposition of Silicon Nitride and Oxynitride

toihiometri silion nitride @i3 x4 A is used for hemil pssivtion nd enpsultion of silion ipolr nd metl oxide semiondutor @wyA deviesD euse of its extremely good rrier properties for wter nd sodium ion di'usionF ter uses devie metlliztion to orrodeD nd sodium uses devies to eome eletrilly unstleF ilion nitride is lso used s msk for the seletive oxidtion of silionD nd s strong dieletri in wxy @metlEnitrideEoxideEsilionA struturesF he use of ion implnttion for the formtion of tive lyers in qes wipi devies @pigure TFIUA llow for ontrol of the tive lyer thikness nd doping densityF ine implnttion uses struturl disorderD the rystl lttie of the qes must e sujeted to post implnttion rpid therml nnel step to repir the dmge nd to tivte the implnted speiesF he required nneling temperture @> VHH gA is higher thn the temperture t whih qes deomposesF ilion nitride enpsultion is used to prevent suh dissoitionF ilion nitride is lso used for the (nl enpsultion of qes wipi devies @pigure TFIUAF
7 8
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PPQ
Figure 6.17: Schematic diagrams of a GaAs metal-semiconductor eld eect transistor (MESFET). Adapted from A. R. Barron, in CVD of Nonmetals, Ed. W. S. Rees, Jr., Wiley, NY (1996).
he deposition of i3 x4 is rodly prtied industril proess using either grown y low pressure gh @vghA or plsm enhned gh @ighA with omprle properties for the grown (lms @le TFWAF
Deposition LPCVD PECVD
qrowth temperture @ gA gomposition iGx rtio etom7 r hieletri onstnt efrtive index esistivity @FmA fnd gp @eA
Table 6.9
UHH E VHH i3 x4 @rA HFUS REV TEU PFHI IHIT S
PSH E QSH ixx ry HFV E IFP PH E PS TEW IFV E PFS IHT E IHIS RES
X ummry of the properties of silion nitride grown in typil ommeril systemsF
yne of the disdvntges of i3 x4 is its high dieletri onstnt tht my limit devie speed t higher operting frequeniesF st is hoped tht silion oxynitride @iyxA (lms will exhiit the est properties of iQxR nd iy2 D nmely the pssivtion nd mehnil properties of i3 x4 nd the low dieletri onstnt nd low stress of iy2 F e summry of some typil gh systems for silion nitride is given in le TFIHF
Silicon cursor preNitrogen source Carrier gas CVD method Deposition temp. ( C) Comment
PPR ir4 ir4 ir4 igl2 r2 i2 gl6 it2 ir2 i@x3 A3 @ a itD t fuA weir@xrAn i@xwe2 A4-n rn i@xwe2 A4-n rn xr3 xr3 x2 xr3 xr3 xr3 E x2 erGx2 x2 x2 E E E

egh igh igh vgh vgh vgh vgh UH E WHH PH E THH UH E QHH UHH E WHH RSH E VSH TSH E UPS RSH E THH g impurities hnger preursor explosive igni(nt ontent igni(nt ontent ! gommeril proess orous (lms gommeril proess
E E xr3
xr3 Gr2 re re
egh egh egh
THH E VHH THH E USH THH E USH
g g
xo g ontmiE ntion
Table 6.10
X reursors nd deposition onditions for i3 x4 ghF
6.5.2.2 CVD of silicon nitride from hydrides and chlorides
he (rst ommeril growth of silion nitride ws y the retion of ir4 nd xr3 y either tmospheri pressure gh @eghA or ighF pilm growth using egh is slower nd requires higher tempertures nd so it hs een generlly supplnted y plsm growthD howeverD (lm qulity for egh is higher due to the lower hydrogen ontentF hile thermlly grown (lms re lose to stoihiometriD igh (lms hve omposition in whih the Gx rtio is oserved to vry from HFU E IFIF he nonEstoihiometri nture of igh (lms is explined y the inorportion of signi(nt hydrogen in the (lms @IH E QH7AF igh of ixx using ir4 Gx2 leds to eletronilly leky (lms due to the porous nture of the (lmsD howeverD if n eletron ylotron resonne @igA plsm is employedD ixx (lms of high qulity my e deposited on mient temperture sustrtesF he more reent ommeril methods for silion nitride deposition involves vgh using igl2 r2 s the silion soure in omintion with xr3 t UHH E WHH gF he redued pressure of vgh hs the dvntges of high purityD low hydrogen ontentD stoihiometri (lmsD with high degree of uniformityD nd high wfer throughputF st is for these resons tht vgh is now the method of hoie in ommeril systemsF e lrge exess of xr3 is therefore used in ommeril systems to otin stoihiometri (lmsF ilion nitride hs lso een prepred from igl4 Gxr4 D ifr4 Gxr3 D ndD more reentlyD i2 gl6 Gxr3 F ilion oxynitride @iyxA my e prepred y the use of ny of the preursors used for silion nitride with the ddition of either x2 y or xy s n oxygen soureF he omposition nd properties of the iyx xy (lms my e vried from iy2 Elike to i3 x4 Elike y the vrition of the retnt )ow rtesF igl2 r2 gs pluming to vgh retor must e thermlly insulted to prevent ondenstion tht would otherwise led to hzy deposits on the (lmF he voltile yEproduts from gh produe xr4 gl t the exhust of the retion tueD nd in the pluming nd pumping systemF st would e desirleD thereforeD to (nd n lterntiveD hlorineEfree silion soure with none of the toxiity or pyrophoriity prolems ssoited with ir4 F st is for this reson tht orgnosilion ompounds hve een investigtedF
PPS
6.5.2.3 CVD from organosilicon precursors
hiethylsilneD it2 ir2 D hs shown promise s replement for ir4 in the low temperture vgh of iy2 D nd hs een investigted s soure for ixx nd iyx xy (lmsF heposition y vgh in the presene of xrQ produes ixx (lmsD in whih the ron ontmintion @R E W7A depends on the prtil pressure of the it2 ir2 F he presene of ron rises the refrtive index @PFHPS E PFPVA with respet to trditionl vgh (lms @PFHIAF wixtures of it2 ir2 D xr3 D nd x2 y deposit iyx xy (lms where the omposition is ontrolled y the xr3 Xx2 y rtioF
6.5.2.3.1 CVD from silicon-nitrogen compounds
he inorportion of ron into silion nitride (lms is persistent prolem of orgnosilion preursorsF everl studies hve een imed t developing single soure preursors ontining iEx ond rther thn iEg ondsF olyzidosilnesD n i@x3 A4-n D re low in ron nd hydrogenD resonly voltileD nd ontin highly tivted nitrogenD howeverD they represent signi(nt explosive hzrdX they are explosive with an equivalent force to TNTF pilms deposited using iti@x3 A3 nd @tfuAi@x3 A3 showed promiseD despite the oservtion of oxygen nd ronF yrolyti studies on the zide preursors suggest tht the primry deomposition step is the loss of dinitrogenD whih is followed y migrtion of the lkyl onto the remining nitrogenD @TFSRAF he ft tht neither the ddition of xr3 or r2 in)uene the (lm deposition rte suggest tht the intrmoleulr nitride formtion proess is fstD reltive to retion with xr3 D or hydrogentionF @TFSRA gron inorportion is lso oserved for the egh deposition from i@xwe2 An r4-n @n a P E RAF roweverD using the ro'mn trnsmintion retionD deposition in the presene of xr3 ompletely removed ron inorportion into the stoihiometri i3 x4 (lmF prom ps dtD the hydrogen ontent ws estimted to e V E IH tom perentF hile the i@xwe2 An r4-n Gxr3 system does not provide sustntilly lower temE pertures thn egh using ir4 Gxr3 growth rtes re signi(ntly higherF nlike the zide preursorsD i@xwe2 An r4-n re esier to hndle thn either ir4 or igl2 r2 F
tF gF frourD rF tF teinD yF eF opovD wF oderD nd gFeF yuttenD J. Vac. Sci. Technol. A.D IWWID 9D RVHF tF eF riggensD F vF uuvsD pF rF iisenD nd hF F ghenD IEEE Trans. Electron. DevicesD IWUVD 25D SVUF hF wF ro'mnD PolyhedronD IWWRD 13D IITWF F uellnerD rF uniepkmpD hF epowD wF reinzelD nd rF forolekD Solid State Electron.D IWUUD 20D RSWF F wkinoD J. Electrochem. Soc.D IWVQD 130D RSHF gF F xer nd qF gF vokwoodD in Semiconductor SiliconD idsF rF F ru' nd F F furgessF he iletrohemil oietyD oftound roeedings eriesD rinetonD xt @IWUQAF tF iF hoenholtzD hF F ressD Thin Solid FilmsD IWVUD 148D PVSF
6.5.3 Chemical Vapor Deposition of Aluminum Nitride

eluminum nitride @elxA hs potentil for signi(nt pplitions in miroeletroni nd optil deviesF st hs lrge diret ndgp @ig,dir a TFPV eAD extremely high melting point @QHHH gAD high therml
9
PPT
ondutivity @PFT GmFuAD nd lrge dieletri onstnt @ a WFIRAF sn present ommeril miroeletroni deviesD elx is used most often s pkging mterilD llowing for the onstrution of omplex pkges with mny signlD groundD powerD ondingD nd seling lyersF eluminum nitride is espeilly useful for high power pplitions due to its enhned therml ondutivityF ghemil vpor deposition @ghA grown thin (lms of elx hve een entered upon its use s high gteEinsultion lyer for ws deviesD nd dieletri in highEperformne pitorsF yne dditionl property of elx tht mkes it promising insulting mteril for oth i nd qes devies is tht its therml expnsion oe0ient is lmost identil to oth of these semiondutorsF he lk of suitly voltile homolepti hydride for luminum @elr3 is n involtile polymeri speiesA led to the pplition of luminum hlides nd orgnometlli ompounds s preursorsF e summry of seleted preursor omintions is given in le TFIIF
Aluminum precursor Nitrogen source Carrier gas CVD method Deposition temp. ( C) Comments
elgl3 @xr3 A elfr3 elfr3 elwe3 elwe3 elwe3
E xr3 x2 xr3 xr3 preErked xr3

t i
x2 x2 x2 r2 re r2 Gre
vgh egh vgh vgh egh egh
UHH E IRHH RHH E WHH SPH E STH IPHH QSH E RHH QIH E RTH
xr4 gl present fr present oriented growth
xEr nd elxE x onds deE teted high g ontentD low x very high ontent g
elwe3 elwe3 2 el@xr2 A3 @ a weD itA 2 elx3 3 @ a weD itA el@xwe2 A3
fuxr2 rxr2
or
r2 r2 r2
egh egh vgh
RHH E THH QHH E RSH RHH E VHH
we3 ix3
poor (lm qulE ityD high g onE tent unreted preE ursor present on (lm morphous IHH E PHH gD rysE tlline QHH E SHH g
vgh
RHH E SHH
xr3
re
egh
IHH E SHH
Table 6.11
X reursors nd deposition onditions for elx ghF
6.5.3.2 CVD from halides
he oservtion tht elx powder my e produed upon the therml deomposition of the elgl3 @xr3 A omplexD prompted initil studies on the use of elgl3 Gxr3 for the gh of elx (lmsF snitillyD the low voltility of elgl3 @ polymeri hin strutureA required tht the elgl3 @xr3 A omplex to e used s single preursorF vow pressure gh @vghA t S EIH orr resulted in deposition of elx (lmsD lthough
PPU (lms deposited elow IHHH g were ontminted with xr4 glD nd ll the (lms ontined hlorineF pilms with resonle eletril properties were prepred y the use of the more voltile tris Emmoni omplexD elgl3 @xr3 A3 F he dieletri onstnt for (lms grown t VHH E IHHH g @IIFSA is higher thn ulk elx @WFIRA nd lso thn tht of the (lms grown t IIHH g @VFIAF ell the (lms were polyrystlline with the grin size inresing with inresing deposition tempertures nd preferred orienttion ws oserved only for the (lms grown elow IHHH gF eluminum romide is dimeri voltile ompoundD fr2 el@EfrA2 D nd is more ttrtive s gh soureD thn elgl3 F heposition of elx (lms n e omplished using elfr3 nd xr3 in n egh system with r2 s the rrier gsF he mehnism of (lm growth hs een proposed @pigure TFIVAF
Figure 6.18:
Mechanism of APCVD lm growth of AlN using AlBr3 and NH3 .
hue to the high tempertures required @USH gA for good qulity elx (lm growth from elfr3 D igh ws investigtedF sing n elfr3 Er2 Ex2 gs mixture nd PRSH wrz mirowve @IHH E IHHH A plsm soureD elx (lms were grownF he mximum deposition rte ourred with n x2 Gelfr3 rtio of caF PH nd sustrte temperture caF THH gF
6.5.3.3 CVD from aluminum alkyls
fsed upon the suessful metl orgni gh @wyghA growth of elqes using the lkyl derivtivesD el3 D it ws logil to extend wygh to luminum nitrideF snitil studies were performed using elwe3 nd xr3 with r2 rrier gsF hile these (lms re generlly of high qulityD the temperture of deposition is inomptile with semiondutor proessing @eing ove oth the melting point of most metlliztion lloys nd the temperture t whih dopnt migrtion eomes deleteriousAF vower tempertures @s low s QSH gA were exploredD however signi(nt preEretion ws oserved etween elwe3 nd xr3 Y using depletion of the retnts in the deposition zoneD reduing the growth rte nd leding to nonEuniform depositsF wo routes hve een investigted y whih this prolem n e irumventedF igh suessfully lowers the deposition tempertureD lthoughD degrdtion of the sustrte surfe y ion omrdment is signi(nt drwkF qiven tht it is the mmoni deomposition tht represents the highest energy proessD preErking should lower the overll deposition tempertureF his is indeed oserved for the elwe3 Gxr3 Esed elx system where growth is hieved s low s SVR g if the xr3 is tlytilly rked over heted tungsten (lment @IURU gAF sn ftD with tlyti preErkingD deposition rtes were oserved to e n order of mgnitude greter thn for igh t the sme temperturesD resulting in (lms tht were rystlline with olumnr growthF por this pproh to lowEtemperture wygh growth of elx the only mjor drwk is the presene of residul xEr nd elxEx groups deteted y pEsF ghemil solutions to the high stility of xr3 hve primrily entered upon the use of lterntive nitrogen souresF he use of the voltile nitrogen soure hydrzine @x2 r4 AD hs llowed for the growth
PPV
of elx t tempertures s low s PPH gD howeverD hydrzine is extremely toxi nd highly unstleD restriting its ommeril pplitionF rimry minesD suh s t fuxr2 or i rxr2 D llow for deposition t modest tempertures @RHH E THH gAF he high ron inorportionD s high s IU7 preludes their doptionF e similr prolem is oserved with the use of trimethylsilylzideD we3 ix3 F he presene of ron ontmintion in the deposition of el (lms nd elqes epitxil lyers hs een ttriuted to the use of elwe3 F herefore ttempts hve een mde to use lterntive luminum preursorsF snterest in the mehnism of nuletion nd tomi lyer growth of elx hs prompted severl mehnisti studies of the formtion of elEx onds on the growth surfeF ell the studies onurred tht the mehnism involves stepEwise retion where the mide @Exr2 EA groups form ovlent onds to luminum irrespetive of sustrteF e shemti representtion of the proess is shown in pigure TFIWF
A schematic representation of the proposed step-wise reaction involving the formation of amide (-NH2 -) groups covalently bound to aluminum during the MOCVD growth of AlN using AlMe3 /NH3 . (Adapted from M. E. Bartram, T. A. Michalske, J. W. Rogers, Jr., and R. T. Paine, Chem. Mater., 1993, 5, 1424).
Figure 6.19:
6.5.3.4 CVD from aluminum amide and related compounds
he retion etween luminum lkyls nd mines @@TFSSAAD s well s the formtion of elx powders from the pyrolysis of elwe3 @xr3 A @@TFSTAAD led to the misguided onept tht the route to highEpurity elx would e through the soElled single soure preursor routeF @TFSSA
@TFSTA he trimeri dimethylluminum mideD we2 el@xr2 A3 @pigure TFPHAD ws originlly used s single soure preursor for growth of elx under vgh onditions using hot wlled retorD lthough susequent deposition ws lso demonstrted in old wlled systemF pilm qulity ws never demonstrted for eletroni pplitionsD ut the (lms showed promise s (er otings for ompositesF he onept of using trimeri
PPW single soure preursor for elx ws derived from the oservtion of el3 x3 yles s the smllest struturl frgment in wurtzite elxF roweverD detiled mehnisti studies indite tht under gs phse thermolysis the trimeri preursor we2 el@xr2 A3 is in equilirium with @or deomposes toA dimeri @pigure TFPHA nd monomeri @pigure TFPHA ompoundsF purthermoreD nitrogenEpoor speies @pigure TFPHdA were lso oserved y ypEmss spetrometryF
Figure 6.20: The trimeric dimethylaluminum amide (a) used as a single source precursor for growth of AlN, and the decomposition products (b - d) observed by TOF-mass spectrometry.
pollowing the erly reports of single soure preursor routesD wide rnge of ompounds hve een investigtedD inluding el@x2 A3 2 D rel@x2 A2 2 @ a weD itAD nd we2 elx@i rA2 2 D ll of whih gve elxD ut none of these preursors give (lms of superior qulity omprle to tht otined from trditionl ghF sn prtiulrD the (lms ontined signi(nt ron ontmintionD prompting further investigtions into the e0y ofD xEg ond freeD dilkylluminum zidesD 2 el@x3 A3 D s vgh preursorsF hile luminum tris EmidesD el@x2 A3 were shown to give ronEontminted (lmsD egh rriedE out with xr3 s the rrier gs results in ronEfree elx (lm growth s low s IHH gF he reson for the deposition of high qulity (lms t suh low tempertures resides with the ro'mn trnsmintion retion etween the primry mido unit nd mmoniF he rystllinityD ndgp nd refrtive index for the elx grown y egh using el@xwe2 A3 2 nd xr3 re dependent on the deposition tempertureF pilms grown t IHH E PHH g re morphous nd hve low ndgp nd low refrtive indexF eove QHH gD the (lms re rystllineD nd hve refrtive index lose to tht of ulk elx @IFWW E PFHPAD with ndgp @ SFUU eA pprohing the vlues reported for polyrystlline elx @SFV E SFW eAF
tF vF hupuie nd iF qulriD J. Vac. Sci. Technol. AD IWWPD 10D IVF hF wF ro'mnD PolyhedronD IWWRD 13D IITWF vF F snterrnteD F veeD wF wgonnellD xF vewisD nd iF rllD J. Electrochem. Soc.D IWVWD 136D RUPF rF wF wnsevitD pF wF irdmnnD nd F sF impsonD J. Electrochem. Soc.D IWUID 118D IVTRF
PQH
F uleuD eF foutevilleD tFtF rntzpergueD tF g emyD nd eF ghrdD J. Electrochem. Soc.D IWVHD 127D ISQPF F omenoD wF skiD nd F ririD Jpn. J. Appl. Phys.D IWWHD 29D vQSVF
6.6 Metal Organic Chemical Vapor Deposition of Calcium Fluoride
10
he hemil vpor deposition @ghA of metl )uorides hs een muh less studied thn tht of oxidesD pnitidesD or hlgogenidesF es my e expeted where voltile )uoride preursor is ville then suitle (lms my e grownF por exmpleD qroup S @D xD AD T @woD AD nd U @eA trnsition metls re redily deposited from )uorideEhydrogen mixturesF hile the use of )uorine is disourged on sfety groundsD mny of the )uorinted lkoxide or Ediketonte lignds employed for metl oxide metl orgni hemil vpor deposition @wyghA re predisposed to depositing metl )uoridesF he use of )uorine sustituted derivtives is euse they re often more voltile thn their hydroron nlogsD nd therefore redily used for oth tmospheri nd low pressure ghF o minimize the unwnted formtion of metl )uoridesD wter vpor is inorported in the gs stremD nd it is ommon to perform postEdeposition hydrolyti nnelsF roweverD there exist numer of pplitions where )uorides re requiredF por exmpleD the highly insulting nture of gp2 nd rp2 hs prompted investigtions into their use s gte insultor in qesEsed metl insultor semiondutor (eld e'et trnsistor @wspiA deviesF st should e noted tht while gp2 is good insultorD the gp2 Gqes interfe hs high interfe trp densityD requiring pssivtion u'er lyer to e deposited on qes prior to gp2 growthF yne of the di0ulties with the use of gp2 @nd rp2 A on qes is the lttie mismth @le TFIPAD ut this my e minimized y the use of solid solutions etween gp2 Erp2 F he omposition g0.44 r0.56 p2 is lmost perfetly lttieEmthed to qesF nfortuntelyD the therml expnsion oe0ient di'erenes etween qes nd gp2 Erp2 produe strins t the (lmGsustrte interfe under high temperture growth onditionsF he solution to this ltter prolem lies in the low temperture deposition of gp2 Erp2 y ghF
Compound Lattice constant ()
gp2 rp2 fp2 qes

