photonics colloidal High-performancecrqsslinked quantum-dot diodes light-emitting

Tae-HoKimr,SangJin Leer, EuniooJangz, Won-JaeJoo2, Chol,Eun Kyung Leer, Kyung-Sang Jai Kwon2, Yong Han3,Byung-KiKim2,ByoungLyongChoil* and Jong Min Kimt Soon-Jae
Colloidal quanEmdot light emitting diodes hrue recently received considerable attention due to their ease of colour tunability, high brightress and narrow emission bandwidth. Although there have been rapid advances in luminance, efficiencyand tifetime, device per{onnance is still limited by the large energiybarriers for hole and electrcn iniection irto the guanhrmdot layer. Here, we show that by crossllnldngthe colloidal quantum-dot layer, the charge iniection barrier in a r"a.lieht'"-ltting quanhrrn-dotlight-emitting diode may be considerablyreduced by using a sol-gel Tl0, layer for electron transport The device archltecture is compatible wfth alFsoluton devlce fabricatlon and the resulting devlce shows a high luminance (12,380 cd m-1, low turn-on voltage (1.9 V) and high power efficiency (2.41 lm W-r). lncorporation of the technologyinto a display device with an active matrix drive backplanesuggeststhat the approach has promise for use in easy-to.fabrlcate,large-ateadlsplaysand lllumlnation sources. higtr-pedormance,

light-emitting with the HTL and substantially improving charge injection. ince the first rePo4on colloidalquantum-dot (QD-LEDIs) 1994, variousapproaches beenfol- Additionally, thermal annealing of the crosslinkedQD layer further have in diodes devices, including improvesdeviceluminance and luminous efficiencydue to a decrease of lowed improve performance these to the
the design of novel device structures, the development of novel QD and transport materials,and the optimization of carrier injectionr-r2. Compared to early structures, which had thick QD layers that actedboth as emissiveand electron transport layers (ETL)r'3'a, the luminous efficiency of QD-LEDs has been vastly improved by that minimize electrithe use of ordered anays of QD monolayers5 and enable efficient confinement of excitons. As a cal resistance result, deviceswith QD monolayers demonstrate record Ievels of luminance(2,000cd.-:1 and luminous efficienry(l.9cdA-r). Recentwork by other groups has shown that even better QD-LED performance (a maximum luminance of 9,034 cd m-2 and luminous efficiency of 2.8 cd A-r) could be achieved by optimizing the thicknessof the QD layer and QD purificationrr. Much effort has been made to replace the organic charge transport Iayers of QD-LEDs with inorganic ones to overcome the persistent drawback of organic materials, in particular their thermal instability Recently,a coland moistue/orygerr-induceddegradatione'r0'r2. loidal QD-LED with inorganic charge transport layersl2consisting of a NiO hole transport layer (HTL) and a doped ZnO ETL maximum luminance of 1,950cd m-r comshowed a reasonable pared to all-organic-based QD-LEDs, but the luminous effrciency was still low (0.064cdA-'). Further development of colloidal QD-LEDs featuring inorganic layers could potentially allow for the realizationof encapsulation-free QD-LEDs with long lifetimes. Although the perfbrmanceof colloidal QD-LEDs has improved dramatically in recent years, control over carrier injection, electronhole recombination and carrier balance still requires improvement before commercialization. Commonly used n-u colloidal QDs have intrinsically high valence levels (>6.5 eV); this createsa large potential barrier betweenthe QD valencelevel and that for the typical transparent anode, ITO (4,5-5.I eV). This is perhaps the major factor limiting QD-LED per{ormance. Here, we show that croslinking the QD layer can shift its valenceband, thus reducing the band offset in through the removal of orgpnic residues in the contact resistance the QD layer. We investigatedthese treatmentsand their effect on deviceperformanceusing a combination of ulraviolet photoelectron specboscopy (UPS), photoluminescence (PL), thermogravimetric (EL) characteristics. analysis(TGA) and electroluminescence

Resultsand discussion of Structural design of the QD-LED. A schematic the device electronmicroscopy transmission structurand cross-sectional (TEM) imageof the QD-LED and corresponding energyband of diagramare shownin Fig. l. The deviceconsists a patterned ITO anode, a 50-nm poly(ethylenedioxythiophene):polystyrene
(PEDOT:PSS) hole injection layer (HIL), e-2q-n!L

