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Atoms:
Electronsofasingleatomoccupyadiscretesetofenergylevels.Whenmeasuringthe
energiesofelectronsinanisolatedatom,wedonotfindacontinuousdistributionof
energies,butasetofquantizedenergies.

Theplotaboveshowsthepotentialenergyofanelectronandthreepossiblevaluesforthe
totalenergy.Thismodelofdiscreteenergylevelscanalsobeextendedtosimplecompound
molecules,andexperimentalevidencecaneasilybefoundintheemissionandabsorption
spectraofgases.
Electronenergiesarearequantized
Onlytwoelectronsareallowedtooccupyanenergylevelcharacterizedbythe
quantumnumbersn,l,andm.
Oneoftheseelectronwillhavespinupandtheotherwillhavespindown.
Electronsthataremoretightlyboundaremorelikelytobefoundclosertothenucleus.
Webuildatomsbyfillingenergylevelsfromthemostnegativetotheleastnegative.
Solids:
Whenatomsformasolid,thepotentialenergyofeachelectronchanges,anditspossible
energyvalueschange.Theenergyofthemoretightlyboundelectronschangesverylittle,
andtheseelectronsremainlocalizedaboutasingleatom.Thelesstightlyboundelectrons
donotremainlocalized,andtheirpossibleenergyvaluesnowfallintobandsofallowed
valuesseparatedbygaps.

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Theplotaboveshowsthepotentialenergyofanelectron,onepossibleenergyfora
localizedelectron,andtwoenergybandsfordelocalizedelectrons.
Considerasingleatomofaparticularspecies.Thisatomhasadiscretesetofenergy
levels.Whenanotheratomofthesamespeciesisbroughtclosetothefirstatom,eachof
theenergylevelsbecomesdegenerate.Buttheinteractionbetweentheatomsbreaksthe
degeneracyandthelevelsplitsintotwoseparateenergylevels.Ifthisprocedureisrepeated
>1020times,eachenergylevelwillhavesplitinto>1020level,effectivelyforminga
continuousbandofenergystates.
Simulation:Quantumboundstates
Althoughtheremaybeaninfinitenumberofbandsinthebandstructureofagivenmaterial,
therearetwobandsthatareofparticularsignificanceindeterminingtheelectronicand
opticalpropertiesofamaterial.Thesearetheconductionbandandthevalenceband.
Note:Thesetermsaredefinedbelowandmayrefertothesamebandinmaterialsthatare
conductors.
Oneofthemostusefulaspectsofthebandstructureisthefeatureknownasthebandgap.
Insemiconductorandinsulatormaterials,thisusuallyreferstothegapbetweenthevalence
bandandtheconductionband.Thebandgapanddefectstatescreatedinthebandgapby
dopingcanbeusedtocreatedevicessuchassolarcells,laserdiodes,transistors,anda
rangeofotherelectronicdevices.
Crystallinesolidsarecollectionsofatomsarrangedinarepetitivethreedimensional
structure.
Theenergylevelsinsolidsbecomegroupedinto"bands"whichareseparatedby
"gaps".
Electronscannothaveenergiesthatwouldfallintothegaps.

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Thehighestlyingbandcontainingfilledstates(asT>0)iscalledthevalenceband.
Thelowestlyingbandbandcontainingemptystates(asT>0)iscalledthe
conductionband.
Therearethreetypesofsolids:
metals
insulators
semiconductors
Thepropertiesofconductors,semiconductorsandinsulatorsaredeterminedbythenumber
ofelectronsthatoccupythetwohighestlyingenergybandsthatcanholdelectronsunder
normalcircumstances.Wethereforeoftenonlyshowthesetwobandsinanenergylevel
diagram.Eachofthetwobandscanonlyacceptafixednumberofelectronsbecauseitonly
containsafixednumberofstates.

Ifallthestatesinabandareoccupied,nonetmovementofelectronscanoccurandthe
bandcannotcontributetotheconductionofcurrent.(Allthewavefunctionsofallthe
electronsinterfereinsuchawayastoonlyformstandingwaveswithzeroaveragevaluefor
themomentum.Wecannotbuildtravelingwavepackets.)Anunoccupiedbandalsodoes
notcontributetotheconductionofcurrent.
Metals(conductors)havenogapbetweenthevalenceandtheconductionband.