Table 6.12
SFRT SFVT TFPH SFTSQP
X vttie prmeters of qroup P @ssA )uorides in omprison with qesF
olyrystlline gp2 my e grown y the pyrolyti deomposition of g@g5 we5 A2 @pigure TFPIA in either ip4 or xp3 F heposition t ISH g results in polyrystlline (lms with high levels of ron @IV7A nd oxygen @U7A impurities limiting the (lms usefulness in eletroni pplitionsF roweverD signi(ntly higher purity (lms my e grown t IHH g using the photoEssisted deomposition of g@hfA2 @pigure TFPIAF hese (lms were deposited t QH Gmin nd showed high degree of rystllogrphi preferred orienttionF
10
PQI
Figure 6.21:
CaF2 MOCVD precursors.
he mehnism eneling )uoride trnsfer to the metl @from the ron of )uorinted lkoxide ligE ndsA hs een investigtedF wygh employing x@yf A4 nd r@yf A4 yf a ygr@gp3 A2 nd ygwe3-n @gp3 An D n a I E Q gives xp nd rp4 (lmsD respetivelyD with voltile )uororon sideEprodutsF enlysis of the orgni sideEproduts indited tht deomposition ours y trnsfer of )uorine to the metl in onjuntion with IDPEmigrtion of residul group on the lkoxideD to form ketone @pigure TFPPAF he migrtion is inresingly file in the order gp3 gr3 rF he initil wEp ond formtion hs een proposed to e s onsequene of the lose w... p gosti intertions oserved for some )uorolkoxide nd )uoroE EdiketontesF
Proposed mechanism for the decomposition of uorinated alkoxide compounds. (Adapted from J. A. Samuels, W. -C. Chiang, C. -P. Yu, E. Apen, D. C. Smith, D. V. Baxter, K. G. Caulton, Chem. Mater., 1994, 6, 1684).
Figure 6.22:
6.6.1 Bibliography
eF F frronD in CVD of NonmetalsD F F eesD trF @edAD ileyD xew ork @IWWTAF
PQP
fF hF phlmn nd eF F frronD Adv. Mater. Opt. Electron.D PHHHD 10D PPQF rF rerlF vF fernrdD eF oherD gF pontineD eF wunozEtgueD J. Appl. PhysFD IWVUD 61D PRIHF tF eF muelsD F EgF ghingD gF EF uD iF epenD hF gF mithD hF F fxterD uF qF gultonD Chem. MaterFD IWWRD 6D ITVRF F ereD uF tF wkeyD hF gF odwyD F gF mithD hF w prigoD hF gF frdleyD Angew. Chem. Int. Ed. Engl. Adv. Mater.D IWVWD 28D ISVIF
6.7 Precursors for Chemical Vapor Deposition of Copper

note:
11
Electronic MaterialsF his module ws prepred with the ssistne of ei hoF
6.7.1 Introduction
ghemil vpor deposition @ghA is proess for depositing solid elements nd ompounds y retions of gsEphse moleulr preursorsF heposition of mjority of the solid elements nd lrge nd everEgrowing numer of ompounds is possile y ghF wost metlliztion for miroeletronis tody is performed y the physil vpor deposition @hA proE esses of evportion nd sputteringD whih re often oneptully nd experimentlly more strightforwrd thn ghF roweverD the inresing importne of gh is due to lrge degree to the dvntges tht it holds over physil vpor depositionF poremost mong these re the dvntges of onforml overge nd seletivityF puttering nd evportion re y their nture lineEofEsight deposition proesses in whih the sustrte to e oted must e pled diretly in front of the h soureF sn ontrstD gh llows ny sustrte to e oted tht is in region of su0ient preursor prtil pressureF his llows the uniform oting of severl sustrte wfers t oneD of oth sides of sustrte wferD or of sustrte of lrge size ndGor omplex shpeF he h tehniques lerly will lso deposit metl on ny surfe tht is in line of sightF yn the other hndD it is possile to deposit seletively on some sustrte mterils in the presene of others using ghD euse the deposition is ontrolled y the surfe hemistry of the preursorGsustrte pirF husD it my e possileD for exmpleD to synthesize gh preursor tht under ertin onditions will deposit on metls ut not on n insulting mteril suh s iy2 D nd to exploit this seletivityD for exmpleD in the frition of very lrgeEsle integrted @vsA iruitF st should lso e pointed out thtD unlike some h pplitionsD gh does not use rdition dmge of the sustrteF ine the IWTHsD there hs een onsiderle interest in the pplition of metl gh for thinE(lm deposition for metlliztion of integrted iruitsF eserh on the therml gh of opper is motivted y the ft tht opper hs physil properties tht my mke it superior to either tungsten or luminum in ertin miroeletronis pplitionsF he resistivity of opper @IFTU mFmA is muh lower thn tht of tungsten @SFT mFmA nd signi(ntly lower thn tht of luminum @PFU mFmAF his immeditely suggests tht opper ould e superior mteril for mking metl interonnetsD espeilly in devies where reltively long interonnets re requiredF he eletromigrtion resistne of opper is higher thn tht of luminum y four orders of mgnitudeF gopper hs inresed resistne to stressEindued voidge due to its higher melting point versus luminumF here re lso reported dvntges for opper relted devie performne suh s greter speed nd redued ross tlk nd smller g time onstntsF yn the wholeD the omintion of superior resistivity nd intermedite reliility properties mkes opper promising mteril for mny pplitionsD provide tht suitle gh proesses n e devisedF
6.7.1.1 Applications of metal CVD
here re numer of potentil miroeletroni pplitions for metl ghD inluding gte metlliztion @deposit on semiondutorAD ontt metlliztion @deposit on semiondutorAD di'usion rrier metlliztion
11
PQQ @deposit on semiondutorAD interonnet metlliztion @deposit on insultor nd ondutor or semionduE torAF wost of the relevnt fetures of metl gh re found in the interonnet nd vi (ll pplitionsD whih we rie)y desrie hereF here re silly two types of metl gh proesses tht my ourX @IA flnket or nonseletive depositionD in whih deposition proeeds uniformly over vriety of surfesF @PA eletive deposition in whih deposition only ours on ertin types of surfes @usully semiondutors or ondutorsD ut not insultorsAF e primry pplition of lnket metl gh is for interonnetsF he onforml nture of the gh proess is one of the key dvntges of gh over h nd is driving fore for its reserh nd developmentF he degree of onformlity is usully desried s the step overgeD whih is normlly de(ned s the rtio of the deposit thikness on the step sidewll to the deposit thikness on the top surfeF enother pplition for lnket metl gh is vi hole (lling to plnrize eh level for susequent proessingD his is hieved y depositing onforml (lm nd ething k to the insultor surfeD leving the metl plug inttF enother unique spet of gh is its potentil to deposit (lms seletivelyD whih would eliminte severl proessing steps required to perform the sme tskF he primry pplition for seletive metl gh would e for vi hole (llingF sdellyD deposition only ours on exposed ondutor or semiondutor surfesD so (lling of the vi hole is hieved in single stepF
6.7.2 Copper CVD

he hemil vpor deposition of opper originlly su'ered from lk of redily ville opper ompounds with the requisite properties to serve s gh preursorsF he suessful development of tehnologilly useful opper gh proess requires (rst nd foremost the design nd synthesis of opper preursor whih is voltileD iFeFD possesses n ppreile vpor pressure nd vporiztion rte to llow ese in trnsporttion to the retion zone nd deposition t high growth rtesF sts deomposition mehnism@sA should preferly e strightforwrd nd led to the formtion of pure opper nd voltile yEproduts tht re nonretive nd n e lenly removed from the retion zone to prevent (lmD sustrteD nd retor ontmintionF qseous or liquid soures re preferred to solid soures to void undesirle vritions in vporiztion rtes euse of surfeEre hnges during evportion of solid soures nd to permit high levels of reproduiility nd ontrol in soure deliveryF yther desirle fetures in preursor seletion inlude hemil nd therml stility to llow extended shelf life nd ese in trnsport nd hndlingD reltive sfety to minimize the industril nd environmentl impt of proessing nd disposlD nd low synthesis nd prodution osts to ensure n eonomilly vile proessF everl lsses of inorgni nd metlorgni soures hve een explored s opper souresF snorgni preursors for opper gh used hydrogen redution of opper hlide soures of the type gu or gu2 D where is hlorine @glA or )uorine @pAX P gu C r2 P gu C P r gu2 C r2 gu C P r he voltility of opper hlides is lowD the retions involved require prohiitively high tempertures @RHH E IPHH gAD led to the prodution of orrosive yEproduts suh s hydrohlori nd hydro)uori ids @rgl nd rpAD nd produe deposits with lrge onentrtions of hlide ontminntsF wenwhileD the explortion of metlorgni hemistries hs involved vrious opper@ssA nd opper@sA soure preursorsD with signi(nt dvntges over inorgni preursorsF
6.7.3 From Cu(II) precursors

6.7.3.1 Volatile Cu(II) compounds
gopper ws known to form very few stleD voltile lkyl or ronyl ompoundsF his ws thought to elimE inte the two mjor lsses of ompounds used in most existing proesses for gh of metls or ompound semiondutorsF gopper hlides hve een used for hemil vpor trnsport growth of guEontining semiE ondutor rystlsF fut the evportion tempertures needed for opper hlides re muh higher thn those
PQR
needed for metlEorgni ompoundsF pilm purity nd resistivity were lso prolemD possily re)eting the high retivity of i sustrtes with metl hlidesF gu@ssA ompounds tht hve een studied s gh preursors re listed in le TFIQF he struturl formuls of these ompounds re shown in pigure TFPQ long with the lignd revitions in le TFIRF ih ompound ontins entrl gu@ssA tom onded to two singly hrged Ediketonte or Eketoiminte ligndsF wost of them re stleD esy to synthesizeD trnsport nd hndleF
Compound Evaporation temp. ( C) Deposition temp. ( C) Carrier gas Reactor pressure (Torr)
gu@A2 gu@hfA2 gu@tfA2 gu@dpmA2 gu@ppmA2 gu@fodA2 gu@imA2 gu@nonEpA2 gu@enA2

Table 6.13
IVH E PHH VH E WS IQS E ITH IHH IHH E PVU VS E IHS PHR
PPS E PSH PSH E QHH PSH E QHH RHH RHH QHH E RHH RHH PUH E QSH RSH
r2 Ger r2 r2 none none r2 r2 r2 r2
UTH UTH UTH
<IH-2 <HFQ
IH-3 E UTH UQH IH E UH UQH
X tudies of gu gh using gu@ssA ompoundF edpted from F uods nd wF rmpdenEmithD The Chemistry of Metal CVDD gr ulishers snFD xew orkD x @IWWRAF
Figure 6.23:
Structures of Cu(II) compounds studied as CVD precursors.
PQS
Ligand abbreviation
R1
R2
Structural type
hf tf dpm ppm fod im nonEp en

Table 6.14
gr3 gp3 gr3 g@gr3 A3 g@gr3 A3 g@gr3 A3 gr3 gp3 gr3
gr3 gp3 gp3 g@gr3 A3 gp2 gp3 gp2 gp2 gp3 r gr2 gp3 E
X vignd revitions for the strutures shown in pigure TFPQF
ettention hs foused on gu@ssA Ediketonte iFeFD gu@tfA2 D gu@hfA2 nd gu@ssA Eketoiminte iFeFD gu@imA2 D gu@enA2 F en importnt hrteristi of gu@ssA ompounds s gh preursors is the use of hevily )uorinted lignd suh s gu@tfA2 nd gu@hfA2 versus gu@A2 F he min e'ort of )uorine sustitution is signi(nt inrese in the voltility of the omplexF
6.7.3.2 Synthesis of Cu(II) precursors 6.7.3.2.1 Cu(hfac)2 nH2 O (n = 0, 1, 2)
gu@hfA2 is y fr the most extensively studied of the gu@ssA gh preursorsF reprtions in queous solutions yield the yellowEgreen dihydrteD gu@hfA2 Pr2 yF his is stle in very humid ir or t lower tempertures ut slowly loses one moleule of wter under typil lortory onditions to form the grssE green monohydrteD gu@hfA2 r2 yF he monohydrteD whih is ommerilly villeD n e sulimed unhnged nd melts t IQQ ! IQT gF wore vigorous drying over onentrted r2 y4 produes the purple nhydrous ompound gu@hfA2 @mp a WS ! WV gAF he purple mteril is hydrosopiD onverting redily into the monohydrteF yther Ediketonte gu@ssA omplexes re prepred y the similr methodF
6.7.3.2.2 Schi-base complexes
hi'Ese omplexes inlude gu@imA2 D gu@enA nd gu@nonEpA2 F he (rst two of these n e prepred y mixing gu@xr3 A4 2+ @qA with the pure lignd nd y dding freshly prepred solid gu@yrA2 to solution of the lignd in etoneF he synthesis of gu@nonEpA2 D on the other hndD involved two importnt developmentsX the introdution of the silyl enol ether route to the lignd nd its onversion inEsitu into the desired preursorF he new pproh to the lignd ws required euseD in ontrst to nonE)uorinted EdiketontesD r@hfA rets with mines to produe sltsF
trting from the experimentl resultsD list of possile steps for gu gh vi r2 redution of gu@ssA ompounds would inlude the followingsD where removl of dsored lignd from the surfe is elieved to e the rte limiting stepX gu@ssAv2 @gA gu@sA C P v. @dsA r2 @gA P r. @dsA v. @dsA C r. @dsA rv@gA where v represents ny of the singly hrged Ediketonte or Eketoiminte lignds desried eforeF his mehnism gives ler explntion of the importne of hydrogen eing presentX in the sene of hydrogenD
PQT
rv nnot desor lenly into the gs phse nd lignd will tend to deompose on the surfeD resulting in impurity inorportion into the growing (lmF he mehnism is lso supported y the oservtion tht the deposition retion is enhned y the ddition of lohol ontining Ehydrogen to the retion mixtureF wore reentlyD the fous hs shifted to gu@sA ompounds inluding gu@sA ylopentdienyls nd gu@sA EdiketonteF he gu@sA Ediketonte in prtiulr show gret promise s gu gh preursors nd hve superseded the gu@ssA Ediketonte s the est fmily of preursors urrently villeF
6.7.4 From Cu(I) precursors

6.7.4.1 Precursor design
he gu@sA ompounds tht hve een investigted re desried in pigure TFPRF hese speies n e rodly divided into two lssesD gu nd guvn D where is uninegtive lignd nd v is neutrl vewis se eletron pir donorF he guvn lss n e further sudivided ording to the nture of nd vF
Figure 6.24:
The Chemistry of Metal CVD
Copper(I) precursors used for CVD. Adapted from T. Kodas and M. Hampden-Smith, , VCH Publishers Inc., New York, NY (1994).
gompounds of generl formul gu re likely to e oligomeri resulting in reltively low vpor pressureF he presene of neutrl donor ligndD vD is likely to redue the extent of oligomeriztion ompred to gu y oupying vnt oordintion sitesF wetl lkoxide ompounds re expeted to undergo therml deomposition y levge of either wEy or yEg ondsF yrgnoEopper@sA ompoundsD guvD where is lkylD re thermlly unstleD ut ylopentdienyl ompounds re likely to e more roust due to the Eonding of the ylopentdienyl lignd to the opper enterF et the sme timeD the ylopentdienyl lignd is sterilly demndingD oupies three oordintion sites t the metl enterD nd therey redues the desire for oligomeriztionF sn generlD ylopentdienyl lignd is poor hoie to support gh preursorsD espeilly with eletropositive metlsD euse this lignd is unlikely to e lileF gompounds in the fmily guv2 D where is hlide nd v is triorgnophosE phineD exhiit reltively high voltility ut re thermlly stle with respet to formtion of opper t low temperturesF hese speies re therefore suitle s produts of ething retions of opper (lmsF
PQU e numer of reserhers hve demonstrted the potentil of series of Ediketonte gu@sA ompoundsD @ EdiketonteAguvn D where v is vewis se nd n a I or PD tht ful(ll most of the riteri outlined for preursor design eforeF hese speies were hosen s opper preursors for the following resonsX
hey ontin the Ediketonte lignd whih generlly imprts voltility to metlEorgni omplexesD prtiulrly when )uorintedD s result of redution in hydrogenEonding in the solidEstteF hey re ple of systemti sustitution through oth the Ediketonte nd vewis se lignds to tilor voltility nd retivityF vewis ses suh s phosphinesD ole(ns nd lkynes re unlikely to thermlly deompose t temperE tures where opper deposition oursF hese preursors n deposit opper vi thermlly indued disproportiontion retions nd no lignd deomposition is required sine the voltile vewis se the gu@ssA disproportiontion produts re trnsported out of the retor intt t the disproportiontion tempertureF
e generl feture of the retions of gu@sA preursors is tht they thermlly disproportionteD mehE nism likely to e responsile for the high purity of the opper (lms oserved sine lignd deomposition does not ourF he disproportiontion mehnism is shown in pigure TFPS for @ EdiketonteAguvF he unique pilities of this lss of ompounds result from this retion mehnism y whih they deposit opperF his mehnism is sed on the dissoitive dsorption of the preursor to form gu@hfA nd vD disproportiontion to form gu@hfA2 nd gu nd desorption of gu@hfA2 nd vF
Schematic diagram of the disproportionation mechanism. Adapted from T. Kodas and M. Hampden-Smith, The Chemistry of Metal CVD, VCH Publishers Inc., New York, NY (1994).
Figure 6.25:
husD the strting mteril ts s its own reduing gent nd no externl reduing gent suh s r2 is requiredF enother dvntge of the gu@sA Ediketontes over the gu@ssA Ediketontes is tht in the former the lignd v n e vried systemtillyD llowing the synthesis of whole series of di'erent ut losely relted ompoundsF
6.7.5 Selectivity
eletivity deposition hs een studied in oth hotE nd oldEwll gh retors s funtion of the nture of the sustrteD the temperture of the sustrte nd the nture of the opper sustituentsF eletivity hs
PQV
usully een evluted y using i sustrtes on whih iy2 hs een grown nd ptterned with vrious metls y either eletronEem depositionD gh or sputteringF eserh hs suggested tht seletivity on metlli surfes is ttriutle to the iomoleulr disproportiontion retion involved in preursor deompositionF
6.7.6 Bibliography
tF F greightonD nd tF iF rmeterD Critical Review in Solid State and Materials ScienceD IWWQD 18D IUSF vF rF huois nd fF F egrskiD J. Electrochem. Soc.D IWWPD 139D QPWSF tF tF trvisD F ereD nd wF pF vppertD J. Chem. Soc.D Dalton Trans.D IWUUD WWWF eF iF uloyerosD eF pengD tF qrhrtD uF gF frooksD F uF qhoshD eF xF zenD nd pF vuehersD J. Electronic Mater., IWWHD 19D PUIF F uods nd wF rmpdenEmithD The Chemistry of Metal CVDD gr ulishers snFD xew orkD x @IWWRAF gF pF owellD tF rF yxleyD nd tF wF floher trFD Vapor DepositionD tohn ileyD xew ork @IWTTAF F hingurD F xkskiD nd rF unekoD Appl. Phys. Lett., IWWID 58D RPF
Chapter 7
Materials Characterization
7.1 Rutherford Backscattering of Thin Films
7.1.1 Introduction
yne of the min reserh interests of the semiondutor industry is to improve the performne of semiE onduting devies nd to onstrut new mterils with redued size or thikness tht hve potentil pE plition in trnsistors nd miroeletroni deviesF roweverD the most signi(nt hllenge regrding thin (lm semiondutor mterils is mesurementF roperties suh s the thiknessD omposition t the surE feD nd ontmintionD ll re ritil prmeters of the thin (lmsF o ddress these issuesD we need n nlytil tehnique whih n mesure urtely through the depth of the of the semiondutor surfe without destrution of the mterilF utherford ksttering spetrosopy is unique nlysis method for this purposeF st n give us informtion regrding inEdepth pro(ling in nonEdestrutive mnnerF rowE ever Ery photo eletron spetrosopy @AD energy dispersive Ery nlysis @ihA nd euger eletron spetrosopy re lso le to study the depthEpro(le of semiondutor (lmsF le UFI demonstrtes the omprison etween those tehniques with fF
Method Destructive Incident particle Outgoing Particle Detection limit Depth lution reso1
f ih euger
xo es es es
Table 7.1
son Ery photon iletron iletron
son iletron Ery photon iletron
I HFIEI HFI HFIEI
IH nm
I m
IFS nm IFS nm
X gomprison etween di'erent thin (lm nlysis tehniquesF
7.1.2 Basic concept of Rutherford backscattering spectroscopy

et si levelD f demonstrtes the eletrostti repulsion etween high energy inident ions nd trE get nuleiF he speimen under study is omrded with monoenergeti em of 4 re+ prtiles nd the ksttered prtiles re deteted y the detetorEnlysis system whih mesures the energies of the prE tilesF huring the ollisionD energy is trnsferred from the inident prtile to the trget speimen tomsY the hnge in energy of the sttered prtile depends on the msses of inoming nd trget tomsF por n
1
PQW
PRH
CHAPTER 7. MATERIALS CHARACTERIZATION
inident prtile of mss w1 D the energy is i0 while the mss of the trget tom is w2 F efter the ollisionD the residul energy i of the prtile sttered t ngle n e expressed sX
where k is the kinemti sttering ftorD whih is tully the energy rtio of the prtile efore nd fter the ollisionF ine k depends on the msses of the inident prtile nd trget tom nd the sttering ngleD the energy of the sttered prtile is lso determined y these three prmetersF e simpli(ed lyout of ksttering experiment is shown in pigure I @pigure UFIAF
Figure 7.1:
Schematic representation of the experimental setup for Rutherford backscattering analysis.
he proility of sttering event n e desried y the di'erentil sttering ross setion of trget tom for sttering n inoming prtile through the ngle into di'erentil solid ngle s followsD
where d R is the e'etive di'erentil ross setion for the sttering of prtileF he ove eqution my looks omplited ut it onveys the messge tht the proility of sttering event n e expressed s funtion of sttering ross setion whih is proportionl to the z when prtile with hrge ze pprohes the trget tom with hrge eF relium ions not sttered t the surfe lose energy s they trverse the solidF hey lose energy due to intertion with eletrons in the trgetF efter ollision the re prtiles lose further energy on their wy out to the detetorF e need to know two quntities to mesure the energy lossD the distne t tht the prtiles penetrte into the trget nd the energy loss i in this distne pigure UFPF he rte of energy loss
PRI or stopping power is ritil omponent in ksttering experiments s it determines the depth pro(le in given experimentF
Components of energy loss for a ion beam that scatters from depth t. First, incident beam loses energy through interaction with electrons Ein . Then energy lost occurs due to scattering Ec . Finally outgoing beam loses energy for interaction with electrons Eout . Adapted from L. C. Feldman and J. W. Mayer, Fundamentals of Surface and Thin Film Analysis , North Holland-Elsevier, New York (1986).
Figure 7.2:
sn thin (lm nlysisD it is onvenient to ssume tht totl energy loss i into depth t is only proportionl to t for given trgetF his ssumption llows simple derivtion of energy loss in ksttering s more omplete nlysis requires mny numeril tehniquesF sn onstnt dE Gdx pproximtionD totl energy loss eomes linerly relted to depth tD pigure UFQF
PRP
Figure 7.3:
Variation of energy loss with the depth of the target in constant dE/dx approximation.
7.1.3 Experimental set-up

he pprtus for utherford ksttering nlysis of thin solid surfe typilly onsist of three ompoE nentsX IF e soure of helium ionsF PF en elertor to energize the helium ionsF QF e detetor to mesure the energy of sttered ionsF here re two types of elertorGion soure villeF sn single stge elertorD the re+ soure is pled within n insulting gsE(lled tnk @pigure UFRAF st is di0ult to instll new ion soure when it is exhusted in this type of elertorF woreoverD it is lso di0ult to hieve prtiles with energy muh more thn I we sine it is di0ult to pply high voltges in this type of systemF
PRQ
Figure 7.4:
Schematic representation of a single stage accelerator.
enother vrition is tndem elertorF rere the ion soure is t ground nd produes negtive ionF he positive terminl is loted is t the enter of the elertion tue @pigure UFSAF snitilly the negtive ion is elerted from ground to terminlF et terminl twoEeletron stripping proess onverts the re- to re++ F he positive ions re further elerted towrd ground due to olumi repulsion from positive terminlF his rrngement n hieve highly elerted re++ ions @ PFPS weA with moderte voltge of USH kF
Figure 7.5:
Schematic representation of a tandem accelerator.
rtiles tht re ksttered y surfe toms of the omrded speimen re deteted y surfe rrier detetorF he surfe rrier detetor is thin lyer of pEtype silion on the nEtype sustrte resulting pEn juntionF hen the sttered ions exhnge energy with the eletrons on the surfe of the detetor upon rehing the detetorD eletrons get promoted from the vlene nd to the ondution ndF husD eh exhnge of energy retes eletronEhole pirsF he energy of sttered ions is deteted y simply ounting the numer of eletronEhole pirsF he energy resolution of the surfe rrier detetor in stndrd f experiment is IP E PH keF he surfe rrier detetor is generlly set etween WH nd IUH to the inident emF pilms re usully set norml to the inident emF e simple lyout is shown in pigure UFTF
PRR
Schematic representation general setup where the surface barrier detector is placed at angle of 165 to the extrapolated incident beam.
Figure 7.6:
7.1.4 Depth prole analysis

es stted erlierD it is good pproximtion in thin (lm nlysis tht the totl energy loss i is proportionl to depth tF ith this pproximtionD we n derive the reltion etween energy width i of the signl from (lm of thikness t s followsD i a t@k diGdx in C IGos diGdx out A where a l sttering ngleF st is worth noting tht k is the kinemti ftor de(ned in eqution ove nd the susripts in nd out indite the energies t whih the rte of loss of energy or diGdx is evlutedF es n exmpleD we onsider the ksttering spetrumD t sttering ngle IUH D for P we re++ inidents on silion lyer deposited onto P mm thik nioium sustrte pigure UFUF
PRS
The backscattering spectrum for 2.0 MeV He ions incident on a silicon thin lm deposited onto a niobium substrate. Adapted from P. D. Stupik, M. M. Donovan, A. R. Barron, T. R. Jervis and M. Nastasi, Thin Solid Films, 1992, 207, 138.
Figure 7.7:
he energy loss rte of inoming re++ or diGdx long inwrd pth in elementl i is PRFT eG t P we nd is PT eG for the outgoing prtile t IFIP we @ine u of i is HFST when the sttering ngle is IUH D energy of the outgoing prtile would e equl to P x HFST or IFIP weA F egin the vlue of iSi is IQQFQ keF utting the vlues into ove eqution we get t IQQFQ keG@HFST B PRFT eG C IGos IUH B PT eGA a IQQFQ keG@IQFUU eG C PWGFWVS eGA a IQQFQ keG RHFIU eG a QQIV F rene i lyer of F QQHH thikness hs een deposited on the nioium sustrteF rowever we need to rememer tht the vlue of diGdx is pproximted in this lultionF
7.1.5 Quantitative Analysis