-2,7:_4jy-!Iss:L4l-:(ALg_la.Lurybtre-ayl,))

a 30-nm QD layer as emissive layer,a 40-nm TiO, layer as the ETL and a 150-nm aluminium layer as the cathode. Higttly luminescent, red-lighremitting(PL: 615 nm) CdSe/CdS/ZnS QDs (ttpr > 70%) were prepared according to a previously reported methodra.Our QD-LED structure was designed to achieve efficient electron and hole injection from the electrodes to the QDs. W:4q113ggdJ, effectively block electrons and_lrolesthgt passthrg_ughthe;QD layer in considerationof the electronic band structure of the constituent for layers (Fig. lb). A small injection barrier of 0.4 eV ercists the injection of electrons from aluminium to the QD layer becausethe Fig. Sl) and the TiO, conduction band (3.9 eV; see Supplementary work fi.urctions of aluminium are similar. The small step alignment of the highest occupiedmolecular orbital (HOMO) energylwels of PEDOT and TFB allows for facile injection of holes from the ITO to betweenthe the QD layer, even though a relatively high barrier eicists TFB and the QDs. Meanwhile the high lowestuncrculied molecr'lar Ti0,can orbital :ffectivelyblock injeaed elqrJls_eqd-bols ana confine them --___..-

'Frontier Lab, Research 446'712,South Korea,'Materials Electronics, Gyeonggi-Do Samsung Research Lab,liamsungAdvancedInstituteof Technology, rDisplayLab,Samsung of AdvancedInstitute 446-712, South Korea. Electronics, Gyeonggi-Do Instituteof Technology, Samsung Advanced Samsung *e'mail: choibl@samsung com Gyeonggi-Do446'712,SouthKorea. Samsung Electronics, Technology, PUBLICATION ONLINE NATURE PHOTONICS lw.nature.com./nalurephotonic I AD'VANCE 1

2.0 3.0 4.0 5.0

8.0 (left) and cross-sectionai rEM image(right) of the QD-LEDTFB, FigureI I shur:tureand energylenelsof the eD-LED.a, Devicestructure 'l0o enerSvband with associated structure nm, b, Schematic Scalebar, poly[(g,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl))diphenylamine)J. measurements from UPSand opticalabsorption levetwas estimatedfrom ref.13.The QD and Tio, energybandswere determined The TFBene4Jy diagram. (see Supplementary Sl,S2). Figs

within the QD layer, enhancing the probability of carrier The r;ol-gelTiO, layer wasdepositedby spin-coating, recombination. enablingour QD-LtiD to be fabricatedby means of an all-solution processwith the o<cr:ptionof the aluminium electrode layer. Because ihe TiO, laler was annealed at low temPeratue (<150'C)' it it neither in a crystalline phase nor fi.rlly inorganic. Nevertheless,this layer has good semiconductingbehavior,with a-bandgapof 3'9 eV' Such behiviour has been documented previously in polymer solar cells, the sol-gel TiCr, layer showing a relatirly high carrier mobility are of 1.7x lO-a cm2V-r s-r (ref. l5). Although its characteristics the not well understood, TiOr layer, fabricatedin a low-temperature sol-gel process,is r.lseftrlfor various electronic devices,especially plastlc ones. As a result of the low-temPeratureprocessused for 1iO2 deposition, the QD-LED can also be realiz:d without any of degtadation the organiclayers. Carrier transPort in the QD-LED. Figure2 showsa comparisonof properties the QD-LED with a TiO, ETL and thoseof a of the electrical dsrice witltout a QD layerand with a QD-LED with an Alq, reference device,the slope of the cwrent density-voltage ETL. In the reference (/-V) curve showed traP-limited behaviour (,loc V, n) 2) over a relatively small voltage range, which changed to space-charge limited conduction (,fc< V2) as the oPeratingvoltagewas increased' The TiOr-based QD-LED, however' demonstrated trap-limited conduction that lastedlong beyond the hrn-on voltagewith much lower currerrt densiity, suggating that the QDs act as traP sitesr6. Comparedto the organic-based QD-LED using Alq, asthe ETI- the TiOr-basedQD-LED givestwo orders of magnitude larger current denJityover the enlire voltage range, and shows a similar tendency for the longJasting traP-limited conduction region in the /-V From the enlargedcurrent density,we concludedthat chancteristics. electron injection into and transPort through TiOt is superior to when that for Alq, in our devicestructure;this becomesself-evident considering-thelower band offset (0'4 eV) Sr Al/TiO*t-994!af-d to that for Al/Alq' (l.2ev) and the higher electron mobility (1.7 x 10:? cm2V=t=t) of the sol=gelTiO, comparedto that for For the samereason, Alo, (-1.0 x lO-scm2V-r s-r) (refs 15,12)' -the"t,rn-or, voltagein the TiOr-base?-QD-LEDalso significantly decreasedl'o 1.9\r, which is smaller than the QD barr-{gap-of 2.1 eV and much lower than that observed for the Alqr-based device(-4.9 V). The onset of EL occurs after the minority carriers have been injectecl into the emitting layer. To determine which carriers are dominant in the QD-LED, we adjusted the hole conductivity of the HIL by blending PEDOT polymers with differing armounts of PSS. In Fig. 3a, it can be observed that *HIL conductivity increasesfrom 3.6 x 10-a S cm-t to as the 7.1 x l0-2 S cm-r, the maximum luminance and luminous