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Itiseasytoaddasmallamountofenergytosomeoftheelectrons,sothattheycan
moveeasilyandconductelectricity.Butunlessweapplyavoltageelectronswillmove
inrandomdirections,andnonetcurrentwillflow.Electronscanbeacceleratedbyan
electricfield.
Eventhoughanelectricforceiscontinuouslyactingoneachelectronwhenasteady
currentisflowinginawire,theelectronsdonotcontinuetoaccelerateindefinitely,but
reachanaverageterminalvelocity,calledthedriftvelocity.Whentheelectronsmove
withthedriftvelocity,thentheresistiveforces(frictionalforces)actingonthemare
equalinmagnitudeandoppositeindirectiontotheelectricforces.Typicaldriftspeeds
areontheorderof1mm/s.
Theterminalvelocitydependsontheelectricforceandtheresistiveforce.Thehigher
theterminalvelocity,thelargeristhecurrent.Thecurrentwillincreaseifthevoltage
acrossthewireincreases,(thisincreasesthestrengthoftheelectricfield),and
decreaseiftheresistiveforcesincreaseinstrength.Electricalconductivityisa
measureofamaterialsabilitytoconductcurrent.Theconductivityofgoodconductors
decreaseswithtemperature.

Insulatorshavealargegapbetweenvalenceandconductionband.Inaninsulator,
thevalancebandistotallyoccupied,buttheconductionbandisempty.

Alargeamountofenergyisrequiredtomoveelectronsfromthevalencetothe
conductionband.Onlyintheconductionbandcanelectronsmoveeasilyandconduct
electricity.Ininsulatorstherearepracticallynoelectronsintheconductionband.The
amountofenergyelectronscangainfromthermalagitationisnotenoughtoliftthem
fromthevalencebandintotheconductionband.Theenergygapistoolarge.No
currentcanflow.
Problem:
Whatistheprobabilitythatanelectronatthetopofthehighestfilledbandwilljumpan
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energygapof3eVtotheconductionbandatroomtemperature?
Solution:
TheaveragenumberoffermionsinauniquelydefinedquantumstatewithenergyEis
givenby
PFermiDirac(E)=1/(exp((EEF)/kT)+1).
With(EEF)ontheorderofeVandkT=k*300K=2.58*102eV,wehaveexp((E
EF)/kT>>1,
andtheexpression1/(exp((EEF)/kT)+1)canbeapproximatedbyexp((EEF)/kT.
TheratiooftheaveragenumberofelectronsinastatewithenergyE2inthevalence
bandtotheaveragenumberofelectronsinastatewithenergyE1intheconduction
bandthereforeis
R=exp((E2E1)/kT=exp((3eV)/kT)=4*1051.
Theprobabilitythatanelectronwilljumpthegapisessentiallyzero.

Semiconductorshaveasmallgapbetweenthevalenceandtheconductionband.In
asemiconductortheenergygapbetweenthevalenceandtheconductionbandis
small,andathighertemperaturessomeelectronscangainenoughenergyfrom
thermalagitationtoliftthemfromthevalencebandtotheconductionband.The
valencebandnowcontainsholes,i.e.somestatesinthatbandareempty,andthe
conductionbandisnolongertotallyempty,butcontainssomeelectrons.Bothbands
cancontributetotheconductionofcurrent,buttheconductivityislow,becausethe
numberofunoccupiedstatesinthevalencebandandthenumberofoccupiedstatein
theconductionbandissmall.

Thepropertiesofsemiconductorsliebetweenthoseofmetalsandinsulators.For
intrinsicsemiconductorslikesiliconandgermanium,theFermilevelisessentially
halfwaybetweenthevalenceandconductionbands.Althoughnoconductionoccursat
0K,athighertemperaturesafinitenumberofelectronscanreachtheconductionband
andsomecurrentcanflowwhenavoltageisapplied.Indopedsemiconductors,extra
energylevelsareadded.

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TheincreaseinconductivitywithtemperaturecanbemodeledintermsoftheFermi
function,whichallowsonetocalculatethepopulationoftheconductionband.
Wheredoestheenergycomefromtoputelectronsinconductionband?
light
heat
appliedvoltage
Simulation:Conductivity
Doping
Theadditionofasmallpercentagetypically(108%103%)offoreignatomsintheregular
crystallatticeofsiliconorgermaniumproducesdramaticchangesintheirelectrical
properties,producingntypeandptypesemiconductors.Bothsiliconandgermaniumhave
4valenceelectronsperatom.Impurityatomwith5valenceelectronsproducentype
semiconductorsbycontributingextraelectrons.

Impurityatomwith3valenceelectronsproduceptypesemiconductorsbyleavinga
deficiencyandthuscreatingahole.