sn ddition to depth pro(le nlysisD we n study the omposition of n element quntittively y kstE tering spetrosopyF he si eqution for quntittive nlysis is a F F F xt
PRT
here is the yield of sttered ions from thin lyer of thikness tD is the numer of inident ions nd is the detetor solid ngleD nd xt is the numer of speimen toms @tomGm2 AF shows the f spetrum for smple of silion deposited on nioium sustrte nd sujeted to lser mixingF he x hs reted with the silion to form xi2 interphse lyerF he x signl hs rodened fter the retion s show in F
Backscattering spectra of Si diused into Nb and Si as deposited on Nb substrate. Adapted from P. D. Stupik, M. M. Donovan, A. R. Barron, T. R. Jervis and M. Nastasi, Thin Solid Films, 1992, 207, 138.
Figure 7.8:
e n use rtio of the heights rSi GrNb of the ksttering spetrum fter formtion of xi2 to determine the omposition of the siliide lyerF he stoihiometri rtio of x nd i n e pproximted sD xSi GxNb rSi B Si GrNb B Nb rene the onentrtion of i nd x n e determined if we n know the pproprite ross setions Si nd Nb F rowever the yield in the ksttering spetr is etter represented s the produt of signl height nd the energy width iF hus stoihiometri rtio n e etter pproximted s xSi GxNb rSi B iSi B Si GrNb B iNb B Nb
PRU
7.1.6 Limitations
st is of interest to understnd the limittions of the ksttering tehnique in terms of the omprison with other thin (lm nlysis tehnique suh s eiD nd sw @le UFIAF ei hs etter mss resolutionD lterl resolution nd depth resolution thn fF fut ei su'ers from sputtering rtiftsF gompred to fD sw hs etter sensitivityF f does not provide ny hemil onding informtion whih we n get from F eginD sputtering rtift prolems re lso ssoited in F he strength of f lies in quntittive nlysisF roweverD onventionl f systems nnot nlyze ultrthin (lms sine the depth resolution is only out IH nm using surfe rrier detetorF
7.1.7 Summary
utherford fksttering nlysis is strightforwrd tehnique to determine the thikness nd omposition of thin (lms @< RHHH AF eres tht hve een ltely explored re the use of ksttering tehnique in omposition determintion of new superondutor oxidesY nlysis of lttie mismthed epitxil lyersD nd s proe of thin (lm morphology nd surfe lusteringF
7.1.8 Bibliography
vF gF peldmn nd tF F wyerD Fundamentals of Surface and Thin Film AnalysisD xorth rollndE ilsevierD xew ork @IWVTAF Ion Spectroscopies for Surface AnalysisD idF eF F gzndern nd hF wF rerulesD lenum ress @xew orkAD IWWIF F hF tupikD wF wF honovnD eF frronD F F tervisD nd wF xstsiD Thin Solid FilmsD IWWPD 207D IQV
7.2 The Application of VSI (Vertical Scanning Interferometry) to the Study of Crystal Surface Processes
2
7.2.1 Introduction
he proesses whih our t the surfes of rystls depend on mny externl nd internl ftors suh s rystl struture nd ompositionD onditions of medium where the rystl surfe exists nd othersF he pperne of rystl surfe is the result of omplexity of intertions etween the rystl surfe nd the environmentF he mehnisms of surfe proesses suh s dissolution or growth re studied y the physil hemistry of surfesF here re lot of omputtionl tehniques whih llows us to predit the hnging of surfe morphology of di'erent minerls whih re in)uened y di'erent onditions suh s tempertureD pressureD pr nd hemil omposition of solution reting with the surfeF por exmpleD wonte grlo method is widely used to simulte the dissolution or growth of rystlsF roweverD the theoretil models of surfe proesses need to e veri(ed y nturl oservtionsF e n extrt lot of useful informtion out the surfe proesses through studying the hnging of rystl surfe struture under in)uene of environmentl onditionsF he hnges in surfe struture n e studied through the oservtion of rystl surfe topogrphyF he topogrphy n e diretly oserved mrosopilly or y using mirosopi tehniquesF wirosopi oservtion llows us to study even very smll hnges nd estimte the rte of proesses y oserving hnging the rystl surfe topogrphy in timeF wuh lortory worked under the reonstrution of surfe hnges nd interprettion of dissolution nd preipittion kinetis of rystlsF snvention of epw mde possile to monitor hnges of surfe struture during dissolution or growthF roweverD to detet nd quntify the results of dissolution proesses or growth it is neessry to determine surfe re hnges over signi(ntly lrger (eld of view thn epw n
2
PRV
provideF wore reentlyD vertil snning interferometry @sA hs een developed s new tool to distinguish nd tre the retive prts of rystl surfesF s nd epw re omplementry tehniques nd prtilly well suited to detet surfe hngesF s tehnique provides method for qunti(tion of surfe topogrphy t the ngstrom to nnometer levelF imeEdependent s mesurements n e used to study the surfeEnorml retret ross rystl nd other solid surfes during dissolution proessF hereforeD s n e used to diretly nd nondiretly mesure minerl dissolution rtes with high preisionF enlogillyD s n e used to study kinetis of rystl growthF
7.2.2 Physical principles of optical interferometry

yptil interferometry llows us to mke extremely urte mesurements nd hs een used s loE rtory tehnique for lmost hundred yersF homs oung oserved interferene of light nd mesured the wvelength of light in n experimentD performed round IVHIF his experiment gve n evidene of oung9s rguments for the wve model for lightF he disovery of interferene gve sis to development of interferomertry tehniques widely suessfully used s in mirosopi investigtionsD s in stronomi investigtionsF he physil priniples of optil interferometry exploit the wve properties of lightF vight n e thought s eletromgneti wve propgting through speF sf we ssume tht we re deling with linerly polrized wve propgting in vuum in z diretionD eletri (eld i n e represented y sinusoidl funtion of distne nd timeF
E (x, y, z, t) = aos [2 (vt z/)]
@UFIA
here a is the mplitude of the light wveD v is the frequenyD nd is its wvelengthF he term within the squre rkets is lled the phse of the wveF vet9s rewrite this eqution in more ompt formD
E (x, y, z, t) = aos t kz
@UFPA
where = 2v is the irulr frequenyD nd k = 2/ is the propgtion onstntF vet9s lso trnsform this seond eqution into omplex exponentil formD
E (x, y, z, t) = e{aexp (i) exp (it)} = e{Aexp (it)}
@UFQA
where = 2z/ nd A = exp (i) is known s the omplex mplitudeF sf n is refrtive index of medium where the light propgtesD the light wve trverses distne d in suh mediumF he equivlent optil pth in this se is
p=nd
@UFRA
hen two light wves re superposedD the result intensity t ny point depends on whether reinfore or nel eh other @pigure UFWAF his is well known phenomenon of interfereneF e will ssume tht two wves re propgting in the sme diretion nd re polrized with their (eld vetors in the sme plneF e will lso ssume tht they hve the sme frequenyF he omplex mplitude t ny point in the interferene pttern is then the sum of the omplex mplitudes of the two wvesD so tht we n writeD
A = A1 + A2
@UFSA
where A1 = a1 exp (i1 ) nd A2 = a2 exp (i2 ) re the omplex mplitudes of two wvesF he resultnt intensity isD thereforeD
I = | A | = I1 + I2 + 2 (I1 I2 )
1/2
os
@UFTA
PRW where I1 nd I2 re the intensities of two wves ting seprtelyD nd = 1 2 is the phse di'erene etween themF sf the two wves re derived from ommon soureD the phse di'erene orresponds to n optil pth di'ereneD
p = (/2)
@UFUA
The scheme of interferometric wave interaction when two waves interact with each other, the amplitude of resulting wave will increase or decrease. The value of this amplitude depends on phase dierence between two original waves.
Figure 7.9:
sf D the phse di'erene etween the emsD vries linerly ross the (eld of viewD the intensity vries osinusoidllyD giving rise to lternting light nd drk nds or fringes @pigure UFWAF he intensity in n interferene pttern hs its mximum vlue
Imax = I1 + I2 + 2 (I1 I2 )
when = 2m D where m is n integer nd its minimum vlue
1/2
@UFVA
Imin = I1 + I2 2 (I1 I2 )
1/2
@UFWA
when = (2m + 1) F he priniple of interferometry is widely used to develop mny types of interferometri set upsF yne of the erliest set ups is wihelson interferometryF he ide of this interferometry is quite simpleX interferene
PSH
fringes re produed y splitting em of monohromti light so tht one em strikes (xed mirror nd the other movle mirrorF en interferene pttern results when the re)eted ems re rought k togetherF he wihelson interferometri sheme is shown in pigure UFIHF
Figure 7.10:
Schematic representation of a Michelson interferometry set-up.
he di'erene of pth lengths etween two ems is Px euse ems trverse the designted distnes twieF he interferene ours when the pth di'erene is equl to integer numers of wvelengthsD
p = 2x = m, m = 0, 1, 2FFF
@UFIHA
wodern interferometri systems re more omplitedF sing speil phseEmesurement tehniques they ple to perform muh more urte height mesurements thn n e otined just y diretly looking t the interferene fringes nd mesuring how they deprt from eing stright nd eqully spedF ypilly interferometri system onsist of lights soureD emsplitterD ojetive systemD system of registrtion of signls nd trnsformtion into digitl formt nd omputer whih proess dtF ertil snning interferometry is ontins ll these prtsF pigure UFII shows on(gurtion of s interferometri systemF
PSI
Figure 7.11:
Schematic representation of the Vertical scanning interferometry (VSI) system.
wny of modern interferometri systems use wiru ojetive in their onstrutionsF wireu ojetive is sed on wihelson interferometerF his ojetive onsists of lensD referene mirror nd emsplitterF he ide of getting interfering ems is simpleX two ems @red linesA trvel long the optil xisF hen they re re)eted from the referene surfe nd the smple surfe respetively @lue linesAF efter this these ems re reomined to interfere with eh otherF en illumintion or light soure system is used to diret light onto smple surfe through ue em splitter nd the wireu ojetiveF he smple surfe within the (eld of view of the ojetive is uniformly illuminted y those ems with di'erent inidene nglesF eny point on the smple surfe n re)et those inident ems in the form of divergent oneF imilrlyD the point on the referene symmetril with tht on the smple surfe lso re)ets those illuminted ems in the sme formF he wireu ojetive direts the ems re)eted of the referene nd the smple surfe onto ggh @hrgeEoupled devieA sensor through tue lensF he ggh sensor is n nlog shift register tht enles the trnsporttion of nlog signls @eletri hrgesA through suessive stges @pitorsAD ontrolled y lok signlF he resulting interferene fringe pttern is deteted y ggh sensor nd the orresponding signl is digitized y frme grer for further proessing with omputerF he distne etween minimum nd mximum of the interferogrm produed y two ems re)eted from the referene nd smple surfe is knownF ht isD extly hlf the wvelength of the light soureF hereforeD with simple interferogrm the vertil resolution of the tehnique would e lso limited to GPF sf we will use lser light s light soure with wvelength of QHH nm the resolution would e only ISH
PSP
nmF his resolution is not good enough for detiled nerEtomi sle investigtion of rystl surfesF portuntelyD the vertil resolution of the tehnique n e improved signi(ntly y moving either the referene or the smple y frtion of the wvelength of the lightF sn this wyD severl interferogrms re produedF hen they re ll overlyedD nd their phse shifts ompred y the omputer softwre pigure UFIPF his method is widely known s phse shift interferometry @sAF
Sketch illustrating phase-shift technology. The sample is continuously moved along the vertical axes in order to scan surface topography. All interferograms are automatically overlayed using computer software.
Figure 7.12:
wost optil testing interferometers now use phseEshifting tehniques not only euse of high resolution ut lso euse phseEshifting is high ury rpid wy of getting the interferogrm informtion into the omputerF elso usge of this tehnique mkes the inherent noise in the dt tking proess very lowF es the result in good environment ngstrom or suEngstrom surfe height mesurements n e performedF es it ws sid oveD in phseEshifting interferometry the phse di'erene etween the interfering ems is hnged t onstnt rte s the detetor is red outF yne the phse is determined ross the interferene (eldD the orresponding height distriution on the smple surfe n e determinedF he phse distriution (x, y) is reorded y using the ggh merF vet9s ssign A(x, y)D B(x, y)D C(x, y) nd D(x, y) to the resulting interferene light intensities whih re orresponded to phseEshifting steps of HD / PD nd Q / PF hese intensities n e otined y moving the referene mirror through displements of / VD / R nd Q/ VD respetivelyF he equtions for the resulting intensities would eX
A (x, y) = I1 (x, y) + I2 (x, y) os (x, y) B (x, y) = I1 (x, y) I2 (x, y) sin (x, y)
@UFIIA @UFIPA
PSQ
C (x, y) = I1 (x, y) I2 (x, y) os (x, y) D (x, y) = I1 (x, y) + I2 (x, y) sin (x, y)
@UFIQA @UFIRA
where I1 (x, y)nd I2 (x, y) re two overlpping ems from two symmetri points on the test surfe nd the referene respetivelyF olving equtions @UFIIA!@UFIRAD the phse mp (x, y) of smple surfe will e given y the reltionX
(x, y) =
B (x, y) D (x, y) A (x, y) C (x, y)
@UFISA
yne the phseis determined ross the interferene (eld pixel y pixel on twoEdimensionl ggh rryD the lol height distriution/ ontourD h(x, y)D on the test surfe is given y
(x, y) @UFITA 4 xormlly the resulted fringe n e in the form of liner fringe pttern y djusting the reltive position etween the referene mirror nd smple surfesF rene ny distorted interferene fringe would indite lol pro(le/ ontour of the test surfeF st is importnt to note tht the wireu ojetive is mounted on pitive losedEloop ontrolled @piezoeletri tutorA s to enle phse shifting to e urtely implementedF he is sed on piezoeletri e'et referred to the eletri potentil generted y pplying pressure to piezoeletri mterilF his type of mterils is used to onvert eletril energy to mehnil energy nd vieEversF he preise motion tht results when n eletri potentil is pplied to piezoeletri mteril hs n importne for nnopositioningF etutors using the piezo e'et hve een ommerilly ville for QS yers nd in tht time hve trnsformed the world of preision positioning nd motion ontrolF ertil snning interferometer lso hs nother nmeY whiteElight interferometry @vsA euse of using the white light s soure of lightF ith this type of soure seprte fringe system is produed for eh wvelengthD nd the resultnt intensity t ny point of exmined surfe is otined y summing these individul ptternsF hue to the rod ndwidth of the soure the oherent length v of the soure is shortX h (x, y) = 2 @UFIUA n where is the enter wvelengthD n is the refrtive index of the mediumD is the spetrl width of the soureF sn this wy good ontrst fringes n e otined only when the lengths of interfering ems pthwys re losed to eh otherF sf we will vry the length of pthwy of em re)eted from smpleD the height of smple n e determined y looking t the position for whih fringe ontrst is mximumF sn this se interferene pttern exist only over very shllow depth of the surfeF hen we vry pthwy of smpleEre)eted em we lso move the smple in vertil diretion in order to get the phse t whih mximum intensity of fringes will e hievedF his phse will e onverted in height of point t the smple surfeF he omintion of phse shift tehnology with whiteElight soure provides very powerful tool to mesure the topogrphy of quite rough surfes with the mplitude in heights out nd the preision up to IEP nmF hrough developed softwre pkge for quntittively evluting the resulting interferogrmD the proposed system n retrieve the surfe pro(le nd topogrphy of the smple ojets pigure UFIQF L=
PSR
Figure 7.13:
Example of muscovite surface topography, obtained by using VSI- 50x objective.
7.2.3 A comparison of common methods to determine surface topography: SEM, AFM and VSI
ixept the interferometri methods desried oveD there re severl other mirosopi tehniques for studying rystl surfe topogrphyF he most ommon re snning eletron mirosopy @iwA nd tomi fore mirosopy @epwAF ell these tehniques re used to otin informtion out the surfe strutureF rowever they di'er from eh other y the physil priniples on whih they sedF
7.2.3.1 Scanning electron microscopy
iw llows us to otin imges of surfe topogrphy with the resolution muh higher thn the onventionl light mirosopes doF elso it is le to provide informtion out other surfe hrteristis suh s hemil ompositionD eletril ondutivity etD see pigure UFIRF ell types of dt re generted y the re)eting of elerted eletron ems from the smple surfeF hen eletrons strike the smple surfeD they lose their energy y repeted rndom sttering nd dsorption within n outer lyer into the depth vrying from IHH nm to S mironsF
PSS
Figure 7.14:
Scheme of electron beam-sample interaction at SEM analysis
he thikness of this outer lyer lso knows s intertive lyer depends on energy of eletrons in the emD omposition nd density of smpleF esult of the intertion etween eletron em nd the surfe provides severl types of signlsF he min type is seondry or inelsti sttered eletronsF hey re produed s result of intertion etween the em of eletrons nd wekly ound eletrons in the ondution nd of the smpleF eondry eletrons re ejeted from the kEoritls of toms within the surfe lyer of thikness out few nnometersF his is euse seondry eletrons re low energy eletrons @<SH eAD so only those formed within the (rst few nnometers of the smple surfe hve enough energy to espe nd e detetedF eondry ksttered eletrons provide the most ommon signl to investigte surfe topogrphy with lterl resolution up to HFR E HFU nmF righ energy em eletrons re elsti sttered k from the surfeF his type of signl gives inforE mtion out hemil omposition of the surfe euse the energy of ksttered eletrons depends on the weight of toms within the intertion lyerF elso this type of eletrons n form seondry eletrons nd espe from the surfe or trvel fther into the smple thn the seondryF he iw imge formed is the result of the intensity of the seondry eletron emission from the smple t eh xDy dt point during the snning of the surfeF
7.2.3.2 Atomic force microscopy
epw is very populr tool to study surfe dissolutionF epw set up onsists of snning shrp tip on the end of )exile ntilever whih moves ross smple surfeF he tips typilly hve n end rdius of P to PH nmD depending on tip typeF hen the tip touh the surfe the fores of these intertions leds to de)etion of ntileverF he intertion etween tip nd smple surfe involve mehnil ontt foresD vn der ls foresD pillry foresD hemil ondingD eletrostti foresD mgneti fores etF he de)etion of ntilever is usully mesured y re)eting lser em o' the k of the ntilever into split photodiode detetorF e shemti drwing of epw n e seen in pigure UFISF he two most ommonly used modes of opertion re ontt mode epw nd tpping mode epwD whih re onduted in ir or liquid environmentsF
PST
Figure 7.15:
Schematic drawing of an AFM apparatus.
orking under the ontt mode epw sns the smple while monitoring the hnge in ntilever de)etion with the split photodiode detetorF voop mintins onstnt ntilever re)etion y vertilly moving the snner to get onstnt signlF he distne whih the snner goes y moving vertilly t eh xDy dt point is stored y the omputer to form the topogrphi imge of the smple surfeF orking under the tpping mode epw osilltes the ntilever t its resonne frequeny @typillyQHH krzA nd lightly tps the tip on the surfe during snningF he eletrostti fores inrese when tip gets lose to the smple surfeD therefore the mplitude of the osilltion deresesF he lser de)etion method is used to detet the mplitude of ntilever osilltionF imilr to the ontt modeD feedk loop mintins onstnt osilltion mplitude y moving the snner vertilly t every xDy dt pointF eording this movement forms the topogrphil imgeF he dvntge of tpping mode over ontt mode is tht it elimintes the lterlD sher fores present in ontt modeF his enles tpping mode to imge softD frgileD nd dhesive surfes without dmging them while work under ontt mode llows the dmge to ourF
7.2.3.3 Comparison of techniques
ell tehniques desried ove re widely used in studying of surfe nnoE nd miromorphologyF roweverD eh method hs its own limittions nd the proper hoie of nlytil tehnique depends on fetures of nlyzed surfe nd primry gols of reserhF ell these tehniques re ple to otin n imge of smple surfe with quite good resolutionF he lterl resolution of s is muh lessD then for other tehniquesX ISH nm for s nd HFS nm for epw nd iwF ertil resolution of epw @HFS A is etter then for s @I E P nmAD however s is ple to mesure high vertil rnge of heights @I mmA whih mkes possile to study even very rough surfesF yn the ontrryD epw llows us to mesure only quite smooth surfes euse of its reltively smll vertil sn rnge @U mAF iw hs less resolutionD thn epw euse it requires oting of ondutive mteril with the thikness within severl nmF he signi(nt dvntge of s is tht it n provide lrge (eld of view @VRS TQH m for IHx ojetiveA of tested surfesF eent studies of surfe roughness hrteristis showed tht the surfe roughness prmeters inrese with the inresing (eld of view until ritil size of PSHDHHH m is rehedF his vlue is lrger then the mximum (eld of view produed y epw @IHH IHH mA ut n e esily otined y sF iw is lso ple to produe imges with lrge (eld of viewF roweverD iw is le to provide only Ph imges from one sn while epw nd s let us to otin Qh imgesF st mkes quntittive
PSU nlysis of surfe topogrphy more omplitedD for exmpleD topogrphy of memrnes is studied y ross setion nd top view imgesF
VSI AFM SEM
vterl resolution ertil resolution pield of view ertil rnge of sn reprtion of smple equired environment
Table 7.2
HFSEIFP m P nm VRS TQH m @IHx oE jetiveA I mm E eir
HFS nm HFS IHH IHH m IH m E eirD liquid
HFSEI nm ynly Ph imges IEP mm E equired oting of onduted mteril uum
X e omprison of s smple nd resolution with epw nd iwF
7.2.4 The experimental studying of surface processes using microscopic techniques

he limittions of eh tehnique desried ove re ritilly importnt to hoose pproprite tehnique for studying surfe proessesF vet9s explore pplition of these tehniques to study dissolution of rystlsF hen rystlline mtter dissolves the hnges of the rystl surfe topogrphy n e oserved y using mirosopi tehniquesF sf we will pply n unretive msk @silion for exmpleA on rystl surfe nd ple rystlline smple into the experiment retor then we get two types of surfesX dissolving nd remining the sme or unretedF efter some period of time the rystl surfe strts to dissolve nd hnge its zElevelF sn order to study these hnges ex situ we n pull out smple from the retion ell then remove msk nd mesure the verge height di'erene hetween the unreted nd dissolved resF he verge heights of dissolved nd unreted res re otined through digitl proessing of dt otined y mirosopesF he veloity of norml surfe retret vSNR during the time intervl t is de(ned s vSNR = h t hividing this veloity y the molr volume V @m3 GmolA gives glol dissolution rte in the fmilir units of moles per unit re per unit timeX
vSNR @UFIVA V his method llows us to otin experimentl vlues of dissolution rtes just y preise mesuring of verge surfe heightsF woreoverD using this method we n mesure lol dissolution rtes t eth pits y monitoring hnges in the volume nd density of eth pits ross the surfe over timeF s tehnique is ple to perform these mesurements euse of lrge vertil rnge of snningF sn order to get preise vlues of rtes whih re not depend on oserving ple of rystl surfe we need to mesure enough lrge resF s tehnique provides dt from res whih re lrge enough to study surfes with heterogeneous dissolution dynmis nd otin verge dissolution rtesF hereforeD s mkes possile to mesure rtes of norml surfe retret during the dissolution nd oserve formtionD growth nd distriution of eth pits on the surfeF roweverD if the mehnism of dissolution is ontrolled y dynmis of tomi steps nd kink sites within smooth tomi surfe reD the oservtion of the dissolution proess need to use more preise tehniqueF epw is ple to provide informtion out hnges in step morphology in situ when the dissolution R=
PSV
oursF por exmpleD immedite response of the dissolved surfe to the hnging of environmentl onditions @onentrtions of ions in the solutionD pr etFA n e studied y using epwF iw is lso used to exmine miro nd nnotexture of solid surfes nd study dissolution proessesF his method llows us to oserve lrge res of rystl surfe with high resolution whih mkes possile to mesure high vriety of surfesF he signi(nt disdvntge of this method is the requirement to over exmine smple y ondutive sustne whih limits the resolution of iwF he other disdvntge of iw is tht the nlysis is onduted in vuumF eent tehniqueD environmentl iw or iiw overomes these requirements nd mkes possile even exmine liquids nd iologil mterilsF he third disdvntge of this tehnique is tht it produes only Ph imgesF his retes some di0ulties to mesure h within the dissolving reF yne of dvntges of this tehnique is tht it is le to mesure not only surfe topogrphy ut lso hemil omposition nd other surfe hrteristis of the surfeF his ft is used to monitor hnging in hemil omposition during the dissolutionF
7.2.5 Bibliography