ro'I

r=v?-'
', "n

102

rnl

t=vl! E < lao

c

/=\
I urn-On

10-r
t-\/13-.

'r0-:

z,ITurn-on

l0-3

0.1

1 (V) Voltage

10

Figwe 2 | Current density versus vohage characteristicsof the QD'LED' of QD-LEDas shownin Fig l (blacksolid J-Vcharacterrstics a TiOr-based l a l i n e ) , Q D - L E Dw i t h A l q , a s t h e E T L( b l u eb r o k e ni n e ) , n da r e f e r e n c e ' a liOr-based QD'LEDwithout the QD layer(red brokenline) Threedifferent device(ohmic, regimesare apparentin the reference conduction t ), t on an t r a p - l i m i t e d , d s p a c e - c h a r g e - l i m ice d d u c t i o n w h e r e a sh e o t h e r (for the QD-LED)or no change show partial(for the TiOr-based devices due to conduction from trap- to space-charge-limited Alqr-based QD-LED) QD-LEDis The deviceturn-on voltageol the Alqt-based largetrap densities. ( ( l a r g e r 4 . 0 V ) t h a nt h e T i O r - b a s e d D - L E D 1 . 9V ) . Q efficiency graduaily increases and the ,l-V characteristics remain

that our QD-LED the approximaiely same(Fig. 3b). This indicates -an ij electron-dominant device and that increasingthe hole concentntion within the QD layer improves charge balance At a conductivityof 7.1 x 10-2 S cm-r (sampleC), the PEDOT:PSS shows maximum luminance and luminous efficiency QD-LED Beyond valuesof 12,380cdm-2 and l.67cdA-t' respectively. 7.1 x l0-2 S cm-r, further increases in the PEDOT:PSS conductivity did not result in increasedluminance and luminous 'ih" hol. concentration is believedto be limited by the efficiency. properties of TFB at such high HIL conductivities' hole transport AU QD-LLD diviles in this study, unless otherwise mentioned, used unmixed HIL (Bay'tron AI4083) for convenience of fabrication(conductivity$pically -1 x l0-3 S cm-r)' position Crosslinking of the QD layer. In QD-LEDs,the energyband of the QD is located-1 eV belowthat for typicalorganiclight-emitting the largeband offsetbenveen HTL a This produces relatively materials.
nature comlnaturephotonrcs