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Theadditionofimpuritiesinaptypesemiconductorcreatessomeholesinthevalence
band.Theadditionofimpuritiesinantypesemiconductorputssomeelectronsinthe
conductionband.(Theadditionofimpuritiesalsochangesthebandstructureslightly,butwe
ignorethisinasimplemodel.)Theholesinthevalencebandoftheptypematerialandthe
electronsintheconductionbandofthentypematerialcanhavenetmovementthroughthe
materialandwecallthemfreecarriers.Thedopedmaterialcanconductcurrent.

pnjunctions
OneofthecrucialkeystosolidstateelectronicsisthenatureofthePNjunction.Whenp
typeandntypematerialsareplacedincontactwitheachother,thejunctionbehavesvery
differentlythaneithertypeofmaterialalone.Specifically,currentwillflowreadilyinone
direction(forwardbiased)butnotintheother(reversebiased),creatingthebasicdiode.
Thisnonreversingbehaviorarisesfromthenatureofthechargetransportprocessinthe
twotypesofmaterials.
Theopencirclesontheleftsideofthejunctionaboverepresent"holes"ordeficienciesof
electronsinthelatticewhichcanactlikepositivechargecarriers.Thesolidcirclesonthe
rightofthejunctionrepresenttheavailableelectronsfromthentypedopant.Whenapn
junctionisformed,someofthefreeelectronsinthenregiondiffuseacrossthejunctionand
combinewithholestoformnegativeions.Insodoingtheyleavebehindpositiveionsatthe
donorimpuritysites.

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Howdoesavoltageaffecttheenergylevels?
Assumeyouestablishedanelectricfieldbetweenthetwosemiconductors.Assumetheyare
notincontactandnocurrentflows.

Ifthefieldpointsfromthentypetotheptypesemiconductor,thenthepotentialishigherin
thentypesemiconductor,andthepotentialenergyoftheelectronsishigherintheptype
semiconductor.(Electronsarenegativelychargedandtheirpotentialenergyhasthe
oppositesignasthepotential.)
Apnjunctionphotodiode
Thesimplemodelpresentedheremixesaquantummechanicalwithaclassicaldescription.
Assumeyoubringantypeandaptypesemiconductorincontactwitheachother.

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Electronsinthentypesemiconductorfillsomeoftheholesintheptypesemiconductor
becausetheseholesareavailablelowerenergystates.Thisleavespositivelychargedcores
inthentypeandextranegativelychargedelectronsintheptypesemiconductormaterial.
Thentypesemiconductorbecomespositivelychargedandtheptypesemiconductor
becomesnegativelycharged.Adepletionlayerfreeofmobileelectronsandholesforms.
Anelectricfieldpointsfromthentypetotheptypesemiconductorinthisdepletionlayer.
Thisisequivalenttoanappliedvoltageasinthepreviousfigure.Theenergybandsinthep
typesemiconductormoveupandtheenergybandsinthentypesemiconductormove
down.Whentheenergyofthestatesintheconductionbandofthentypesemiconductoris
equaltotheenergyofthestatesinthevalencebandoftheptypesemiconductor,lower
lyingenergystatesarenolongeravailablefortheelectronsintheconductionbandofthen
typesemiconductor,andthefillingoftheholesstops.
Exposingthejunctiontolight

Ifaphotonstrikesthepnjunctionandcreatesanfreeelectronholepairinthedepletion
layer,thentheelectronwillbeacceleratedtowardsthentypeandtheholetowardsthep
typeside.Ifmanyphotonscreateelectronholepairs,apicoammeterconnectedacrossthe
junctionwillregistertheflowofasmallcurrent.Thiscurrentcrossesthejunctionfromthen
typetotheptypematerial.
Reversebiasingthejunction,i.e.connectingthepositiveterminalofanexternalpower
supplytothentypesideandthenegativeterminaltotheptypesidewillincreasethesizeof
thedepletionlayer.Theexternalfieldwillpullfreeelectronsinthentypematerialandand
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holesintheptypematerialawayfromthejunction.
Anordinarydiode
Anordinarydiodeisforwardbiased.Connectingthepositiveterminalofanexternalpower
supplytotheptypesideandthenegativeterminaltothentypesidepreventsashiftofthe
energylevelsduetothethebuildupofnegativechargeontheptypesideandpositive
chargeonthentypeside.Theexternalfieldcancelstheinternalfield,erasingthedepletion
layer.Recombinationofelectronsandholescancontinueandacurrentwillflowacrossthe
junctionfromtheptypetothentypematerial.

Duringtherecombinationenergyisreleased.Itcanbereleasedintheformofheat,orinthe
formoflight,asinLED'sandLaserdiodes.
Problem:
AnLEDemitslightwithawavelengthof500nm.TheLEDisconstructedfromapn
junction.Whatisthemagnitudeoftheenergygapofthematerial?
Solution:
Assumethetransitionsarefromthebottomoftheconductionbandtothetopofthe
valenceband.
ThenEgap=hf=hc/.Egap=(4.136*1015eVs)*(3*108m/s)/(500*109m)=2.48eV.
Simulation:Semiconductors

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