eF gF vsgD Kinetic Theory in the Earth SciencesF rineton nivF ressD rinetonD xt @IWWVAF eF vuttgeD iF F foltonD nd eF gF vsg eFgFD Am. J. Sci.D IWWWD 299D TSPF hF uzmrekD VacuumD PHHID 62D QHQF F rrihrnF Optical interferometryD eond editionD edemi press @PHHQA sfx HEIPEQIITQHEWF eF vuttge nd F qF gonrdD Appl. Environ. Microbiol.D PHHRD 70D ITPUF eF gF vsg nd eF vuttgeD American MineralogistD PHHRD 89D SPUF uF tF hvis nd eF vuttgeD Am. J. Sci.D PHHSD 305D UPUF F rF ng nd yD Meas. Sci. Technol.D PHHTD 17D TIUF eF vuttge nd F F ervidsonD in Kinetics of water-rock interactionD idF F frntleyD tF uuikiD nd eF hiteD pringer @PHHUAF vF hng nd eF vuttgeD American MineralogistD PHHUD 92D IQITF gF pisher eF nd vuttgeD Am. J. Sci.D PHHUD 307D WSSF F yrtD qF qeorgesD gF heumieD gF emrD nd F woulinD J. Membrane Sci.D PHHVD 315D VPF F gF imkisD iF hF ionomouD nd gF gF rplisD J. Therm. Anal. Cal.D PHHVD 92D UVQF
Chapter 8
Nanotechnology
8.1 Introduction to Nanoparticle Synthesis
1
he frition of nnomterils with strit ontrol over sizeD shpeD nd rystlline struture hs inspired the pplition of nnohemistry to numerous (elds inluding tlysisD mediineD nd eletronisF he use of nnomterils in suh pplitions lso requires the development of methods for nnoprtile ssemly or dispersion in vrious mediF e mjority of studies hve een imed t dispersion in queous medi imed t their use in medil pplitions nd studies of environmentl e'etsD howeverD the priniples of nnoprtile frition nd funtionliztion of nnoprtiles trnsends their eventul pplitionF rereinD we review the most generl routes to nnoprtiles of the key types tht my hve prtiulr pplition within the oil nd gs industry for sensorD ompositeD or devie pplitionsF ynthesis methods for nnoprtiles re typilly grouped into two tegoriesX topEdown nd ottomE upF he (rst involves division of mssive solid into smller portionsF his pproh my involve milling or ttritionD hemil methodsD nd voltiliztion of solid followed y ondenstion of the voltilized omponentsF he seondD ottomEupD method of nnoprtile frition involves ondenstion of toms or moleulr entities in gs phse or in solutionF he ltter pproh is fr more populr in the synthesis of nnoprtilesF hispersions of nnoprtiles re intrinsilly thermodynmilly metstleD primrily due to their very high surfe reD whih represents positive ontriution to the free enthlpy of the systemF sf the tivtion energies re not su0iently highD evolution of the nnoprtile dispersion ours using n inrese in nnoprtile size s typi(ed y n ystwld ripening proessF husD highly dispersed nnoprtiles re only kinetilly stilized nd nnot e prepred under onditions tht exeed some thresholdD mening tht soElled softEhemil or chemie duce methods re preferredF sn dditionD the use of surfe stiliztion is employed in mny nnomterils to hinder sinteringD rerystlliztion nd ggregtionF
8.1.1 Bibliography
tF qoplkrishnnD Chem. MaterFD IWWSD 7D IPTSF
8.2 Semiconductor Nanoparticles
he most studied nonEoxide semiondutors re dmium hlogenides @gdiD with i a sul(deD selenide nd tellurideAF gdi nnorystls were proly the (rst mteril used to demonstrte quntum size e'ets orresponding to hnge in the eletroni struture with sizeD iFeFD the inrese of the nd gp energy with
1 2
This content is available online at <http://cnx.org/content/m22372/1.2/>. This content is available online at <http://cnx.org/content/m22374/1.4/>.
PSW
PTH
CHAPTER 8. NANOTECHNOLOGY
the derese in size of prtiles @pigure VFIAF hese semiondutors nnorystls re ommonly synthesized y therml deomposition of n orgnometlli preursor dissolved in n nhydrous solvent ontining the soure of hlogenide nd stilizing mteril @polymer or pping ligndAF tilizing moleules ound to the surfe of prtiles ontrol their growth nd prevent prtile ggregtionF
Picture of cadmium selenide (CdSe) quantum dots, dissolved in toluene, uorescing brightly, as they are exposed to an ultraviolet lamp, in three noticeable dierent colors (blue 481 nm, green 520 nm, and orange 612 nm) due to the quantum dots' bandgap (and thus the wavelength of emitted light) depends strongly on the particle size; the smaller the dot, the shorter the emitted wavelength of light. The "blue" quantum dots have the smallest particle size, the "green" dots are slightly larger, and the "orange" dots are the largest.
Figure 8.1:
elthough dmium hlogenides re the most studies semionduting nnoprtilesD the methodology for the formtion of semionduting nnoprtiles ws (rst demonstrted independently for sn nd qesD eFgFD @VFIAF his method hs een dpted for rnge of semiondutor nnoprtilesF @VFIA sn the se of gdiD dimethyldmium gd@gr3 A2 is used s dmium soure nd is@trimethylsilylAsul(deD @we3 iA2 D triotylphosphine selenide or telluride @yeD yeA serve s soures of selenide in triE otylphosphine oxide @yyA used s solvent nd pping moleuleF he mixture is heted t PQHEPTH g over few hours while modulting the temperture in response to hnges in the size distriution s estimted from the sorption spetr of liquots removed t regulr intervlsF hese prtilesD pped with yGyy moleulesD re nonEggregted @pigure VFPA nd esily dispersile in orgni solvents forming optilly ler dispersionsF hen similr syntheses re performed in the presene of surftntD strongly nisotropi nnoprtiles re otinedD eFgFD rodEshped gde nnoprtiles n e otinedF
PTI
Figure 8.2:
TEM image of CdSe nanoparticles.
feuse gd@gr3 A2 is extremely toxiD pyrophori nd explosive t elevted tempertureD other gd soures hve een usedF gdy ppers to e n interesting preursorF gdy powder dissolves in yy nd re or he @tetrdeylphosphoni idA t out QHH g giving olorless homogeneous solutionF fy introduing selenium or tellurium dissolved in yD nnorystls grow to the desired sizeF xnorods of gde or gde n lso e produed y using greter initil onentrtion of dmium s ompred to retions for nnoprtilesF his pproh hs een suessfully pplied for synthesis of numerous other metl hlogenides inluding nD neD nd n1-x gdx F imilr proedures enle the formtion of wnD dD xiD gu2 nnoprtilesD nno rodsD nd nno disksF
8.2.1 Bibliography
gF F ferryD Phys. Rev.D IWTUD 161D VRVF wF hF relyD F iF viinisD F hF tupikD nd eF F frronD J. Chem. Soc., Chem. Commun.D IWVWD QSWF vF wnnD iF gF herD nd eF F elivistosD J. Am. Chem. Soc.D PHHHD 122D IPUHHF gF fF wurryD hF tF xorrisD nd wF qF fwendiD J. Am. Chem. Soc.D IWWQD 115D VUHTF F eF eng nd F engD J. Am. Chem. Soc.D PHHPD 12D QQRQF F vF ellsD gF qF ittD eF F whilD eF F urdyD F F fF h(eezdD nd rllok Chem. Mater.D IWVWD 1D RF F ongD F pengD F unollD nd rF wnD J. Am. Chem. Soc.D PHHQD 125D IQSSWF
8.3 Carbon Nanomaterials

8.3.1 Introduction
elthough nnomterils hd een known for mny yers prior to the report of g60 the (eld of nnosle siene ws undoutedly founded upon this seminl disoveryF rt of the reson for this explosion in nnohemistry is tht while ron mterils rnge from wellEde(ned nno sized moleules @iFeFD g60 A to tues with lengths of hundreds of mironsD they do not exhiit the instilities of other nnomterils s result of the very high tivtion rriers to their struturl rerrngementF es onsequene they re
3
PTP
highly stle even in their unfuntionlized formsF hespite this rnge of ron nnomterils possile they exhiit ommon retion hemistryX tht of orgni hemistryF he previously unknown llotrope of ronX g60 D ws disovered in IWVSD nd in IWWTD gurlD urotoD nd mlley were wrded the xoel rize in ghemistry for the disoveryF he other llotropes of ron re grphite @sp2 A nd dimond @sp3 AF g60 D ommonly known s the ukyll or fukminsterfullereneD hs spheril shpe omprising of highly pyrmidlized sp2 ron tomsF he g60 vrint is often ompred to the typil soer footllD hene ukyllF roweverD onfusinglyD this term is ommonly used for higher derivtivesF pullerenes re similr in sheet struture to grphite ut they ontin pentgonl @or sometimes heptgonlA rings tht prevent the sheet from eing plnrF he unusul struture of g60 led to the introdution of new lss of moleules known s fullerenesD whih now onstitute the third llotrope of ronF pullerenes re ommonly de(ned s ny of lss of losed hollow romti ron ompounds tht re mde up of twelve pentgonl nd di'ering numers of hexgonl fesF he numer of ron toms in fullerene rnge from g60 to g70 D g76 D nd higherF righer order fullerenes inlude ron nnotues tht n e desried s fullerenes tht hve een strethed long rottionl xis to form tueF es onsequene of di'erenes in the hemistry of fullerenes suh s g60 nd g70 s ompred to nnotuesD these will e delt with seprtely hereinF sn ddition there hve lso een reports of nnohorns nd nno(ersD howeverD these my e onsidered s vritions on the generl themeF st should e noted tht fullerenes nd nnotues hve een shown to e in )mes produed y hydroron omustionF nfortuntelyD these nturlly ourring vrieties n e highly irregulr in size nd qulityD s well s eing formed in mixturesD mking them unsuitle for oth reserh nd industril pplitionsF
8.3.2 Fullerenes
gronETH @g60 A is proly the most studied individul type of nnomterilF he spheril shpe of g60 is onstruted from twelve pentgons nd twenty hexgons nd resemles soer ll @pigure VFQAF he next stle higher fullerene is g70 @pigure VFQA tht is shped like rugy or emerin footllF he progression of higher fullerenes ontinues in the sequene g74 D g76 D g78 D etF he struturl reltionship etween eh involves the ddition of six memered ringsF wthemtilly @nd hemillyA two priniples de(ne the existene of stle fullereneD iFeFD iuler9s theorem nd isolted pentgon rule @sAF iuler9s theorem sttes tht for the losure of eh spheril networkD n @n PA hexgons nd IP pentgons re required while the s sys no two pentgons my e onneted diretly with eh other s destiliztion is used y two djent pentgonsF
Figure 8.3:
Molecular structures of (a) C60 and (b) C70 .
elthough fullerenes re omposed of sp2 rons in similr mnner to grphiteD fullerenes re solule in vrious ommon orgni solventsF hue to their hydrophoi ntureD fullerenes re most solule in g2
PTQ @g60 a UFW mgGmvA nd toluene @g60 a PFV mgGmvAF elthough fullerenes hve onjugted systemD their romtiity is distintive from enzene tht hs ll gEg onds of equl lengthsD in fullerenes two distint lsses of onds existF he shorter onds re t the juntions of two hexgons @TD T ondsA nd the longer onds t the juntions of hexgon nd pentgon @SDT ondsAF his di'erene in onding is responsile for some of the oserved retivity of fullerenesF
8.3.2.1 Synthesis of fullerenes
he (rst oservtion of fullerenes ws in moleulr em experiments t ie niversityF usequent studies demonstrted tht g60 it ws reltively esy to produe grms of fullerenesF elthough the synthesis is reltively strightforwrd fullerene puri(tion remins hllenge nd determines fullerene9s ommeril prieF he (rst method of prodution of mesurle quntities of fullerenes used lser vporiztion of ron in n inert tmosphereD ut this produed mirosopi mounts of fullerenesF vortory sles of fullerene re prepred y the vporiztion of ron rods in helium tmosphereF gommeril prodution ordinrily employs simple or d rF he fullerenes in the lk soot olleted re extrted in toluene nd puri(ed y liquid hromtogrphyF he mgent g60 omes o' the olumn (rstD followed y the red g70 D nd other higher fullerenesF iven though the mehnism of ron r di'ers from tht of resistively heted ron rod @euse it involves plsmA the re pressure for optimum g60 formtion is very similrF e rtio etween the mss of fullerenes nd the totl mss of ron soot de(nes fullerene yieldF he yields determined y Eis sorption re pproximtely RH7D IHEIS7D nd IS7 in lserD eletri rD nd solr proessesF snterestinglyD the lser ltion tehnique hs oth the highest yield nd the lowest produtivity ndD thereforeD sleEup to higher power is ostlyF husD fullerene ommeril prodution is hllenging tskF he world9s (rst omputer ontrolled fullerene prodution plnt is now opertionl t the wi gorportionD who pioneered the (rst ommeril prodution of fullerene nd fullerene produtsF
8.3.2.2 Endohedral fullerenes
indohedrl fullerenes re fullerenes tht hve inorported in their inner sphere tomsD ions or lustersF indohedrl fullerenes re generlly divided into two groupsX endohedrl metllofullerenes nd nonEmetl doped fullerenesF he (rst endohedrl metllofullerenes ws lled vdg60 F he d sign in the nme re)ets the notion of smll moleule trpped inside shellF hoping fullerenes with metls tkes ple in-situ during the fullerene synthesis in n r retor or vi lser evportionF e wide rnge of metls hve een ensed inside fullereneD iFeFD D D vD geD fD rD uD D rD nd rfF nfortuntelyD the synthesis of endohedrl metllofullerenes is unspei( euse in ddition high yield of un(lled fullerenesD ompounds with di'erent ge sizes re prepred @eFgFD vdg60 or vdg82 AF e hrteristi of endohedrl metllofullerenes is tht eletrons will trnsfer from the metl tom to the fullerene ge nd tht the metl tom tkes position o'Eenter in the geF he size of the hrge trnsfer is not lwys simple to determineD ut it is usully etween P nd Q units @eFgFD v2 dg80 A ut n e s high s T eletrons @eFgFD 3 xdg80 AF hese nioni fullerene ges re very stle moleules nd do not hve the retivity ssoited with ordinry empty fullerenes @see elowAF his lk of retivity is utilized in method to purify endohedrl metllofullerenes from empty fullerenesF he endohedrl redg60 nd xedg60 form when g60 is exposed to pressure of round Q r of the pproprite nole gsesF nder these onditions it ws possile to dope I in every TSHDHHH g60 ges with helium tomF indohedrl omplexes with reD xeD erD ur nd e s well s numerous dduts of the redg60 ompound hve lso een proven with operting pressures of QHHH rs nd inorportion of up to HFI 7 of the nole gsesF he isoltion of xdg60 D xdg70 nd dg60 is very unusul nd unlike the metl derivtives no hrge trnsfer of the pnitide tom in the enter to the ron toms of the ge tkes pleF
8.3.2.3 Chemically functionalized fullerenes
elthough fullerenes hve onjugted romti system ll the rons re quternry @iFeFD ontining no hydrogenAD whih results in mking mny of the hrteristi sustitution retions of plnr romtis
PTR
impossileF husD only two types of hemil trnsformtions existX redox retions nd ddition retionsF yf theseD ddition retions hve the lrgest syntheti vlueF enother remrkle feture of fullerene ddition hemistry is the thermodymis of the proessF ine the sp2 ron toms in fullerene re prmidlized there is signi(nt strin energyF por exmpleD the strin energy in g60 is ca V klGmolD whih is VH7 of its het of formtionF o the relief of this strin energy leding to sp3 hyridized g toms is the mjor driving fore for ddition retions @pigure VFRAF es onsequeneD most dditions to fullerenes re exothermi retionsF
Figure 8.4:
Strain release after addition of reagent A to a pyramidalize carbon of C60 .
gyli voltmmetry @gA studies show tht g60 n e redued nd oxidized reversily up to T eletrons with oneEeletron trnsfer proessesF pulleride nions n e generted y eletrohemil method nd then e used to synthesize ovlent orgnofullerene derivtivesF elkli metls n hemilly redue fullerene in solution nd solid stte to form wx g60 @x a Q E TAF g60 n lso e redued y less eletropositive metls like merury to form g60 - nd g60 2- F sn dditionD slts n lso e synthesized with orgni moleulesD for exmple hei+ g60 - possesses interesting eletroni nd mgneti ehviorF qeometri nd eletroni nlysis predited tht fullerene ehves live n eletroEpoor onjugted polyE ole(nF sndeed g60 nd g70 undergo rnge of nuleophili retions with ronD nitrogenD phosphorous nd oxygen nuleophilesF gTH rets redily with orgnolithium nd qrignrd ompounds to form lkylD phenyl or lknyl fullerenesF ossily the most widely used dditions to fullerene is the fingel retion @pigure VFSAD where ron nuleophileD generted y deprotontion of Ehlo mlonte esters or ketonesD is dded to form ylopropntion produtF he Ehlo esters nd ketones n lso e generted in situ with s2 or gfr4 nd wek se s IDVEdiziyloSFRFHundeEUene @hfAF he fingel retion is onsidered one of the most verstile nd e0ient methods to funtionlize g60 F
Figure 8.5:
Bingel reaction of C60 with 2-bromoethylmalonate.
gyloddition is nother powerful tool to funtionlize fullerenesD in prtiulr euse of its seletivity with the TDT ondsD limiting the possile isomers @pigure VFTAF he dienophili feture of the TDT doule
PTS onds of g60 enles the moleule to undergo vrious yloddition retions in whih the monodduts n e generted in high yieldsF he est studies ylodditon retions of fullerene re QCP dditions with dizoderivtives nd zomethine ylides @rto retionsAF sn this retionD zomethine ylides n e generted in situ from ondenstion of Emino ids with ldehydes or ketonesD whih produe IDQ dipoles to further ret with g60 in good yields @pigure VFUAF rundreds of useful uilding loks hve een generted y those two methodsF he rto retions hve lso een suessfully pplied to ron nnotuesF
Geometrical shapes built onto a [6,6] ring junction: a) open, b) four-membered ring, c) ve-membered ring, and d) six-membered ring.
Figure 8.6:
Figure 8.7:
Prato reaction of C60 with N-methyglycine and paraformaldehyde.
he oxidtion of fullerenesD suh s g60 D hs een of inresing interest with regrd to pplitions in photoeletri deviesD iologil systemsD nd possile remedition of fullerenesF he oxidtion of g60 to g60 yn @n a ID PA my e omplished y photooxidtionD ozonolysisD nd epoxidtionF ith eh of these methodsD there is limit to the isolle oxygented produtD g60 yn with n < QF righly oxygented fullerenesD g60 yn with Q n WD hve een prepred y the tlyti oxidtion of g60 with ewey3 Gr2 y2 F
8.3.3 Carbon nanotubes

e key rekthrough in ron nnohemistry me in IWWQ with the report of needleElike tues mde exE lusively of ronF his mteril eme known s ron nnotues @gxsAF here re severl types of nnotuesF he (rst disovery ws of multi wlled tues @wxsA resemling mny pipes nested within eh otherF hortly fter wxs were disovered single wlled nnotues @xsA were oservedF ingle wlled tues resemle single pipe tht is potentilly pped t eh endF he properties of single wlled nd multi wlled tues re generlly the smeD lthough single wlled tues re elieved to hve superior mehnil strength nd therml nd eletril ondutivityY it is lso more di0ult to mnufture themF
PTT
ingle wlled ron nnotues @xsA re y de(nition fullerene mterilsF heir struture onsists of grphene sheet rolled into tue nd pped y hlf fullerene @pigure VFVAF he ron toms in xD like those in fullereneD re spP hyridizedF he struture of nnotue is nlogous to tking this grphene sheet nd rolling it into semless ylinderF he di'erent types of xs re de(ned y their dimeter nd hirlityF wost of the presently used singleEwll ron nnotues hve een synthesized y the pulsed lser vporiztion methodD howeverD inresingly xs re prepred y vpor liquid solid tlyzed growthF
Structure of single walled carbon nanotubes (SWNTs) with (a) armchair, (b) zig-zag, and (c) chiral chirality.
Figure 8.8:
he physil properties of xs hve mde them n extremely ttrtive mteril for the mnufturE ing of nno deviesF xs hve een shown to e stronger thn steel s estimtes for the oung9s modulus pprohes I pF heir eletril ondutne is omprle to opper with ntiipte urrent densities of up to IH13 eGm2 nd resistivity s low s HFQR x IH-4 Fm t room temperturesF pinllyD they hve high therml ondutivity @QHHH E THHH FmGuAF he eletroni properties of prtiulr x struture re sed on its hirlity or twist in the struture of the tue whih is de(ned y its n,m vlueF he vlues of n nd m determine the hirlityD or 4twist4 of the nnotueF he hirlity in turn 'ets the ondutne of the nnotueD its densityD its lttie strutureD nd other propertiesF e x is onsidered metlli if the vlue n-m is divisile y threeF ytherwiseD the nnotue is semiEondutingF he externl environment lso hs n e'et on the ondutne of tueD thus moleules suh s y2 nd xr3 n hnge the overll ondutne of tueD while the presene of metls hve een shown to signi(ntly e'et the optoEeletroni properties of xsF wulti wlled ron nnotues @wxsA rnge from doule wlled xsD through mnyEwlled xs @pigure VFWA to ron nno(ersF gron nno(ers re the extreme of multi wlled tues @pigure VFIHA nd they re thiker nd longer thn either xs or wxsD hving rossEsetionl of F SHH 2 nd re etween IH to IHH m in lengthF hey hve een used extensively in the onstrution of high strength ompositesF
PTU
Figure 8.9:
TEM image of an individual multi walled carbon nanotube (MWNTs). Copyright of Nanotech Innovations.
Figure 8.10:
SEM image of vapor grown carbon nanobers.
8.3.3.1 Synthesis of carbon nanotubes
e rnge of methodologies hve een developed to produe nnotues in sizele quntitiesD inluding r dishrgeD lser ltionD high pressure ron monoxide @rioAD nd vpor liquid solid @vA growthF ell
PTV
these proesses tke ple in vuum or t low pressure with proess gsesD lthough v growth n tke ple t tmospheri pressureF vrge quntities of nnotues n e synthesized y these methodsY dvnes in tlysis nd ontinuous growth proesses re mking xs more ommerilly vileF he (rst oservtion of nnotues ws in the ron soot formed during the r dishrge prodution of fullerenesF he high tempertures used y the dishrge used the ron ontined in the negtive eletrode to sulime nd the gxs re deposited on the opposing eletrodeF ues produed y this method were initilly multi wlled tues @wxsAF roweverD with the ddition of olt to the vporized ronD it is possile to grow single wlled nnotuesF his method it produes mixture of omponentsD nd requires further puri(tion to seprte the gxs from the soot nd the residul tlyti metlsF roduing gxs in high yield depends on the uniformity of the plsm rD nd the temperture of the deposit forming on the ron eletrodeF righer yield nd purity of xs my e prepred y the use of dulEpulsed lserF xs n e grown in SH7 yield through diret vporiztion of goGxi doped grphite rod with highEpowered lser in tue furne operting t IPHH gF he mteril produed y this method ppers s mt of ropesD IH E PH nm in dimeter nd up to IHH m or more in lengthF ih rope onsists of undle of xsD ligned long ommon xisF fy vrying the proess prmeters suh s tlyst omposition nd the growth tempertureD the verge nnotue dimeter nd size distriution n e vriedF elthough rEdishrge nd lser vporiztion re urrently the prinipl methods for otining smll quntities of high qulity xsD oth methods su'er from drwksF he (rst is tht they involve evporting the ron soureD mking sleEup on n industril level di0ult nd energetilly expensiveF he seond issue reltes to the ft tht vporiztion methods grow xs in highly tngled formsD mixed with unwnted forms of ron ndGor metl speiesF he xs thus produed re di0ult to purifyD mnipulteD nd ssemle for uilding nnotueEdevie rhitetures for prtil pplitionsF sn order to overome some of the di0ulties of these highEenergy proessesD the hemil tlysis method ws developed in whih hydroron feedstok is used in omintion with metl tlystF he tlyst is typillyD ut not limited to ironD olltD or ironGmolydenumD it is heted under reduing onditions in the presene of suitle ron feedstokD eFgFD ethyleneF his method n e used for oth xs nd wxsY the formtion of eh is ontrolled y the identity of the tlyst nd the retion onditionsF e onvenient lortory sle pprtus is ville from xnoteh snnovtionsD snFD for the synthesis of highly uniformD onsistentD reserh smple tht uses preEweighed tlystGron soure mpoulesF his systemD llows for PHH mg smples of wxs to e prepred for reserh nd testingF he use of gy s feedstokD in ple of hydroronD led to the development of the highEpressure ron monoxide @rioA proedure for x synthesisF fy this methodD it is possile to produe grm quntities of xsD unfortuntelyD e'orts to sle eyond tht hve not met with omplete suessF snitilly developed for smllEsle investigtions of tlyst tivityD vpor liquid solid @vA growth of nnotues hs een highly studiedD nd now shows promise for lrgeEsle prodution of nnotuesF eent pprohes hve involved the use of wellEde(ned nnoprtile or moleulr preursors nd mny di'erent trnsition metls hve een employedD ut ironD nikelD nd olt remin to e the fous of most reserhF he nnotues grow t the sites of the metl tlystY the ronEontining gs is roken prt t the surfe of the tlyst prtileD nd the ron is trnsported to the edges of the prtileD where it forms the nnotueF he length of the tue grown in surfe supported tlyst v systems ppers to e dependent on the orienttion of the growing tue with the surfeF fy properly djusting the surfe onentrtion nd ggregtion of the tlyst prtiles it is possile to synthesize vertilly ligned ron nnotuesD iFeFD s rpet perpendiulr to the sustrteF yf the vrious mens for nnotue synthesisD the hemil proesses show the gretest promise for industril sle deposition in terms of its prieGunit rtioF here re dditionl dvntges to the v growthD whih unlike the other methods is ple of growing nnotues diretly on desired sustrteF he growth sites re ontrollle y reful deposition of the tlystF edditionllyD no other growth methods hve een developed to produe vertilly ligned xsF
PTW
8.3.3.2 Chemical functionalization of carbon nanotubes
he limittion of using ron nnotues in ny prtil pplitions hs een its soluilityY for exmple xs hve little to no soluility in most solvent due to the ggregtion of the tuesF eggregtionGroping of nnotues ours s result of the high vn der ls inding energy of caF SHH e per mm of tue onttF he vn der ls fore etween the tues is so gretD tht it tke tremendous energy to pry them prtD mking it very to mke omintion of nnotues with other mterils suh s in omposite pplitionsF he funtionliztion of nnotuesD iFeFD the tthment of hemil funtionl groups provides the pth to overome these rriersF puntionliztion n improve soluility s well s proessiilityD nd hs een used to lign the properties of nnotues to those of other mterilsF he lerest exmple of this is the ility to soluilize nnotues in vriety of solventsD inluding wterF st is importnt when disussing funtionliztion tht distintion is mde etween ovlent nd nonEovlent funtionliztionF gurrent methods for soluilizing nnotues without ovlent funtionliztion inlude highly romti solventsD super idsD polymersD or surftntsF xonEovlent funtionliztion is generlly on the onept of suprmoleulr intertions etween the x nd some mromoleule s result of vrious dsorption foresD suh s vn der ls9 nd Estking intertionsF he hemil speition of the nnotue itself is not ltered s result of the intertionF sn ontrstD ovlent funtionliztion relies on the hemil retion t either the sidewll or end of the xF es my e expeted the high spet rtio of nnotues mens tht sidewll funtionliztion is muh more importnt thn the funtionliztion of the pF hiret ovlent sidewll funtionliztion is ssoited with hnge of hyridiztion from sp2 to sp2 nd simultneous loss of onjugtionF en lterntive pproh to ovlent funtionliztion involves the retion of defets present @or genertedA in the struture of the nnotueF hefet sites n e the open ends nd holes in the sidewllsD nd pentgon nd heptgon irregulrities in the hexgon grphene frmework @often ssoited with ends in the tuesAF ell these funtionliztions re exohedrl derivtiztionsF king the hollow struture of nnotues into onsidertionD endohedrl funtionliztion of xs is possileD iFeFD the (lling of the tues with toms or smll moleulesF st is importnt to note tht ovlent funtionliztion methods hve one prolem in ommonX extensive ovlent funtionliztion modi(es x properties y disrupting the ontinuous !system of xsF rious pplitions of nnotues require di'erentD spei( modi(tion to hieve desirle physil nd hemil properties of nnotuesF sn this regrdD ovlent funtionliztion provides higher degree of (neEtuning the hemistry nd physis of xs thn nonEovlent funtionliztionF ntil nowD vriety of methods hve een used to hieve the funtionliztion of nnotues @pigure VFIIAF
Figure 8.11:
Schematic description of various covalent functionalization strategies for SWNTs.
king hemistry developed for g60 D xs my e funtionlized using IDQ dipolr ddition of zomeE thine ylidesF he funtionlized xs re solule in most ommon orgni solventsF he zomethine ylide funtionliztion method ws lso used for the puri(tion of xsF nder eletrohemil onditionsD ryl
PUH
dizonium slts ret with xs to hieve funtionlized xsD lterntively the dizonium ions my e generted in-situ from the orresponding nilineD while solvent free retion provides the est hne for lrgeEsle funtionliztion this wyF sn eh of these methods it is possile to ontrol the mount of funtionliztion on the tue y vrying retion times nd the regents usedY funtionliztion s high s I group per every IH E PS ron toms is possileF yrgni funtionliztion through the use of lkyl hlidesD rdil pthwyD on tues treted with lithium in liquid mmoni o'ers simple nd )exile route to rnge of funtionl groupsF sn this retionD funtionliztion ours on every IU ronsF wost suess hs een found when the tues re dodeyltedF hese tues re solule in hloroformD hwpD nd rpF he ddition of oxygen moieties to x sidewlls n e hieved y tretment with id or wet ir oxidtionD nd ozonolysisF he diret epoxidtion of xs my e omplished y the diret retion with peroxide regentD or tlytillyF gtlyti deEepoxidtion @pigure VFIPA llows for the quntittive nlysis of sidewll epoxide nd led to the surprising result tht previously ssumed pure xs tully ontin caF I oxygen per PSH ron tomsF
Figure 8.12:
Catalytic oxidation and de-epoxidation of SWNTs.
yne of the esiest funtionliztion routesD nd useful synthon for susequent onversionsD is the )uorintion of xsD using elementl )uorineF smportntlyD gXp rtios of up to PXI n e hieved without disruption of the tuulr strutureF he )uorinted xs @pExsA proved to e muh more solule thn pristine xs in lohols @I mgGmv in iso EpropnolAD hwp nd other seleted orgni solventsF nning tunneling mirosopy @wA reveled tht the )uorine formed nds of pproximtely PH nmD while lultions using hp reveled IDP ddition is more energetilly preferle thn IDR dditionD whih hs een on(rmed y solid stte 13 g xwF pExs mke highly )exile synthons nd susequent elortion hs een performed with orgno lithiumD qrignrd regentsD nd minesF puntionlized nnotues n e hrterized y vriety of tehniquesD suh s tomi fore mirosopy @epwAD trnsmission eletron mirosopy @iwAD Evis spetrosopyD nd mn spetrosopyF ghnges in the mn spetrum of nnotue smple n indite if funtionliztion hs ourredF ristine tues exhiit two distint ndsF hey re the rdil rething mode @PQH m-1 A nd the tngentil mode @ISWH m-1 AF hen funtionlizedD new ndD lled the disorder ndD ppers t ca.IQSH m-1 F his nd is ttriuted to sp3 Ehyridized rons in the tueF nfortuntelyD while the presene of signi(nt h mode is onsistent with sidewll funtionliztion nd the reltive intensity of h @disorderA mode versus the tngentil q mode @ISSH ! ITHH m-1 A is often used s mesure of the level of sustitutionF roweverD it hs een shown tht mn is n unrelile method for determintion of the extent of funtionliztion sine the reltive intensity of the h nd is lso funtion of the sustituents distriution s well s onentrtionF
PUI eent studies suggest tht solid stte 13 g xw re possily the only de(nitive method of demonstrting ovlent tthment of prtiulr funtionl groupsF
8.3.3.3 Coating carbon nanotubes: creating inorganic nanostructures
pullerenesD nnotues nd nno(ers represent suitle sustrtes for the seeding other mterils suh s oxides nd other minerlsD s well s semiondutorsF sn this regrdD the ron nnomteril ts s seed point for the growth s well s method of de(ning unusul spet rtiosF por exmpleD sili (ers n e prepred y numer of methodsD ut it is only through oting xs tht sili nnoE(ers with of miron lengths with tens of nnometers in dimeter my e prepredF hile g60 itself does not redily seed the growth of inorgni mterilsD liquid phse deposition of oxidesD suh s siliD in the presene of fullerenolD g60 @yrAn D results in the formtion of uniform oxide spheresF st ppers the fullerenol ts s oth regent nd physil point for susequent oxide growthD nd it is g60 D or n ggregte of g60 D tht is present within the spheril prtileF he ddition of fullerenol lters the morphology nd rystl phse of ggy3 preipittes from queous solutionD resulting in the formtion of spheril feturesD SEpointed )ower shped lustersD nd tringulr rystls s opposed to the usul rhomi rystlsF sn dditionD the metEstle vterite phse is oserved with the ddition of g60 @yrAn F es noted ove individul xs my e otined in solution when ensed in ylindril mielle of suitle surftntF hese individulized nnotues n e oted with rnge of inorgni mterilsF viquid phse deposition @vhA ppers to hve signi(nt dvntges over other methods suh s inorporting surfted xs into preermi mtrixD in situ growth of the x in n oxide mtrixD nd solEgel methodsF he primry dvntge of vh growth is tht individul xs my e oted rther thn undles or ropesF por exmpleD xs hve een oted with sili y liquid phse deposition @vhA using siliGr2 ip6 solution nd surftntEstilized solution of xsF he thikness of the oting is dependent on the retion mixture onentrtion nd the retion timeF he x ore n e removed y thermolysis under oxidizing onditions to leve sili nno (erF st is interesting to note tht the use of surftnt is ounter produtive when using wxs nd qpsD in this se surfe tivtion of the nnotue o'ers the suitle growth inititionF reEoxidtion of the wx or qp llows for uniform otings to e depositedF he oted xsD wxsD nd qps n e susequently reted with suitle surfe regents to imprt misiility in queous solutionsD gur gelsD nd orgni mtrixesF sn ddition to simple oxidesD oted nnotues hve een prepred with minerls suh s rontes nd semiondutorsF
8.3.4 Bibliography
F wF fhiloD wF F trnoD gF uittrellD F rF rugeD F iF mlleyD nd F fF eismnD ScienceD PHHPD 298D PQTIF hF F fethuneD gF rF ulngD wF F deriesD qF qormnD F voyD tF zquezD nd F feyersD NatureD IWWQD 363D THSF tD tF fregeD gF qllwyD nd eF F frronD J. Phys. Chem., CD PHHUD 111D IUVIPF gF eF hyke nd tF wF ourD J. Am. Chem. Soc.D PHHQD 125D IISTF F qeD tF gF huhmpD F giD rF F qisonD nd rF gF hornD J. Am. Chem. Soc.D PHHSD 127D ITPWPF vF eF qirifloD wF rodkD nd F F veeD Phys. Rev. BD PHHHD 62D IQIHRF F quoD F xikolevD eF qF inzlerD hF omnekD hF F golertD nd F iF mlleyD J. Phys. Chem.D IWWSD 99D IHTWRF tF rF rfnerD wF tF fronikowskiD fF F ezminD F xikolevD eF qF inzlerD hF F golertD uF eF mithD nd F iF mlleyD Chem. Phys. Lett.D IWWVD 296D IWSF eF rirshD Angew. Chem. Int. Ed.D PHHPD 40D RHHPF F sijim nd F shihshiD NatureD IWWQD 363D THQF rF F tfryD iF eF hitsittD nd eF F frronD J. Mater. Sci.D PHHUD 42D UQVIF rF F urotoD tF F rethD F gF y9frienD F pF gurlD nd F iF mlleyD NatureD IWVSD 318D ITPF pF vingD eF uF dnD eF eerD tF ghttopdhyyD F quD F rF rugeD nd F iF fillupsD Nano Lett.D PHHRD 4D IPSUF
PUP
hF ygrin nd eF F frronD J. Mol. Cat. A: Chem.D PHHTD 244D PTUF hF ygrinD tF ghttopdhyyD eF uF dnD iF fillupsD nd eF F frronD J. Am. Chem. Soc.D PHHTD 128D IIQPPF F iF mlleyD Acc. Chem. Res.D IWWPD 25D WVF wF wF tF reyD F F iesenD nd tF wF qisonD NatureD IWWTD 381D TUVF iF eF hitsitt nd eF F frronD Nano Lett.D PHHQD 3D UUSF tF ng nd eF F frronD Chem. Commun.D PHHRD PVVRF vF engD vF fF elemnyD gF vF idwrdsD nd eF F frronD Nano Res.D PHHVD 1D UPF
8.4 Graphene
8.4.1 Introduction
qrphene is oneEtomEthik plnr sheet of sp2 Eonded ron toms tht re densely pked in honeyE om rystl lttie @pigure VFIQAF he nme omes from grphite nd lkeneY grphite itself onsists of mny grphene sheets stked togetherF
Figure 8.13:
Idealized structure of a single graphene sheet.
ingleElyer grphene nnosheets were (rst hrterized in PHHRD prepred y mehnil exfolition @the sothEtpe methodA of ulk grphiteF vter grphene ws produed y epitxil hemil vpor deposition on silion ride nd nikel sustrtesF wost reentlyD grphene nnorions @qxsA hve een prepred y the oxidtive tretment of ron nnotues nd y plsm ething of nnotues emedded in polymer (lmsF
8.4.2 Physical properties of graphene

qrphene hs een reported to hve oung9s modulus of I nd intrinsi strength of IQH qY similr to single wlled ron nnotues @xsAF he eletroni properties of grphene lso hve some similrity with ron nnotuesF qrphene is zeroEndgp semiondutorF iletron moility in grphene is extrordinrily high @ISDHHH m2 GFs t room tempertureA nd llisti eletron trnsport is reported to
4
PUQ e on length sles omprle to tht of xsF yne of the most promising spets of grphene involves the use of qxsF gutting n individul grphene lyer into long strip n yield semionduting mterils where the ndgp is tuned y the width of the rionF hile grphene9s novel eletroni nd physil properties gurntee this mteril will e studied for yers to omeD there re some fundmentl ostles yet to overome efore grphene sed mterils n e fully utilizedF he forementioned methods of grphene preprtion re e'etiveY howeverD they re imprtil for lrgeEsle mnufturingF he most plentiful nd inexpensive soure of grphene is ulk grphiteF ghemil methods for exfolition of grphene from grphite provide the most relisti nd slle pproh to grphene mterilsF qrphene lyers re held together in grphite y enormous vn der ls foresF yveroming these fores is the mjor ostle to grphite exfolitionF o dteD hemil e'orts t grphite exfolition hve een foused primrily on interltionD hemil derivtiztionD therml expnsionD oxidtionEredutionD the use of surftntsD or some omintion of theseF
8.4.3 Graphite oxide

roly the most ommon route to grphene involves the prodution of grphite oxide @qyA y extremely hrsh oxidtion hemistryF he methods of tudenmeier or rummers re most ommonly used to produe qyD highly exfolited mteril tht is dispersile in wterF he struture of qy hs een the sujet of numerous studiesY it is known to ontin epoxide funtionl groups long the sl plne of sheets s well s hydroxyl nd roxyl moieties long the edges @pigure VFIRAF sn ontrst to other methods for the synthesis of qyD the the mEperoxyenzoi id @mEgfeA oxidtion of mirorystlline syntheti grphite t room temperture yields grphite epoxide in high yieldD without signi(nt dditionl defetsF
Idealized structure proposed for graphene oxide (GO). Adapted from C. E. Hamilton, PhD Thesis, Rice University (2009).
Figure 8.14:
es grphite oxide is eletrilly insultingD it must e onverted y hemil redution to restore the eletroni properties of grpheneF ghemilly onverted grphene @ggqA is typilly redued y hydrzine or orohydrideF he properties of ggq n never fully mth those of grphene for two resonsX IF yxidtion to qy introdues defetsF PF ghemil redution does not fully restore the grphiti strutureF
PUR
es would e expetedD ggq is prone to ggregtion unless stilizedF qrphene mterils produed from pristine grphite void hrsh oxidtion to qy nd susequent @inompleteA redutionY thusD mterils proE dued re potentilly muh etter suited to eletronis pplitionsF e tlyti pproh to the removl of epoxides from fullerenes nd xs hs een pplied to grphene epoxide nd qyF retment of oxidized grphenes with methyltrioxorhenium @weey3 D wyA in the presE ene of h3 results in the oxygen trnsferD to form yah3 nd llow for qunti(tion of the gXy rtioF
8.4.4 Homogeneous graphene dispersions

en lternte pproh to produing grphene mterils involves the use of pristine grphite s strting mterilF he fundmentl vlue of suh n pproh lies in its voidne of oxidtion to qy nd suseE quent @inompleteA redutionD therey preserving the desirle eletroni properties of grpheneF here is preedent for exfolition of pristine grphite in net orgni solvents without oxidtion or surftntsF st hs een reported tht NDN Edimethylformmide @hwpA dispersions of grphene re possileD ut no detiled hrteriztion of the dispersions were reportedF sn ontrstD golemn nd oworkers reported similr disE persions using N Emethylpyrrolidone @xwAD resulting in individul sheets of grphene t onentrtion of HFHI mgGmvF xw nd hwp re highly polr solventsD nd not idel in ses where retion hemistry requires nonpolr mediumF purtherD they re hygrosopiD mking their use prolemti when wter must e exluded from retion mixturesF pinllyD hwp is prone to therml nd hemil deompositionF eentlyD dispersions of grphene hs een reported in ortho Edihloroenzene @yhgfA using wide rnge of grphite souresF he hoie of yhgf for grphite exfolition ws sed on severl riteriX IF PF QF RF yhgf is ommon retion solvent for fullerenes nd is known to form stle x dispersionsF yhgf is onvenient highEoiling romtiD nd is omptile with vriety of retion hemistriesF yhgfD eing romtiD is le to intert with grphene via E stkingF st hs een suggested tht good solvents for grphite exfolition should hve surfe tension vlues of RH ! SH mtGm2 F yhgf hs surfe tension of QTFT mtGm2 D lose to the proposed rngeF
qrphite is redily exfolited in yhgf with homogeniztion nd sonitionF hree strting mterils were suessfully dispersedX mirorystlline synthetiD thermlly expndedD nd highly ordered pyrolyti grphite @ryqAF hispersions of mirorystlline syntheti grphite hve onentrtion of HFHQ mgGmvD determined grvimetrillyF hispersions from expnded grphite nd ryq re less onentrted @HFHP mgGmvAF righ resolution trnsmission eletron mirosopy @riwA shows mostly fewElyer grphene @n < SA with single lyers nd smll )kes stked on top @pigure VFISAF vrge grphiti domins re visileY this is further supported y seleted re eletron di'rtion @eihA nd fst pourier trnsform @ppA in seleted resF etomi fore mirosope @epwA imges of dispersions spryed onto silion sustrtes shows extremely thin )kes with nerly ll elow IH nmF everge height is U E IH nmF he thinnest re less thn I nmD grphene monolyersF vterl dimensions of nnosheets rnge from IHH ! SHH nmF
PUS
TEM images of single layer graphene from HOPG dispersion. (a) monolayer and few layer of graphene stacked with smaller akes; (b) selected edge region from (a), (c) selected area from (b) with FFT inset, (d) HRTEM of boxed region in (c) showing lattice fringes with FFT inset. Adapted from C. E. Hamilton, PhD Thesis, Rice University (2009).
Figure 8.15:
esEdeposited (lms st from yhgf grphene show poor eletril ondutivityD howeverD fter vuum nneling t RHH g for IP hours the (lms improve vstlyD hving sheet resistnes on the order of TH GsqF fy omprisonD grphene epitxilly grown on xi hs reported sheet resistne of PVH GsqF
8.4.5 Covalent functionalization of graphene and graphite oxide

he ovlent funtionliztion of xs is well estlishedF ome routes to ovlently funtionlized xs inlude esteri(tionG midtionD redutive lkyltion @fillups retionAD nd tretment with zomethine ylides @rto retionAD dizonium sltsD or nitrenesF gonverselyD the hemil derivtiztion of grphene nd qy is still reltively unexploredF ome methods previously demonstrted for xs hve een dpted to qy or grpheneF qy rE oxyli id groups hve een onverted into yl hlorides followed y midtion with longEhin minesF
PUT
edditionllyD the oupling of primry mines nd mino ids vi nuleophili ttk of qy epoxide groups hs een reportedF et nother route oupled isoyntes to roxyli id groups of qyF puntionliztion of prtilly redued qy y ryldizonium slts hs lso een demonstrtedF he fillups retion hs een performed on the interltion ompound potssium grphite @g8 uAD s well s grphite )uorideD nd most reently qyF qrphene lkyltion hs een omplished y treting grphite )uoride with lkyllithium regentsF yhgf dispersions of grphene my e redily onverted to ovlently funtionlize grpheneF herml deomposition of enzoyl peroxide is used to initite rdil ddition of lkyl iodides to grphene in yhgf dispersionsF
@VFPA edditionllyD funtionlized grphene with nitrenes generted y therml deomposition of ryl zides
@VFQA
8.4.6 Bibliography
F flkeD F hF frimiomeD F F xirD F tF foothD hF tingD pF hedinD vF eF onomrenkoD F F worozovD rF pF qleesonD iF F rillD eF uF qeimD nd uF F xovoselovD Nano LettFD PHHVD 8D IUHRF tF ghttopdhyyD eF wukherjeeD gF iF rmiltonD tFErF ungD F ghkrortyD F quoD uF pF uellyD eF F frronD nd F iF fillupsD J. Am. Chem. SocFD PHHVD 130D SRIRF qF idD qF pnhiniD nd wF ghhowllD Nat. NanotechnolFD PHHVD 3D PUHF wF F rnD fF yzyilmzD F hngD nd F uimD Phys. Rev. LettFD PHHVD 98D PHTVHSF F rernndezD F xiolosiD wF votyD pF wF fligheD F unD F heD sF F wqovernD fF rollndD wF fyrneD F uF qun9uoD tF tF folndD F xirjD qF huesergD F urishnmurthyD F qoodhueD tF ruthinsonD F rdiD eF gF perrriD nd tF xF golemnD Nat. Nanotechnol.D PHHVD 3D STQF F F rummers nd F iF y'emnD J. Am. Chem. SocFD IWSVD 80D IQQWF vF tioD vF hngD F ngD qF hinkovD nd rF hiD NatureD PHHWD 458D VUUF hF F uosynkinD eF vF rigginothmD eF initskiiD tF F vomedD eF himievD fF uF rieD nd tF wF ourD NatureD PHHWD 458D VUPF hF viD wF fF wuellerD F qiljeD F fF unerD nd qF qF lleD Nat. NanotechnolFD PHHVD 3D IHIF F xiyogiD iF fekyrovD wF iF stkisD tF vF willimsD wF eF rmonD nd F gF rddonD J. Am. Chem. SocFD PHHTD 128D UUPHF F i nd iF F mulskiD Nano LettFD PHHVD 8D ITUWF vF tudenmierD Ber. Dtsch. Chem. GesFD IVWVD 31D IRVIF
PUU
8.5 Rolling Molecules on Surfaces Under STM Imaging

8.5.1 Introduction to surface motions at the molecular level
es single moleule imging methods suh s snning tunneling mirosope @wAD tomi fore mirosope @epwAD nd trnsmission eletron mirosope @iwA developed in the pst dedesD sientists hve gined powerful tools to explore moleulr strutures nd ehviors in previously unknown resF emong these imging methodsD w is proly the most suitle one to oserve detil t moleulr levelF w n operte in wide rnge of onditionsD provides very high resolutionD nd le to mnipulte moleulr motions with the tipF en interesting erly exmple me from sfw in IWWHD in whih the w ws used to position individul toms for the (rst timeD spelling out 4sEfEw4 in enon tomsF his work reveled tht oservtion nd ontrol of single toms nd moleulr motions on surfes were possileF he sfw workD nd susequent experimentsD relied on the ft tht w tip lwys exerts (nite fore towrd n dsorte tom tht ontins oth vn der ls nd eletrostti fores ws utilized for mnipultion purposeF fy djusting the position nd the voltge of the tipD the intertions etween the tip nd the trget moleule were hngedF hereforeD pplyingGrelesing fore to single tom nd mke it move ws possile pigure VFITF
Manipulation of STM tip toward a xenon atom. a) STM tip move onto a target atom then change the voltage and current of the tip to apply a stronger interaction. b) Move the atom to a desire position. c) After reaching the desire position, the tip released by switching back to the scanning voltage and current.
Figure 8.16:
he tul positioning experiment ws rried out in the following proessF he nikel metl sustrte ws prepred y yles of rgonEion sputteringD followed y nneling in prtil pressure of oxygen to
5
PUV
remove surfe ron nd other impuritiesF efter the lening proessD the smple ws ooled to R uD nd imged with the w to ensure the qulity of surfeF he nikel smple ws then doped with xenonF en imge of the doped smple ws tken t onstntEurrent snning onditionsF ih xenon tom ppers s loted rndomly IFT high ump on the surfe @pigure VFIUAF nder the imging onditions @tip is a HFHIH with tunneling urrent IH-9 eA the intertion of the xenon with the tip is too wek to use the position of the xenon tom to e perturedF o move n tomD the w tip ws pled on top of the tom performing the proedure depited in pigure VFIT to move it to its trgetF epeting this proess gin nd gin led the reserher to uild of the struture they desired pigure VFIU nd F
Figure 8.17:
Manipulation of STM tip starting with a) randomly dosed xenon sample, b) under construction - move xenon atom to desire position, and c) accomplishment of the manipulation. Adapted from D. M. Eigler and E. K. Schweizer, Nature, 1990, 344, 524.
ell motions on surfes t the single moleule level n e desried s y the following @or omintion of the followingA modesX iF iiF iiiF ivF lidingF roppingF ollingF ivotingF
elthough the power of w imging hs een demonstrtedD imging of moleules themselves is still often di0ult tskF he suessful imging of the sfw work ws ttriuted to seletion of hevy tomF yther syntheti orgni moleules without hevy toms re muh more di0ult to e imged under wF hetermintions of the mehnism of moleulr motion is notherF fesides imging methods themselvesD other uxiliry methods suh s hp lultions nd imging of properly designed moleules re required to determine the mehnism y whih prtiulr moleule moves ross surfeF rereinD we re prtiulrly interested in surfeErolling moleulesD iFeFD those tht re designed to roll on surfeF st is strightforwrd to imgine tht if we wnt to onstrut @nd imgeA surfeErolling moleulesD we must think of mking highly symmetril struturesF sn dditionD the mgnitudes of intertions etween the moleules nd the surfes hve to e dequteY otherwise the moleules will e more suseptile to slideGhop or stik on the surfesD insted of rollingF es resultD only very few moleules re known n roll nd e deteted on surfesF
8.5.2 Surface rolling of molecules under the manipulation of STM tips

es desried oveD rolling motions re most likely to e oserved on moleules hving high degree of symmetry nd suitle intertions etween themselves nd the surfeF g60 is not only highly symmetril moleule ut lso redily imgele under w due to its sizeF hese properties together mke g60 nd its derivtives highly suitle to study with regrds to surfeErolling motionF he w imging of g60 ws (rst rried out t et uing gollegeD vondonF imilr to the tom positioning experiment y sfwD w tip mnipultion ws lso utilized to hieve g60 displementF he tip trjetory
PUW suggested tht rolling motion took into ount the displement on the surfe of g60 F sn order to on(rm the hypothesisD the reserhers lso employed ab initio density funtion @hpA lultions with rolling model oundry ondition @pigure VFIVAF he lultion result hs supported their experimentl resultF
Figure 8.18:
Proposed mechanism of C60 translation showing the alteration of C60 ... surface interactions during rolling. a) 2-point interaction. The left point interaction was dissociated during the interaction. b) 1-point interaction. C60 can pivot on surface. c) 2-point interaction. A new interaction formed to complete part of the rolling motion. a) - c) The black spot on the C60 is moved during the manipulation. The light blue Si balls represent the rst layer of molecules the silicon surface, and the yellow balls are the second layer.
he results provided insights into the dynmil response of ovlently ound moleules to mnipultionF he sequentil reking nd reforming of highly diretionl ovlent onds resulted in dynmil moleE ulr response in whih ond rekingD rottionD nd trnsltion re intimtely oupled in rolling motion @pigure VFIWAD ut not performing sliding or hopping motionF e triptyene wheeled dimeri moleule pigure VFIW ws lso synthesized for studying rolling motion under wF his 4tripodElike4 triptyene wheel ulike ll like g60 moleule lso demonstrted rolling motion on the surfeF he two triptyene units were onneted vi dilkynyl xleD for oth desired moleule orienttion sitting on surfe nd diretionl preferene of the rolling motionF w ontrolling nd imging ws demonstrtedD inluding the mehnism pigure VFIWF
PVH
Figure 8.19: Scheme of the rolling mechanism (left to right). Step 1 is the tip approach towards the molecule, step 2 is a 120 degree rotation of a wheel around its molecular axle and in step 3 the tip reaches the other side of the molecule. It shows that, in principle, only one rotation of a wheel can be induced (the direction of movement is marked by arrows).
8.5.3 Single molecule nanocar under STM imaging

enother use of w imging t single moleule imging is the single moleule nnor y the our group t ie niversityF he onept of nnor initilly employed the free rottion of gEg single ond etween spheril g60 moleule nd n lkyneD pigure VFPHF fsed on this oneptD n xle n e designed into whih re mounted g60 wheels onneted with hssis to onstrut the nnorF xnors with this design re expeted to hve diretionl movement perpendiulr to the xleF nfortuntelyD the (rst genertion nnor @nmed nnotruk pigure VFPIA enountered some di0ulties in w imging due to its hemil instility nd insoluilityF hereforeD new of design of nnor sed on yi hs een synthesized pigure VFPPF
PVI
Structure of C60 wheels connecting to an alkyne. The only possible rolling direction is perpendicular to the C-C single bond between C60 and the alkyne. The arrow indicates the rotational motion of C60 .
Figure 8.20:
Structure of the nanotruck. No rolling motion was observed under STM imaging due to its instability, insolubility and inseparable unreacted C60 .The double head arrow indicates the expected direction of nanocar movement. Y. Shirai, A. J. Osgood, Y. Zhao, Y. Yao, L. Saudan, H. Yang, Y.-H. Chiu, L. B. Alemany, T. Sasaki, J.-F. Morin, J. M. Guerrero, K. F. Kelly, and J. M. Tour, J. Am. Chem. Soc., 2006, 128, 4854. Copyright American Chemical Society (2006).
Figure 8.21:
PVP
Nanocar based on OPE structure. The size of the nanocar is 3.3 nm X 2.1 nm (W x L). Alkoxy chains were attached to improve solubility and stability. OPE moiety is also separable from C60 . The bold double head arrow indicates the expected direction of nanocar movement. The dimension of nanocar was 3.3 nm X 2.1 nm which enable direct observation of the orientation under STM imaging. Y. Shirai, A. J. Osgood, Y. Zhao, K. F. Kelly, and J. M. Tour, Nano Lett., 2005, 5, 2330. Copyright American Chemical Society (2005).
Figure 8.22:
he newly designed nnor ws studied with wF hen the nnor ws heted to PHH gD noE tiele displements of the nnor were oserved under seleted imges from IH min w experiment pigure VFPQF he phenomenon tht the nnor moved only t high temperture ws ttriuted their stE ility to reltively strong dhesion fore etween the fullerene wheels nd the underlying goldF he series of imges showed oth pivotl nd trnsltionl motions on the surfesF
PVQ
Pivotal and translational movement of OPE based nanocar. Acquisition time of one image is approximately 1 min with (a e) images were selected from a series spanning 10 min. The conguration of the nanocar on surface can be determined by the distances of four wheels. a) b) indicated the nanocar had made a 80 pivotal motion. b) e) indicated translation interrupted by small-angle pivot perturbations. Y. Shirai, A. J. Osgood, Y. Zhao, K. F. Kelly, and J. M. Tour, Nano Lett., 2005, 5, 2330. Copyright American Chemical Society (2005).
Figure 8.23:
elthough literture studies suggested tht the g60 moleule rolls on the surfeD in the nnor movement studies it is still not possile to onlusively onlude tht the nnor moves on surfe exlusively vi rolling mehnismF roppingD sliding nd other moving modes ould lso e responsile for the movement of the nnor sine the experiment ws rried out t high temperture onditionsD mking the g60 moleules more energeti to overome intertions etween surfesF o tkle the question of the mode of trnsltionD trimeri nnoEtriyle hs een synthesizedF sf the movement of fullereneEwheeled nnor ws sed on hopping or sliding mehnismD the trimer should give
PVR
oservle trnsltionl motions like the fourEwheeled nnorD howeverD if rolling is the operle motion then the nnoEtriyle should rotte on n xisD ut not trnslte ross the surfeF he result of the imging experiment of the trimer t PHH g @pigure VFPRDA yielded very smll nd insigni(nt trnsltionl displements in omprison to REwheel nnor @pigure VFPQAF he trimeri QEwheel nnor showed some pivoting motions in the imgesF his motion type n e ttriuted to the diretionl preferenes of the wheels mounted on the trimer using the r to rotteF ell the experimentl results suggested tht g60 Esed nnor moves vi rolling motion rther thn hopping nd slidingF sn dditionD the ft tht the thermlly driven nnor only moves in high temperture lso suggests tht four g60 hve very strong intertions to the surfeF
PVS
Pivot motion of the trimer. a) - d) Pivot motions of circled trimered were shown in the series of images. No signicant translation were observed in comparison to the nanocar. Y. Shirai, A. J. Osgood, Y. Zhao, K. F. Kelly, and J. M. Tour, Nano Lett., 2005, 5, 2330. Copyright American Chemical Society (2005).
Figure 8.24:
PVT
8.5.4 Bibliography
hF wF iigler nd iF uF hweizerD NatureD IWWHD 344D SPRF vF qrillD uF ErF iederD pF woresoD qF penneD F tojkoviD F foujuD nd gF tohimD Nat. Nanotechnol.D PHHUD 2D WSF F hiriD eF tF ysgoodD F hoD uF pF uellyD nd tF wF ourD Nano Lett.D PHHSD 5D PQQHF F hiriD eF tF ysgoodD F hoD F oD vF udnD rF ngD FErF ghiuD vF fF elemnyD F skiD tFEpF worinD tF wF querreroD uF pF uellyD nd tF wF ourD J. Am. Chem. Soc.D PHHTD 128D RVSRF
Chapter 9
Economic and Environmental Issues

9.1 The Environmental Impact of the Manufacturing of Seminconductors
1
4his module ws developed s prt of ie niversity glss lled 4xnotehnologyX gontent nd gontext2 4initilly funded y the xtionl iene poundtion under qrnt xoF iigE HRHUPQUF st ws oneivedD reserhedD written nd edited y students in the pll PHHS version of the lssD nd reviewed y prtiipting professorsF4
note:
9.1.1 What is a semiconductor?

he semiondutor industry is one of the fstest growing mnufturing setors in not only the nited ttes ut lso in the worldF eording to the emerin iletronis essoitionD the domesti sles of eletroni omponents hve skyroketedD jumping from 6IPU illion to 6QHT illion over the ourse of the IWVH9sF sn the (rst three qurters of the PHHQ (sl yer loneD the export of tehnology goods from the nited ttes inresed y 6IW illion IF he word semiondutor tehnilly refers to ny memer of lss of solidD rystlline mterils tht is hrterized y n eletril ondutivity etter thn tht of insultors @eFgFD plstiA ut less thn tht of good ondutors @eFgFD opperA PF emiondutors re prtiulrly useful s se mteril in the mnufturing of omputer hipsD nd the term semiondutor hs tully ome to e synonymous with the omputer hipsD themselvesF roweverD semiondutors re not only used in omputersF gomputers only mke up RR7 of entire industry onsumption @see pigure WFIAF emiondutors re lso used for militryD utomotiveD industrilD ommunitionsD nd other onsumer purposesF
1 2
This content is available online at <http://cnx.org/content/m14503/1.3/>. http://frazer.rice.edu/nanotech
PVU
PVV
CHAPTER 9. ECONOMIC AND ENVIRONMENTAL ISSUES
Figure 9.1:
Relative consumption of semiconductors by industry [3].
emiondutors seem to e nywhere nd everywhere throughout our everydy livesD yet it is surprising how little most people know out how they tully work or out the potentilly devstting e'ets their mnufturing n hve on the environment nd humn helthF
9.1.2 Why is nanotechnology important to the semiconductor industry?

wuh of the study of nnotehnology hs een entered on the mnufturing of semiondutorsF hough there re numer of highly ntiipted pplitions for nnotehnology in other (eldsD notly in mediine nd in iotehnologyD the most tngile results thus fr n e rgued to hve een hieved in the semiE ondutor industryF
PVW
Figure 9.2:
An example of a semiconductor (photo from PEAK).
por exmpleD sntel reently unveiled its (rst produts sed on genertion of WHEnnometer proess tehnologyD nd its reserhes nd engineers hve uilt nd tested prototype trnsistors ll the wy down to the PPEnnometer rngeF gurrentlyD sntel sientists nd engineers re working on identifying new mterils suh s ron nnotues nd nnowires to reple urrent trnsistorsD nd in prtiulr they hope to develop triEgte trnsistor pproh tht would enle hip designers to uild trnsistors elow the PPEnnometer rnge RF ith the dvent of nnotehnologyD these trnsistors re eoming even fster nd more powerfulD nd in ordne with the lw of elerting returnsD the industry hs een produing smller trnsistors t lower osts with eh nd every pssing yerF es these semiondutors eome smller nd smllerD they re quikly nd surely pushing towrds the limits of the nnoErelmF hese innovtionsD howeverD do not ome without their fir shre of hllengesF hysil issues tht re not prolemti t the miron sle rise t the nnoEsle due to the emergene of quntum e'etsD nd in muh the sme wy tht optil mirosopy nnot e utilized t the nnoEsleD the semiondutor industry is fst pprohing similr di'rtion limitF yptil lithogrphyD for instneD proess tht uses the properties of light to eth trnsistors onto wfers of silionD will soon reh its limitF et its most si levelD nnotehnology involves pushing individul toms together one y oneF ine pproximtely IFU illion trnsistors re required for single hipD this is oviously not relisti method for mss produtionF nless n lterntive method for prodution or solution to this prolem is foundD the development nd mnufturing of trnsistors re expeted to hit proveril rik wll y the yer PHISF his is the reson tht reserh in nnotehnology is so importnt for the world nd future of semiondutorsF
9.1.3 How are semiconductors manufactured?

ody9s semiondutors re usully omposed of silionD nd they re mnuftured in proedure tht omines the fmilir with the izrreY some steps tht re involved in the proess re s everydy s developing roll of photogrphi (lm while others seem s if they would e etter suited to tke ple on speshipF hese semiondutors pper to the nked eye s eing smll nd )tD ut they re tully threeE dimensionl sndwihes tht re ten to twenty lyers thikF st n tke more thn two dozen steps nd up to two full months to produe single one of these silion sndwihesF ome of the si nd more essentil
PWH
steps involved in the mnufturing proess of silion hips re rie)y detiled elowF pirstD silion rystls re melted in vt nd puri(ed to WWFWWWW7 purityF he molten silion is drwn into longD hevyD ylindril ingotsD whih re then ut into thin slies lled wfersout the thikness of usiness rdF yne side of eh wfer must e polished solutely smoothF his proess is lled hemilEmehnil polishingD nd it involves thing the wfers in speil rsive hemilsF efter hemilEmehnil polE ishingD imperfetions nnot e deteted on the wfers even with the id of lortory mirosopeF efter wfer is polishedD lyers of mteril must e stked on top of the silion wfer seF snsulting lyers re lid down in lterntion with onduting lyers in proess lled depositionF his is often hieved y sprying the hemils diretly onto the surfe of the wfer through hemil vpor depositionF pollowing depositionD the wfer is oted with nother lyer of hemils lled photoresist tht is sensitive to lightF xextD mhine lled stepper @pigure WFQA is lirted to projet n extremely (ne nd foused imge through speil type of retile (lm in mnner similr to tht of simple slide projetorF he light tht is trnsmitted through the retile is projeted onto the photoresist lyerD whih rets to the light nd egins to hrdenF ell of the prts of the wfer exposed to this light hrden into tough rust while the prts in shdow remin softF his prtiulr step is known y the nme of photoeletrohemil ething euse it hieves n ething e'etD resulting in hipF
Figure 9.3:
An artist's illustration of a stepper (image from Solid State Electronics).
rundreds of opies of the hip re ethed onto the wfer until the entire surfe hs een exposedF yne this proess is ompleteD the entire wfer is sumerged into n ething thD whih wshes wy ny prts of the photoresist tht remin unexposed long with the insulting hemils undernethF he hrdened res of the photoresistD howeverD remin nd protet the lyers of mteril underneth themF his proess of depositing hemilsD oting with photoresistD exposure to light over (lm mskD nd ething nd wshing wy is repeted more thn dozen timesF he result is n elorteD threeEdimensionl onstrution of
PWI interloking silion wiresF his produt is then oted with nother insulting lyer nd is plted with thin lyer of metlD usully either luminum or opperF et nother photoresist is lid down on top of this metl pltingD nd fter the wfer is exposed in stepperD the proess repets with nother lyer of metlF efter this step hs een repeted severl more timesD (nl wsh step is performedD nd (nished semiondutor produt rolls o' the ssemly lineD t lstF
9.1.4 What is a clean room?

e typil semiondutor frition filityD or f in industry jrgonD looks like norml twoE or threeE story o0e uilding from the outsideD nd most of the interior spe is devoted to one or more len roomsD in whih the semiondutors re tully mdeF e len room is designed with fntil ttention to detil imed towrds keeping the room immulte nd dustEfree @pigure WFRAF
Figure 9.4:
An industry clean room at AP Tech (photo from Napa Gateway).
wost if not ll surfes inside these len rooms re omposed of stinless steelD nd these surfes re sloped whenever possile or perforted y grting to void giving dust ple to settleF he ir is (ltered through oth the eiling nd the )oor to remove prtiles tht re down to IGIHH the width of humn hirF vighting is hrteristilly right nd slightly yellowish to prevent mildew from forming ehind equipment or in reessed ornersD nd even the workers in len room must e solutely spotlessF orkers in these rooms must e overed from hed to toe in unny suits tht ompletely sel the ody in ulky suitD helmetD ttery pkD glovesD nd ootsF yne seled in these suitsD the workers often look more like spe explorers in siene (tion movie thn omputer hip employeesD ut in order to even enter the stinless steel loker room to suit up to egin withD they must (rst pss through series of ir lok doorsD stnd under numer of ir showers tht tully low dust o' of lothingD nd wlk ross stiky )oor mtting tht removes grime from the ottom of shoesF emiondutorEmnufturing ompnies often portry their frition filities s eing lenD environE mentlly friendlyD nd onspiuously free of the lkD illowing smokestks tht hve ome to e ssoited
PWP
with the plnts nd ftories of other mjor industriesF hese filities produe no visile pollution nd erE tinly do not pper to pose ny helth or environmentl risksF sn truthD the term len roomD itself is more thn just it of n understtementF sndustry exeutives often ost tht their len rooms re from IDHHH times to IHDHHH times lener nd more snitry thn ny hospitl operting roomF
9.1.5 What are the health risks involved in the semiconductor industry?
he use of sterile tehniques nd the fstidious ttention devoted to lenliness in the semiondutor industry my perpetute the illusion tht the mnufturing of semiondutors is sfe nd sterile proessF roweverD s rpidly growing ody of evidene ontinues to suggestD hrdly nything ould e further from the truth @pigure WFSAF he question of worker sfety nd hemil ontmintion t hipEmking plnts hs reeived n inresing mount of ttention over the ourse of the pst dedeF
Chemicals used in the manufacturing of semiconductors are known to have toxic eects (image from FARSHA).
Figure 9.5:
he devies eing uilt t semiondutor frition filities re superEsensitive to environmentl onE tminntsF feuse eh hip tkes dozens of trined personnel severl weeks to ompleteD n enormous mount of time nd e'ort is expended to produe single wferF he industry my pride itself on its perE fetly immulte lortories nd its unnyEsuited workersD ut it should e noted tht the unny suits re not designed to protet their werers from hzrdous mterils ut rther to protet the tul semiE ondutor produts from oming into ontt with dirtD hirD )kes of skinD nd other ontminnts tht n e shed from humn odiesF hey protet the silion wfers from the peopleD not the people from the hemilsF
PWQ vee xelD the hed of sfetyD helthD nd environmentl 'irs for the emiondutor sndustry essoE itionD hs een quoted s syingD his is n environment tht is lener thn n operting room t hospitlF roweverD this ost is urrently eing hllenged y industry workersD government sientistsD nd ouptionlEhelth experts ross the ountry nd worldwideF sndustril hygiene hs lwys een n issue in the semiondutor industryF wny of the hemils involved in the mnufturing proess of semiondutors re known humn rinogens or pose some other serious helth risk if not ontined properlyF le WFI lists ten of the hzrdous hemils most ommonly used in mnufturing semiondutors long with their known e'ets on humn helthF
Chemical name Role in manufacturing process Health problems linked to exposure
eetone
ghemilEmehnil polishing of silion wfers
xoseD throtD lungD nd eye irriE ttionD dmge to the skinD onE fusionD unonsiousnessD possile om xuseD deliriumD vomitingD dysE pepsiD dirrheD derese in eryE throyte nd leukoyte produE tionD norml hert rhythmD lood vessel dmgeD extensive tissue dmge to nervesD stomE hD intestineD nd skinD known humn rinogen for lung nE er redheD mliseD weknessD vertigoD dyspneD nuseD domE inl nd k pinD jundieD peE ripherl neuropthyD nemi hmge to one mrrowD neE miD exessive leedingD immune system e'etsD inresed hne of infetionD reprodutive e'etsD known humn rinogen for leukemi
erseni
snreses ondutivity of semiE ondutor mteril
ersine
ghemil vpor deposition
fenzene
hotoeletrohemil ething
PWR gdmium

gretes holes in silion lttie to rete e'et of positive hrge hmge to lungsD renl dysfunE tionD immedite hepti injuryD one defetsD hypertensionD reE produtive toxiityD tertogeniE ityD known humn rinogen for lung nd prostte ner righly orrosiveD severe eye nd skin urnsD onjuntivitisD derE mtitisD respirtory irrittion hmge to renlD reprodutiveD nd immune systemsD spontE neous ortionD premture irthD low irth weightD lerning de(its in hildrenD nemiD memory efE fetsD dementiD deresed reE tion timeD deresed mentl ilE ity redheD entrl nervous sysE tem depressionD poor equiliriumD eyeD noseD throtD nd skin irritE tionD rdi rrhythmi eknessD onfusionD memory lossD nuseD permnent dmE ge to rinD speehD visionD nd hering prolemsD loss of musle ontrolD poor lneD neurologE il prolems nd retrdtion of growth in hildrenD suspeted huE mn rinogen for lung nd liver ner srrittion of skinD eyesD nd resE pirtory trtD dizzinessD drowsiE nessD speeh nd hering imE pirmentD kidney diseseD lood disordersD strokeD dietesD susE peted humn rinogen for reE nl ner
rydrohlori id
hotoeletrohemil ething
ved
iletroplted soldering
wethyl hloroform
shing
oluene
ghemil vpor deposition
rihloroethylene
shing
Table 9.1
X ghemils of onern in the semiondutor industry SF
everl semiondutor mnufturers inluding xtionl emiondutor nd sfw hve een ited in the pst for holes in their sfety proedures nd hve een ordered to tighten their hndling of rinogeni nd toxi mterilsF sn IWWTD IIU former employees of sfw nd the fmilies of II workers who hd died of ner (led suit ginst the hemil mnufturers istmn uodk gompnyD nion gride gorportionD tF F fkerD nd us ghemilsD liming tht they hd su'ered dverse helth e'ets s result of exposure to hzrdous hemils on the jo in the semiondutor industry SF he lwsuit ws (led in xew orkD whih prevented the employees from suing sfw diretlyF e seprte group of former sfw workers who hd developed ner (led suit ginst the ompny in gliforniD lleging tht they hd een exposed to unhelthy doses of rinogeni hemils over the pst three dedesF itnesses who testi(ed in depositions in the xew ork
PWS stte ourt in esthester gounty desried how monitors tht were supposed to wrn workers of toxi leks often did not funtion euse of orrosion from ids nd wterF hey lso lleged tht supervisors sometimes shut down monitors to mintin prodution rtesF hen they lodged omplints with senior o0ils in the ompnyD they lim to hve een told not to mke wves TF wenwhileD UH femle workers in otlnd sued xtionl emiondutor gorportionD nother FFEsed ompnyD liming tht theyD tooD were exposed to rinogens on the joF hese lwsuits nd the resulting puliity prompted groundreking study y the relth nd fety ixeutiveD whih ommissioned ommittee to investigte these llegtions UF he ommittee found tht there were indeed unusully high levels of rest nd other kinds of ner mong workers t xtionl emiondutor9s frition fility in qreenokD otlndF he ommittee onluded tht the ompny hd filed to ensure tht the lol exhust ventiltion systems dequtely ontrolled the potentil exposure of employees to hydro)uori id nd sulphuri id fumes nd to rseni dustF hese (ndings proved to e extremely emrrssing for the ompny nd for the industryF eording to n o0il sttement relesed y sr veightonD ting regionl dministrtor of the xew inglnd rnh of the FF invironmentl rotetion egenyD xtionl emiondutor is ig usiness tht uses lrge mount of hrmful hemils nd other mterilsF yur hzrdous wste regultions were reted to properly monitor dngerous hemils nd prevent spillsF sn order for it to workD it is importnt usinesses to omply with ll of the regultionsF hen ompnies fil to do this they re potentilly putting people ! their employees nd neighors ! t risk VF woreoverD study of (fteen semiondutor mnufturers pulished in the heemer IWWS issue of the emerin tournl of sndependent wediine showed tht women working in the soElled len rooms of the semiondutor fs su'ered from IR7 misrrige rteF
Figure 9.6:
Center).
Protesters at a rally staged against IBM (photo from San Francisco Independent Media
he min prolem in proseution is tht the industry does not hve single overrhing nd de(nitive proess for mnufturingD nd it is di0ult to pinpoint one prtiulr ompound s using ertin helth prolem euse some plnts use s mny s QHH hemilsF elsoD mny of the mnufturing proesses tke
PWT
ple in losed systemsD so exposure to hrmful sustnes is often di0ult to detet unless monitored on dily sisF ixeutives nd spokespeople for the semiondutor industry mintin tht ny hip workers9 ners nd other medil prolems re more likely due to ftors unrelted to the joD suh s fmily historyD drinkingD smokingD or eting hitsF hey lso sy tht over the yersD s wreness of hemil hzrds hs grownD they hve mde e'orts to phse out toxi hemils nd to lower exposure to othersF hey insist tht they use stteEofEtheErt proess equipment nd hemil trnsfer systems tht limit or prevent physil exposure to hemils nd point out tht the sustnes used in the semiondutor industry re used in other industries without mjor helth or sfety prolemF
9.1.6 What environmental risks are involved?

sn theoryD ttention to lenliness is in the mnufturer9s est interest not only from helth perspetive ut lso from n eonomiF wny hemils used in the prodution proess re not expensive in nd of themselvesY howeverD the ost of mintining these mterils in n ultrElen stte n e quite highF his enourges the lose monitoring of usgeD the minimiztion of onsumptionD nd the development of reyling nd reproessing tehniquesF elsoD the rising osts of hemil disposl re prompting ompnies to ondut reserh into lterntives tht use more environmentlly friendly methods nd mterilsF sndividul ompnies nd worldwide trde ssoitions were tive in reduing the use nd emission of greenhouse gses during the IWWH9sD nd the industry s whole hs sustntilly redued emissions over the lst twenty yersF xonethelessD there hs een history of environmentl prolems linked to the industry in ilion lley nd other tehnology entersF o egin withD tremendous mount of rw mterils is invested in the mnufturing of semiondutors every yerF woreoverD typil fility produing semiondutors on sixEinh wfers reportedly uses not only PRHDHHH kilowtt hours of eletriity ut lso over P million gllons of wter every dy WF xewer filities tht produe eightEinh nd twelveEinh wfers onsume even moreD with some estimtes going s high s (ve million gllons of wter dilyF hile reyling nd reusing of wter does ourD extensive hemil tretment is required for remeditionD nd in dry or desert res suh s eluquerqueD xew wexioD home to plnts for wotorolD hilips emiondutorD ellied ignl nd ignetisD sntelD nd other highEteh (rmsD the high onsumption of wter neessry for the mnufturing of semiondutors n pose n espeilly signi(nt drin on n lredy sre nturl resoure IHF he existene of eonomi minstys inluding the mining industry nd the estlished presenes of ndi xtionl vortories nd the vos elmos xtionl vortory mke xew wexio n ttrtive lotion for highEteh tenntsF roweverD the opening of frition filities in the stte leves its frmers nd rnhers in onstnt ompetition with the orportions for rights to wter onsumptionF yn vergeD the mnufturing of just IGVEinh of silion wfer requires out QDUVU gllons of wstewterD not to mention PU pounds of hemils nd PW ui feet of hzrdous gses IIF
PWU
A community near Sutter Creek, California that has been designated as an EPA Superfund site as a result of arsenic contamination (photo from Alexander, Hawes, & Audet).
Figure 9.7:
gontmintion hs lso een n issue in res surrounding frition plntsF hrinking wter ws found to e ontminted with trihloroethne nd preonD toxins ommonly used in the semiondutor industryD in n toseD gliforni in IWVI IPF hese toxins were lter suspeted to e the use of irth defets of mny hildren in the reF he ulprits were pirhild emiondutor nd sfwF he ompnies9 underground storge tnks were found to hve leked tens of thousnds of gllons of the toxi solvents into the groundF here re numer of semiondutorErelted ie lenup sites in ilion lleyD nd there hve een onerns rised out the umultive ir nd groundwter pollution in ilion lleyD s wellF enother re of onern is the eventul fte of disrded eletroni systems suh s omputersD pgersD moile phonesD nd televisions tht ontin semiondutor deviesF ersonl omputers in prtiulr re espeilly prolemti euse they eome osolete firly rpidly nd lose lmost ll of their mrket vlue within (ve or ten yers fter their dte of mnuftureF ens of millions of g9s re sold in the nited ttes eh yerD nd they pose n environmentl risk not only through their sheer ulk in ity dumps nd lnd(lls ut lso euse their semionduting devies often ontin signi(nt mounts of hevy metlsD inluding led nd other potentilly hzrdous sustnesF
9.1.7 Why don't we hear more about this on the news?

eross the nited ttesD pproximtely TH7 of the mnufturing filities for semiondutor devies re loted in six sttesF hese sttes listed in desending order re gliforniD exsD wsshusettsD xew orkD sllinoisD nd ennsylvniF he industry ppers to e onentrted in these prtiulr lotions in prt euse they re ner the primry usersD trnsporttion routesD nd experts in the (eldD ut people of ll ges in ll (fty sttes re impted y semiondutor tehnologyF gonsumerism of semiondutor produts is only expeted to inrese in oming yersF eppleD for instneD expets to hve sold PQFT million iodsD devies tht rely on semiondutor tehnologyD y the yer PHHTF sf semiondutors re so uiquitous in our dyEtoEdy livesD why is there so little wreness out the serious environmentl nd helth risks tht re involved in their mnufturing proessc rt of the prolem is tht little is known out the longEterm helth or environmentl onsequenes of exposure to the hemils tht re used in the proessF feuse the semiondutor industry is still reltively newD not mny studies
PWV
hve een onduted on this topiD nd existing dt is often inonlusiveF his eing sidD some sientists predit tht the ner rte in the silion hip industry will rise signi(ntly in the future euse ner n tke s long s PHEPS yers to mnifest itself in popultions of exposed workersF he ie does hve regultions in e'et tht re imed towrd the purpose of ontrolling the levels of ontminnts relesed nd minimizing humn nd environmentl exposure to themF roweverD urrent regultions do not mndte tht emerin ompnies report on o'shore mnufturingF hereforeD even s medi overge nd generl wreness inreseD ompnies n simply outsoure more nd more of their frition filities toD for exmpleD outhest esiF ome ompniesD in ftD hve egun to do soD nd there hve even lredy een studies onduted on the helth issues of workers in the eletronis nd semiondutor industries of ingpore nd wlysi IQF husD hnges in how nd where semiondutor (rms mnufture hips urrently outstrip the present ility of the nited ttes government nd medi institutions to trk nd monitor their potentil threts to humns nd the environmentF sf this sitution is to hnge for the etter in the ner futureD it is ler tht rdil reforms will need to tke ple on numer of di'erent levelsF roweverD the whoD whtD whenD whereD nd whyD so to spekD of tht reform remins to e ddressedF
9.1.8 Discussion questions

row mny eletronis produts do you use on dyEtoEdy sisc row mny of these produts ontin semiondutorsc ho do you think is ultimtely responsile for inititing reformc he governmentc he orportionc he onsumerc ho you think tht the helth nd environmentl inidents relted to semiondutor mnufturing will remin isolted inidentsc yr do you think tht these inidents will eome epidemi in the futurec ho you think tht nnotehnology will help the prolem or mke the prolem worsec
9.1.9 Endnotes
IF wF uzmierzk nd tF tmesF sndustry ht 8 ulitionsX FF righEeh ixE portsD PHHHEPHHRF IT xovF PHHRF emerin iletronis essoitionF IU ytF PHHS<httpXGGwwwFenetForgGulitionsGidjlushightehexportsIPHRFsp>F PF tF urleyD he issentil quide to emiondutorsF pper ddle iverD xew terseyX rentie rll rofessionl ehnil efereneD PHHQF QF tF urleyD he issentil quide to emiondutorsF pper ddle iverD xew terseyX rentie rll rofessionl ehnil efereneD PHHQF prom rentie rll3 RF sfw eserh xnotehnology romepgeF sfwF IT ytF PHHS <httpXGGdominoFreserhFimFomGommGreserhFnsfGpgesGrFnnotehFhtml>F SF F ghepesiukD here the ghips pllX invironmentl relth in the emiondutor sndustryF inviE ronmentl relth erspetives IHU @IWWWAX RSPERSUF TF ihrdsD sndustry ghllengeX gomputerEghip lnts eren9t s fe end glen es filledD ome y ! omen t ottish ptory ell of pills nd pumesD pe rost of wedil slls ! pirms on9t relp ho tudyF ll treet tournl S ytF IWWVD estern edFX eIF UF eF revensD ghip lnts ke ret por oxisF IR tnF PHHQF ired xewsF IQ ytF PHHSD <httpXGGwwwFwiredFomGnewsGtehnologyGHDIPVPDSUIWIDHHFhtml> VF wF werhntD wine emiondutor lnt pined por rzrdous ste ioltionsF fostonX FF invironmentl rotetion egenyD ress y0eD PHHIF WF F hunnD glenliness yutsideD ome sssues yutsideF P ytF PHHHF he poundtion for emerin gommunitionsF IQ ytF PHHS <httpXGGwwwFfsnetForgGtoolsGsitehGtehGommunityGenvironPFphpQ>
3
http://www.phptr.com/
PWW IHF tF wzurekD wking wirohipsX oliyD qloliztionD nd ionomi estruturing in the emionE dutor sndustryF gmridgeD wsshusettsX ws ressD IWWWF IIF gF ryhurstD oxi ehnologyX iletronis nd the ilion lleyF iX the invironmentl wgzine wyEtunF IWWUX RF IPF fF imentelD he lley9s oxi ristoryF n prniso ghronile QH tnF PHHRD (nl edFX fIF IQF F vinD relthD omen9s orkD nd sndustriliztionX emiondutor orkers in ingpore nd wlysiF xew orkX qrlnd ulishingD snFD IWWIF
QHH
INDEX
Index of Keywords and Terms

re listed y the setion with tht keyword @pge numers re in prenthesesAF ueywords do not neessrily pper in the text of the pgeF hey re merely ssoited with tht setionF Ex. pplesD IFI @IA Terms re referened y the pge they pper onF Ex. pplesD I
Keywords
D TFP@IWPAD TFU@PQPA eti idD RFI@IIQA etyletonteD TFP@IWPA idD RFI@IIQAD RFU@IRUAD TFQFI@PHHA epwD UFP@PRUAD VFQ@PTIAD VFR@PUPAD VFS@PUUA elPyQD TFRFP@PITA elglQD TFSFQ@PPSA evhD SFP@ITWA eviD SFP@ITWAD TFQFP@PHPA lklineD RFI@IIQA lkoxideD QFQ@IHIAD TFT@PQHA llowed stteD IFI@QA lloyD IFS@QVAD RFW@ITHAD SFI@ITQA elweQD TFSFQ@PPSA elxD TFSFQ@PPSA luminD QFQ@IHIAD TFRFP@PITA luminumD IFR@PHAD IFS@QVAD PFS@TTAD QFP@VWAD QFQ@IHIAD RFW@ITHAD SFR@IVRA luminum nitrideD TFSFQ@PPSA luminum siliteD TFRFP@PITA mipolrD IFQ@ITA mideD TFSFQ@PPSA mmoniD TFQFI@PHHAD TFRFI@PHVAD TFSFI@PPPAD TFSFP@PPPAD TFSFQ@PPSA morphousD QFR@IHRAD SFP@ITWAD SFR@IVRA nisotropiD RFI@IIQA nnelingD IQH nnulrD RFI@IIQA nodeD PFS@TTA ntimonyD IFS@QVAD QFP@VWA ntisiteD IFR@PHA eghD TFRFI@PHVAD TFRFP@PITAD TFSFP@PPPA eD PFU@UVA rgonD RFW@ITHAD TFP@IWPAD TFRFI@PHVA errheniusD SFQ@IURA rseniD PFR@TPAD PFT@USAD QFI@VSAD QFP@VWAD SFI@ITQAD TFQFI@PHHAD TFQFP@PHPA rsenideD IFR@PHAD IFS@QVAD QFI@VSAD TFQFI@PHHA
rsineD SFP@ITWAD TFQFI@PHHAD TFQFP@PHPAD TFRFI@PHVA esD QFP@VWA tomD IFR@PHA tom densityD IFR@PHAD IFS@QVA tom positionsD IFR@PHA tomi lyer depositionD SFP@ITWA tomi lyer epitxyD SFP@ITWA eugerD SFI@ITQA
ndD IFI@QA nd digrmD IR nd gpD PFI@SIAD PFR@TPAD PFS@TTAD QFI@VSA ng gpD IFI@QAD IFP@WA seD PFI@SIA tteryD PFP@SQAD PFQ@SVA uxiteD QFI@VSAD QFP@VWAD QFQ@IHIA isD PFI@SIA inderD QFQ@IHIA fingel retionD VFQ@PTIA ipolrD PFI@SIA isErylzideD RFU@IRUA iszideD RFU@IRUA odyEenteredD IFR@PHA oehmiteD QFQ@IHIA oiling pointD TFRFI@PHVA ond energyD SFP@ITWA ori idD SFR@IVRA oronD QFI@VSAD QFP@VWAD RFV@ISQA oron nitrideD SFI@ITQA orophosphorosiliteD RFQ@IQHA ottomEupD VFI@PSWA oundry lyerD SFQ@IURA fqD RFQ@IQHA frvis lttieD IFR@PHA fridgmnD QFI@VSA ulerD SFQ@IURAD TFI@IWIA fukyllD VFQ@PTIA ulkD IFR@PHA yprodutD QFP@VWA
INDEX
QHI otingD PFU@UVAD QFR@IHRA oltD QFP@VWA ohereneD PFT@USA okeD QFP@VWA olletorD PFI@SIA olorD PFS@TTA omplexeD TFP@IWPA ompoundD IFR@PHAD TFP@IWPA ondutionD IFI@QA ondution ndD IFP@WAD RFR@IQRA onjugtedD PFS@TTA oordintion numerD IFR@PHA opperD IFR@PHAD QFP@VWAD TFU@PQPA orundumD QFQ@IHIAD TFRFP@PITA goulomD PFQ@SVA gD RFQ@IQHA grker ellD SFI@ITQA ritil dimensionD RFT@IRQA roppingD RFI@IIQA rossElinkingD RFU@IRUA rystlD IFR@PHAD QFI@VSAD QFR@IHRAD SFI@ITQAD SFP@ITWA rystl xesD IFR@PHA rystl diretionD IFR@PHA rystl growthD QFI@VSA rystl plneD IFR@PHA rystl shpingD RFI@IIQA rystl stressD QFI@VSA rystllogrphyD IFR@PHA guD TFU@PQPA uneD TFP@IWPA uiD IFR@PHAD IFS@QVAD QFP@VWA gurieD QFR@IHRA gurie pointD QFR@IHRA urrentD PFI@SIAD PFQ@SVA ghD RFQ@IQHAD RFR@IQRAD SFP@ITWAD SFQ@IURAD TFI@IWIAD TFP@IWPAD TFQFP@PHPAD TFRFI@PHVAD TFRFP@PITAD TFSFI@PPPAD TFSFP@PPPAD TFSFQ@PPSAD TFT@PQHAD TFU@PQPA gylodditionD VFQ@PTIA gzohrlskiD QFI@VSAD QFR@IHRAD RFI@IIQA
gTHD VFQ@PTIAD VFS@PUUA gUHD VFQ@PTIA dmiumD VFP@PSWA gpPD TFT@PQHA liumD PFS@TTAD QFP@VWAD TFT@PQHA lium )uorideD TFT@PQHA ronD QFP@VWA ron monoxideD QFP@VWA gro9s idD RFI@IIQA rrierD PFI@SIAD QFI@VSA rrier densityD QFI@VSA rrier gsD TFU@PQPA stD QFQ@IHIA thodeD PFS@TTA tionD SFR@IVRA gfhD SFR@IVRA gfiD SFI@ITQA gdeD VFP@PSWA ellsD PFU@UVA ermiD QFQ@IHIAD QFR@IHRA ermi proessingD QFQ@IHIA hlogenideD TFP@IWPA hlopyriteD IFR@PHAD IFS@QVA hmerD RFW@ITHA hnnelD PFQ@SVA hrolD QFP@VWA hrgeD IFP@WAD PFP@SQAD PFQ@SVA hrge oe0ientD QFR@IHRA hemilD WFI@PVUA hemil th depositionD SFR@IVRA hemil em epitxyD SFI@ITQA hemil vpor depositionD RFR@IQRAD SFP@ITWAD SFQ@IURAD TFI@IWIAD TFP@IWPAD TFQFP@PHPAD TFRFI@PHVAD TFRFP@PITAD TFSFP@PPPAD TFSFQ@PPSAD TFT@PQHAD TFU@PQPA hemilly onverted grpheneD VFR@PUPA hemie dueD VFI@PSWA hemisorD SFP@ITWA hemistryD @IA hirlD TFQFI@PHHA hlorteD RFI@IIQA hromiumD QFP@VWA innrD IFR@PHA iruitD RFV@ISQA itri idD RFI@IIQA glusiusEglpeyronD TFP@IWPA leningD RFI@IIQA lose pkedD IFR@PHA gwyD RFQ@IQHA gxED PFS@TTA gyD QFP@VWA
dngling ondD IFR@PHAD IFS@QVA hgD PFI@SIA de foisudrnD QFI@VSA deompositionD TFI@IWIAD TFP@IWPAD TFQFP@PHPA defetD IFR@PHAD SFI@ITQA degredtionD PFS@TTA deloliztionD PFS@TTA depositionD SFQ@IURAD SFR@IVRAD TFQFP@PHPAD TFU@PQPA
QHP depth resolutionD UFI@PQWA desorptionD SFQ@IURAD TFQFP@PHPA detetion limitD UFI@PQWA devieD RFQ@IQHA dimondD IFI@QAD IFR@PHAD IFS@QVAD RFI@IIQA diorneD TFRFI@PHVA dieletriD RFQ@IQHA dieletri onstntD TFRFI@PHVA di'erentil therml nlysisD TFP@IWPA di'usionD IFQ@ITAD RFR@IQRAD SFI@ITQAD SFQ@IURA di'usion rrierD TFU@PQPA di'usion oe0ientD IFQ@ITA diketonteD TFT@PQHA dinitrogenD TFSFP@PPPA diodeD PFR@TPA diphosphineD TFQFI@PHHA diret nd gpD PFR@TPA dislotionD IFR@PHA dispersionD QFQ@IHIA dopntD RFR@IQRAD SFI@ITQAD SFQ@IURAD TFRFI@PHVA doped semiondutorD IFP@WA dopingD IFP@WAD RFP@IPWA drinD RFV@ISQA driveEinD RFV@ISQA dryingD QFQ@IHIA heD TFP@IWPA environmentl helthD WFI@PVUA epitxilD TFRFP@PITA epitxyD IFR@PHAD SFI@ITQA ethD RFI@IIQAD RFS@IQVAD RFT@IRQAD RFU@IRUAD RFV@ISQA ethingD RFI@IIQA iuler9s theoremD VFQ@PTIA exittionD IFI@QA exitonD PFS@TTA exposureD RFS@IQVA eyeD PFR@TPA
INDEX
feEenteredD IFR@PHA fetD PFT@USA permi levelD PFP@SQA piD RFQ@IQHA (erD QFR@IHRA pik9s pirst vwD IFQ@ITA (eld e'et trnsistorD PFQ@SVAD RFQ@IQHA (lmD PFS@TTA (ringD QFQ@IHIA )uidized edD QFP@VWA )uorideD TFT@PQHA )uorineD TFP@IWPA )uorosilii idD SFR@IVRA )uxD TFI@IWIA frequenyD PFR@TPA pullereneD VFQ@PTIA furneD QFP@VWA qD QFP@VWA qesD IFS@QVAD PFR@TPAD PFT@USAD QFI@VSAD RFI@IIQAD SFI@ITQAD SFP@ITWAD TFQFP@PHPAD TFSFP@PPPA qesD PFR@TPA glliD QFI@VSA glliumD IFR@PHAD IFS@QVAD PFR@TPAD PFT@USAD QFI@VSAD QFP@VWAD SFI@ITQAD SFP@ITWAD TFP@IWPAD TFQFP@PHPA gllium rsenideD PFR@TPAD PFT@USAD QFP@VWAD RFI@IIQAD SFI@ITQAD SFP@ITWAD TFQFP@PHPA grnetD QFQ@IHIA gsD TFP@IWPA gs onstntD TFP@IWPA gteD PFP@SQAD PFQ@SVAD RFQ@IQHAD RFV@ISQA qeD IFS@QVA geltionD QFQ@IHIA germiniumD IFR@PHA germniumD IFS@QVAD QFR@IHRA gisiteD QFQ@IHIA qyD VFR@PUPA goldD PFS@TTAD QFP@VWA
ihD UFI@PQWA e0ienyD PFS@TTA e'usion ellD SFI@ITQA ekEluminumD QFI@VSA eletri (eldD PFP@SQA eletri momentD QFR@IHRA eletrodeD QFP@VWA eletroless depositionD SFR@IVRA eletrolyteD QFQ@IHIA eletronD IFI@QAD IFP@WAD IFQ@ITAD PFI@SIAD PFS@TTAD PFU@UVAD QFI@VSAD SFI@ITQA eletron 0nityD PFS@TTA eletron moilityD QFI@VSA eletron trnsportD IFQ@ITA eletroni mterilsD @IA elementD IFR@PHA emissionD PFS@TTAD PFT@USA enpsultionD TFSFP@PPPA endohedrl fullereneD VFQ@PTIA energyD IFI@QAD PFR@TPA enthlpyD TFP@IWPA entropyD TFP@IWPA
INDEX
grpheneD VFR@PUPA grphiteD VFQ@PTIA grphite oxideD VFR@PUPA green odyD QFQ@IHIA grindingD RFI@IIQA qroup IPEITD IFR@PHA qroup IQEISD IFR@PHA qroup IRD IFI@QA qroup ssEsD IFR@PHA qroup sssED IFR@PHA qroup sD IFI@QA growthD SFP@ITWA growth rteD SFQ@IURAD TFQFP@PHPA interEtomiD IFR@PHA interonnetD RFW@ITHA internl e0ienyD PFS@TTA interstitilD IFR@PHA intrEplnrD IFR@PHA ion implnttionD IPW ioniztion potentilD PFS@TTA ionsD RFW@ITHA ironD QFP@VWA isoltionD RFQ@IQHA isopreneD RFU@IRUA isothermlD TFP@IWPA syD PFS@TTA
QHQ
rllEreroultD QFQ@IHIA reD UFI@PQWA heliumD UFI@PQWA hemogloinD TFQFI@PHHA heterojuntionD PFS@TTA hexgonD IFR@PHA hexgonlD IFR@PHA rpD RFI@IIQA hfD TFP@IWPA high pressureD RFR@IQRA rsD QFR@IHRA rxyQD RFI@IIQA holeD IFI@QAD IFP@WAD PFP@SQAD PFS@TTAD SFI@ITQA holesD IFQ@ITA hoppingD VFS@PUUA hot isostti pressD QFR@IHRA hydro)uori idD RFI@IIQAD SFR@IVRA hydrogenD RFR@IQRAD SFQ@IURAD TFP@IWPAD TFQFI@PHHAD TFRFI@PHVA hydrogen peroxideD RFI@IIQA hydrolysisD SFR@IVRAD TFRFP@PITA hydrophoiD VFQ@PTIA hydrotherml synthesisD QFR@IHRA hydroxideD QFQ@IHIA sgD RFV@ISQA idiret nd gpD PFR@TPA imgeD RFU@IRUA indiesD IFR@PHA indiumD IFR@PHAD IFS@QVAD PFS@TTA indium tin oxideD PFS@TTA inert gsD QFP@VWA inhiitorD RFU@IRUA snD IFS@QVA insultionD TFRFI@PHVA insultorD PFQ@SVA integrted iruitD RFT@IRQAD RFV@ISQA
J K L
juntionD PFQ@SVAD PFU@UVA kinetisD TFP@IWPA unudsenD SFI@ITQA veghD SFQ@IURA lppingD RFI@IIQA lserD PFT@USAD RFT@IRQAD SFP@ITWAD SFQ@IURA lttieD IFR@PHAD SFI@ITQA lttie onstntD IFS@QVAD QFI@VSA lttie prmeterD IFR@PHAD IFS@QVA ledD QFP@VWA led metnioteD QFR@IHRA led zironte titnteD QFR@IHRA vihD PFR@TPAD PFS@TTAD QFI@VSA lensD RFS@IQVA vewis seD TFU@PQPA lifetimeD IFQ@ITA ligndD TFU@PQPA lightD PFT@USAD PFU@UVAD RFS@IQVA light mpli(tionD PFT@USA light emitting diodeD PFR@TPA light emitting diodesD PFS@TTA liquidD TFI@IWIA liquid phse depositionD SFR@IVRA lithium nioteD QFR@IHRA lithogrphyD RFT@IRQA low pressureD SFQ@IURA vghD TFRFI@PHVAD TFRFP@PITAD TFSFP@PPPAD TFSFQ@PPSA vhD SFR@IVRA mngneseD QFP@VWA mnufturingD WFI@PVUA mskD RFR@IQRAD RFS@IQVAD RFT@IRQA mss trnsportD SFQ@IURA wfiD SFI@ITQA
M mgnesiumD QFP@VWA
QHR men free pthD IFI@QA mehnil qulity ftorD QFR@IHRA mehnismD TFQFP@PHPA wendeleevD QFI@VSA meruryD QFP@VWA merury sul(deD IFS@QVA wipiD TFSFP@PPPA metlD PFQ@SVAD RFV@ISQAD TFU@PQPA metl metlliztionD RFW@ITHA metl orgni hemil vpor depositionD TFP@IWPAD TFT@PQHA metl oxideD TFRFP@PITA metl oxide semiondutorD PFP@SQA metliztionD RFQ@IQHA metlliztionD TFU@PQPA miroiruitD RFQ@IQHA willerD IFR@PHA minerlD QFQ@IHIA minority rrierD IFQ@ITA mirrorD PFS@TTAD PFT@USA mixedEmetl oxideD QFQ@IHIA moilityD IFP@WAD QFI@VSA wyghD SFP@ITWAD SFQ@IURAD TFP@IWPAD TFQFP@PHPAD TFSFP@PPPAD TFSFQ@PPSAD TFT@PQHA moleulr em epitxyD SFI@ITQA moleulr weightD QFR@IHRA moleuleD TFI@IWIA molydenumD QFP@VWA momentumD PFR@TPA monoliniD IFR@PHA monolyerD SFI@ITQA monosilneD QFP@VWA morphologyD QFR@IHRAD UFP@PRUA wyD PFP@SQAD PFQ@SVAD RFV@ISQA wypiD PFQ@SVAD RFQ@IQHAD RFR@IQRA mulliteD TFRFP@PITA wxD VFQ@PTIA
INDEX
negtive resistD RFU@IRUA xrQD TFSFP@PPPAD TFSFQ@PPSA nikelD QFP@VWA nioiumD UFI@PQWA nitreneD RFU@IRUA nitri idD RFI@IIQA nitrideD IFS@QVAD RFS@IQVAD RFV@ISQAD TFSFI@PPPA nitrogenD RFI@IIQAD RFU@IRUAD TFP@IWPAD TFRFI@PHVAD TFSFI@PPPA nitrous oxideD TFRFI@PHVA nonEentrosymmetriD QFR@IHRA novolk resinsD RFU@IRUA npnD PFI@SIAD RFP@IPWA
othedrlD IFR@PHA yhgfD VFR@PUPA ohmD IFP@WA ole(nD TFU@PQPA orgnosilionD TFSFP@PPPA orienttionD IFR@PHA orthorhomiD IFR@PHA oxidtionD PFS@TTAD RFR@IQRAD RFV@ISQAD TFRFP@PITAD VFQ@PTIA oxideD PFP@SQAD PFQ@SVAD RFS@IQVAD RFV@ISQAD SFR@IVRA oxygenD PFS@TTAD QFP@VWAD RFR@IQRAD RFV@ISQAD TFRFI@PHVAD TFRFP@PITA pEn juntionD IFQ@ITA pEtypeD PFI@SIAD PFP@SQAD PFQ@SVAD PFU@UVAD RFI@IIQAD SFI@ITQAD UFI@PQWA pkgingD RFQ@IQHA eghD SFQ@IURA pssivtionD RFQ@IQHAD TFSFP@PPPA ptternD RFT@IRQAD RFU@IRUAD RFV@ISQAD RFW@ITHA uliD IFI@QA ighD SFQ@IURAD TFRFI@PHVAD TFRFP@PITAD TFSFI@PPPAD TFSFP@PPPAD TFSFQ@PPSA perovskiteD QFQ@IHIA phseD PFT@USA phse digrmD TFRFP@PITA phosphideD IFR@PHAD IFS@QVAD TFQFI@PHHA phosphineD TFQFI@PHHAD TFRFI@PHVAD TFU@PQPA phosphorousD QFP@VWA phosphorous idD TFQFI@PHHA phosphorusD QFI@VSAD TFQFI@PHHA photolithogrphyD RFS@IQVAD RFT@IRQAD RFU@IRUA photolumineseeD PFS@TTA
nEtypeD PFI@SIAD PFP@SQAD PFQ@SVAD PFU@UVAD RFI@IIQAD SFI@ITQA xPD TFSFI@PPPA xPyD TFSFP@PPPA nnorD VFS@PUUA nnorystlD VFP@PSWA nnomterilsD VFQ@PTIA nnoprtileD VFI@PSWAD VFP@PSWA nnosheetD VFR@PUPA nnotueD VFQ@PTIA ntive oxideD QFI@VSA xD UFI@PQWA negtiveD RFS@IQVA
INDEX
photonD PFU@UVA photoresistD RFS@IQVAD RFU@IRUA physil vpor depositionD SFQ@IURA physisoredD SFP@ITWA iezoeletriityD QFR@IHRA pivotingD VFS@PUUA plnriztionD RFQ@IQHAD TFRFI@PHVA lnkD PFR@TPA plsmD RFQ@IQHAD RFR@IQRAD SFQ@IURAD TFRFI@PHVAD TFRFP@PITAD TFSFP@PPPA wweD RFT@IRQA pnitideD QFI@VSA pnpD RFP@IPWA pointD IFR@PHA polingD QFR@IHRA polishingD RFI@IIQA polsihingD QFR@IHRA polymideD QFR@IHRA polymerD PFS@TTAD RFT@IRQA polysilionD QFP@VWA polyureD QFR@IHRA polyvinylidene di)uorideD QFR@IHRA positiveD RFS@IQVA positive resistD RFU@IRUA potssiumD QFQ@IHIA potssium hydroxideD RFI@IIQA powderD QFQ@IHIA D PFS@TTA rto retionD VFQ@PTIA preursorD SFQ@IURAD TFI@IWIAD TFU@PQPA projetionD RFS@IQVA puri(tionD QFP@VWA hD SFQ@IURAD TFU@PQPA pyrolisisD QFR@IHRA pyrolysisD SFQ@IURAD TFQFP@PHPA D QFR@IHRA
QHS reliilityD PFS@TTA resinD RFQ@IQHA resistD RFT@IRQA resistneD IFP@WA resistivityD QFI@VSA riihD SFI@ITQAD SFP@ITWAD TFQFP@PHPA rhomohedrlD IFR@PHAD QFP@VWA rok sltD IFR@PHA rollingD VFS@PUUA ruyD QFQ@IHIA utherfordD UFI@PQWA
quntum devieD PFS@TTA quntum dotD VFP@PSWA quntum e0ienyD PFS@TTA quntum rodD VFP@PSWA qurtzD QFP@VWAD QFR@IHRA quternryD IFS@QVA rditiondiodeD PFT@USA mnD VFQ@PTIA rte limiting stepD RFI@IIQAD SFQ@IURA fD UFI@PQWA reomintionD IFQ@ITA redutionD TFQFI@PHHA refrtive indexD QFI@VSAD RFT@IRQAD TFRFI@PHVA
sri(ilD RFV@ISQA sndD QFP@VWA spphireD QFQ@IHIA eimensD QFP@VWA selenideD IFS@QVA seleniumD IFS@QVAD VFP@PSWA iwD UFP@PRUAD VFQ@PTIA semiEinsultingD QFI@VSA semiondutorD IFI@QAD IFP@WAD IFR@PHAD IFS@QVAD PFP@SQAD PFU@UVAD QFI@VSAD QFP@VWAD RFI@IIQAD RFQ@IQHAD RFR@IQRAD RFS@IQVAD RFT@IRQAD RFU@IRUAD SFP@ITWAD TFQFP@PHPAD TFU@PQPAD VFP@PSWA semiondutorsD RFP@IPWAD WFI@PVUA sensitizerD RFU@IRUA iD IFS@QVAD QFP@VWAD RFI@IIQAD SFI@ITQA iPglPD TFSFP@PPPA iQxRD RFS@IQVAD RFV@ISQAD TFSFP@PPPA iglPrPD TFSFP@PPPA irRD TFSFP@PPPA silneD TFRFI@PHVA silnolD SFR@IVRA siliD PFP@SQAD PFQ@SVAD RFQ@IQHAD RFR@IQRAD SFR@IVRAD TFRFI@PHVA siliteD QFP@VWA silionD IFP@WAD IFR@PHAD IFS@QVAD PFP@SQAD PFQ@SVAD PFR@TPAD PFS@TTAD QFI@VSAD QFP@VWAD QFR@IHRAD RFI@IIQAD RFQ@IQHAD RFR@IQRAD RFS@IQVAD RFV@ISQAD RFW@ITHAD SFI@ITQAD SFQ@IURAD UFI@PQWA silion hipD SFR@IVRA silion dioxideD RFQ@IQHAD RFR@IQRAD SFR@IVRA silion nitrideD TFSFI@PPPAD TFSFP@PPPA silion tetrhlorideD QFP@VWA single rystlD QFR@IHRA single soure preursorD TFSFQ@PPSA single stge elertorD UFI@PQWA iyPD RFQ@IQHAD RFR@IQRAD RFV@ISQAD SFR@IVRA
QHT siverD QFP@VWA slidingD VFS@PUUA slim rodD QFP@VWA slurryD QFQ@IHIA mlleyD VFQ@PTIA nD IFS@QVA sodiumD QFQ@IHIA sodium hydroxideD RFI@IIQA solEgelD QFQ@IHIAD QFR@IHRA solrD PFU@UVA solidD TFI@IWIA solid solutionD IFS@QVA solid stteD IFR@PHA solventD QFQ@IHIAD RFU@IRUA soureD RFV@ISQA spetrumD UFI@PQWA spinEotD RFU@IRUA sputteringD RFW@ITHA stedy stteD IFQ@ITA stemD RFR@IQRA step overgeD TFRFI@PHVAD TFU@PQPA stepperD RFS@IQVA stimulted emissionD PFT@USA wD VFS@PUUA stoihiometriD IFS@QVA stoihiometri rtioD UFI@PQWA strutureD IFR@PHAD UFP@PRUA sulimtionD TFP@IWPA sulimeD QFP@VWAD TFP@IWPA sustitutionD IFR@PHA sustrteD SFI@ITQAD SFQ@IURA sul(deD IFR@PHAD IFS@QVA sulfurD IFS@QVAD VFP@PSWA sunD PFU@UVA superidD TFQFI@PHHA superondutorD SFP@ITWA supersturtionD SFR@IVRA surfeD IFR@PHAD PFP@SQAD PFT@USAD RFI@IIQAD SFI@ITQAD SFQ@IURAD SFR@IVRAD TFU@PQPAD UFP@PRUAD VFS@PUUA surfe ousti wveD QFR@IHRA xD VFQ@PTIA synthesisD QFP@VWAD VFI@PSWA
INDEX
qeD TFP@IWPA thermlD RFR@IQRA thermogrvimetri nlysisD TFP@IWPA thin (lmD RFQ@IQHAD SFI@ITQAD SFP@ITWAD SFQ@IURAD SFR@IVRAD TFRFI@PHVAD TFSFI@PPPAD TFU@PQPAD UFI@PQWA thresholdD PFP@SQA tinD IFR@PHA titniumD QFP@VWA tolueneD RFU@IRUA topEdownD VFI@PSWA topzD QFQ@IHIA toxiD TFQFI@PHHA toxiityD TFI@IWIA trnsmintionD TFSFI@PPPAD TFSFP@PPPAD TFSFQ@PPSA trnsduerD QFR@IHRA trnsistorD PFI@SIAD PFQ@SVA trnsportD TFI@IWIA triliniD IFR@PHA trimethylglliumD SFP@ITWA
rpD QFR@IHRA vsD RFV@ISQA ultr high frequenyD QFR@IHRA ultrhigh vuumD SFI@ITQA umrellD TFQFI@PHHA unit ellD IFR@PHA D SFP@ITWA D RFT@IRQA vniesD IFR@PHA vuumD RFW@ITHAD TFP@IWPA vlne ndD IFP@WA vleneD IFI@QA vlene ndD RFR@IQRA vn der lD SFP@ITWA vndiumD QFP@VWA vpor pressureD QFP@VWAD SFI@ITQAD SFQ@IURAD TFI@IWIAD TFP@IWPA ergrd9s lwD IFR@PHA ertil nning snterferometryD UFP@PRUA qpD VFQ@PTIA visousEsuspensionEspinningD QFR@IHRA vsD RFQ@IQHAD RFV@ISQAD TFU@PQPA voltD PFQ@SVA voltgeD PFI@SIAD PFP@SQAD PFQ@SVA sD UFP@PRUA D QFR@IHRA RFS@IQVAD RFV@ISQAD RFW@ITHA
tndem elertorD UFI@PQWA trgetD RFW@ITHA iwD VFQ@PTIAD VFR@PUPAD VFS@PUUA iyD TFRFI@PHVA ternryD IFS@QVAD QFQ@IHIA tetrgonlD IFR@PHAD IFS@QVA tetrhedrlD IFR@PHA tfD TFP@IWPA
W wferD IFS@QVAD RFI@IIQAD RFR@IQRAD
INDEX
wferingD RFI@IIQA wfersD RFP@IPWA wshD RFT@IRQA wterD RFR@IQRAD SFR@IVRA wve funtionD IFI@QA wvelengthD PFR@TPAD PFU@UVA wellD RFV@ISQA urtziteD IFR@PHAD IFS@QVAD QFI@VSA D SFP@ITWAD TFQFP@PHPAD UFI@PQWA xyleneD RFU@IRUA
QHU
Y Z
eqD QFQ@IHIA zeroEorderD TFP@IWPA zinD IFR@PHA zin lendeD IFR@PHAD IFS@QVAD QFI@VSA zironiumD QFP@VWA zone re(ningD QFP@VWA
EryD RFT@IRQA
QHV
ATTRIBUTIONS
Attributions
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QHW
QIH woduleX 4vser4 fyX endrew F frron vX httpXGGnxForgGontentGmQQVHPGIFIG gesX USEUU gopyrightX endrew F frron vienseX httpXGGretiveommonsForgGliensesGyGQFHG fsed onX vei fyX fill ilson vX httpXGGnxForgGontentGmIHIPGPFITG woduleX 4olr gells4 fyX endrew F frron vX httpXGGnxForgGontentGmQQVHQGIFRG gesX UVEVQ gopyrightX endrew F frron vienseX httpXGGretiveommonsForgGliensesGyGQFHG fsed onX olr gells fyX fill ilson vX httpXGGnxForgGontentGmIHIQGPFIQG woduleX 4roperties of qllium ersenide4 fyX endrew F frron vX httpXGGnxForgGontentGmPPWUHGIFUG gesX VSEVW gopyrightX endrew F frron vienseX httpXGGretiveommonsForgGliensesGyGQFHG woduleX 4ynthesis nd uri(tion of fulk emiondutors4 fyX griss mithD endrew F frron vX httpXGGnxForgGontentGmPQWQTGIFTG gesX VWEIHI gopyrightX griss mithD endrew F frron vienseX httpXGGretiveommonsForgGliensesGyGPFHG woduleX 4germi roessing of elumin4 fyX endrew F frron vX httpXGGnxForgGontentGmPPQUTGIFSG gesX IHIEIHR gopyrightX endrew F frron vienseX httpXGGretiveommonsForgGliensesGyGQFHG woduleX 4iezoeletri wterils ynthesis4 fyX endrew F frron vX httpXGGnxForgGontentGmPSRRIGIFPG gesX IHREIII gopyrightX endrew F frron vienseX httpXGGretiveommonsForgGliensesGyGQFHG woduleX 4pormtion of ilion nd qllium ersenide fers4 fyX endrew F frron vX httpXGGnxForgGontentGmITTPUGIFQG gesX IIQEIPW gopyrightX endrew F frron vienseX httpXGGretiveommonsForgGliensesGyGPFHG
ATTRIBUTIONS
ATTRIBUTIONS
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QII
QIP woduleX 4epplying wetlliztion y puttering4 fyX endrew F frron vX httpXGGnxForgGontentGmQQVHHGIFQG gesX ITHEITP gopyrightX endrew F frron vienseX httpXGGretiveommonsForgGliensesGyGQFHG fsed onX sntrodution to wypis fyX fill ilson vX httpXGGnxForgGontentGmIHPHGPFIPG woduleX 4woleulr fem ipitxy4 fyX endrew F frron vX httpXGGnxForgGontentGmPSUIPGIFPG gesX ITQEITV gopyrightX endrew F frron vienseX httpXGGretiveommonsForgGliensesGyGQFHG woduleX 4etomi vyer heposition4 fyX endrew F frron vX httpXGGnxForgGontentGmPSUQUGIFPG gesX ITWEIUQ gopyrightX endrew F frron vienseX httpXGGretiveommonsForgGliensesGyGQFHG woduleX 4ghemil por heposition4 fyX endrew F frron vX httpXGGnxForgGontentGmPSRWSGIFPG gesX IUREIVR gopyrightX endrew F frron vienseX httpXGGretiveommonsForgGliensesGyGQFHG woduleX 4viquid hse heposition4 fyX ilizeth hitsittD endrew F frron vX httpXGGnxForgGontentGmPWUURGIFIG gesX IVREIVW gopyrightX ilizeth hitsittD endrew F frron vienseX httpXGGretiveommonsForgGliensesGyGQFHG woduleX 4eleting woleulr reursor for ghemil por heposition4 fyX endrew F frron vX httpXGGnxForgGontentGmPUVRTGIFIG gesX IWIEIWP gopyrightX endrew F frron vienseX httpXGGretiveommonsForgGliensesGyGQFHG
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ATTRIBUTIONS
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Chemistry of Electronic Materials

Collection Editor: Andrew R. Barron

Chemistry of Electronic Materials

Online: < http://cnx.org/content/col10719/1.6/ >

8 Nanotechnology 8.1 8.2 8.3 8.4 8.5

9 Economic and Environmental Issues 9.1 he invironmentl smpt of the

Preface to the Chemistry of Electronic Materials

This content is available online at <http://cnx.org/content/m25528/1.1/>. arb@rice.edu

Background to Electronic Materials

This content is available online at <http://cnx.org/content/m33647/1.3/>.

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

Crystal structure of silicon.

A 2-D representation of a silicon crystal.

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

Electron distribution for a metal or good conductor.

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

Thermal excitation of electrons across the band gap.

1.2 Doped Semiconductors

A two dimensional representation of a silicon crystal lattice "doped" with phosphorus.

This content is available online at <http://cnx.org/content/m33703/1.2/>.

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

Silicon doped with phosphorus.

Band full of electrons, with one missing.

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

Motion of the "missing" electron with an electric eld.

Further motion of the "missing electron" spot.

Motion of a "hole" due to an applied electric eld.

A two dimensional representation of a silicon crystal lattice doped with boron.

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

P-type silicon, due to boron acceptors.

An electron band-diagram for a semiconductor.

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

Band diagram for an n-type semiconductor.

This content is available online at <http://cnx.org/content/m33730/1.2/>.

Processes involved in electron transport across a p-n junction.

1.3.2 Diusion process quantied

A schematic representation of a diusion problem.

IV with itD @IFIIAF

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

Flux = (De ) Jediff = qDe

A schematic representation of a diusion from bins.

oD omining @IFIPAD @IFIQA nd @IFIRAD we hveD @IFISAF

1.3.3 What about the electrons?

1 d q dt (x, t) 1 q div (J (x, t))

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

1.4 Crystal Structure

This content is available online at <http://cnx.org/content/m16927/1.10/>.

X qeometril hrteristis of the seven rystl systemsF

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

trilini monolini rhomohedrl hexgonl orthorhomi tetrgonl ui

X ixmples of elements nd ompounds tht dopt eh of the rystl systemsF

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

Some common directions in a cubic unit cell.

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

Examples of Miller indices notation for crystal planes.

1.4.3 Description of crystal structures

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

1.4.3.4.4 Rock salt

CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS

1.4.3.4.7 Cesium Chloride

1.4.4 Defects in crystalline solids

Motion of the "missing" electron with an electric eld.

Motion of a "hole" due to an applied electric eld.

1.3.2 Diusion process quantied

A schematic representation of a diusion problem.

A schematic representation of a diusion from bins.

1.5.6 Orientation eects

Band diagram and carrier uxes in a bipolar transistor.

The start of a eld eect transistor.