ONLINEPUBLICATION l \W PHOTONICS ADVANCE NATURE I

for these QD fiIms are presented in detail in Table l' The ionization potential (valence band level) of the as-coated QD flIm (fi) was o S""el. A o ^O.SS [oI. t- o s"tPtt B V b.lo* the vacuum level, which correlates well with other 5 I E = e I a s a m p lc reported values2o(see Supplementary Fig. S2). A remarkableshift of ! samPteD -b.o.v in the QD band level towards the vacuum level eras r4,000 L t - o 3 "alencl / observed for ciosslinked filrns (O-fa). This energy shift is 6 c - r2,000 sigrrificantly larger than a prwiously rePortd ryuf for InAs QDs U. c o it reasonable (0i eV) 1ief. ia). The magnitude of our- tq E 6 ionsidering the differences in the QD materials and the adsorption 10,000 E ; 0.8 conditionJof the anchors on the QD surfaces.Becausecrosslinking G was carried out on a QD flm for our case, the ctosslilkers are 8,000 orpected to be asTmmetrically adsorbed onto the QD surfaces;for a be distributed 6,000 Qb solution, the cross-linkers would be ecpected to 'tE-4 0.1 0.01 1E-3 We observed that the maximum peak in the EL more uniformlv. (S conductivity cm-t) PEDOT spectra was not influenced by the crosslinking process -(see that the Fig. S3), suggesting Supplementary -up*ards -simultaneously conductionband of the with the valence band' qO'hyer shifu lVtt.tttlt QD flm: are crosslinkd or not, subsequent thermal E annealinghas little effect on the energy band levels-(O-6)' 800 ; figur! I shows the EL characteristicsof QD-LEDs fabricated with E difierint crosslinking and thermal annealing conditions' An as600 ; further treatment was not omined coated QD layer ithout o becauseii *"t p"ttiutty damaged during spin-coating of the soi-gel 6 400 TiO, upper layer. From the data, it is apparent that crosslinking thegreatly improves the luminance and luminous efficiency of aDi+; waspre2oo samplesl:3 (Fib. 4b and c). ln samplel, the QD-LED device p.t a by only irosslinking the QD layer after spin-coating withgul In sariples 2 and 3, QD films-were crosslinlced ilt.t a'"*."tittg. 0 2 4 6 8 1 0 "C and annealedat 810 (sample2) or 180"C (sample3), respectively' (V) Voltage for 30 min under nitrogen. in samplea, the QD layer was annealed at 180"C for 30min without crosslinking' According to the UPS FigFe3|PerforrnancearrdJ.VcharacteristicsforQD.LEDswithdifferent raults, the energy band offset betweenthe QDs and the HTL was and luminous a, conductiviths. Maximum luminance leadsto PEDOTPSS reducedfrom t.i to 0.9 eV for our devicesand consequently conductivity' as ol etlicrencies QD-LEDs a functionof PEDOT:PSS an increaseby over a factor of l0 in the maximum luminous efficiency b,/-Vcharacteristicsfc,rQD-LEDswithditferentPEDOT:PSSconductivities' of (samples and 4) because more efficienthole injectionand enhanced 3 with PEDOT:PSS gradually increased efliciency and The luminance luminous ih.tg. btl.tt... Even though the thermal treatment did not changethe were up improved conductivity to O.Oi'Scm-r, whereasthe ./-Vcharacteristics of enerfy band leuels the dO layer(Table t ), it considerably that the majoritycarrierof the device the approximately same;this suSSests the itiminance and luminous efficiencies(samplesl-3)' Therefore' and luminous 0.07 5 cm-r, the luminance Beyond is the electron, thermal annealing temperature is an additional key parameterinlluene f f i c i e n c i e s n o l o n g e r i n c r e a s e d u e t o h o l e c o n c e n t r a t i o n r e s t r i c t i o n s c a u s e ddevicepe.fo-r-ance. In Fig. 4a, the current density was.mainly cing (12,380cd m-2)' the C by TFB.Sample shorved highestluminance croslinking' eo;rn.d by the annealing teilperature and not-the and 20%of organicsurfactants crosby tnis is exptained the facithat Iinkers *ithin the QO layer are removed during thermal annealing at vo$S9s9$ leads high whichnecessitates operating andtheQD layer, high barrier 180"C for 30 min according to TGA analpis (see Supplementarv As to low powelifficiencies. shownin Fig. lb, a relatively removing a portion of the electrically insulating organi-c the Uetween TFLand the QD layeralsoecistsin our QD-LED' To Fig. 9). By at the QD-HTL we the HTL and QD la1rcr, have tJido"t surrounding-the QDs, the contact resistance reducethe b6?-ofta be-tween a and QD-ETL interfices is effectively decreased'In addition' thermal using band of the QD layerupwards to attempted shift the valence become *eai-i"g provides tight contact between the QDs and HTL which methocl During crosslinkinglinker molecules crosslinking or improves'hole injection and charge balance.The temperaturedepensurfactants with pre-existing to-th. Qp tluougho(change attached wasinvestigated Accordingto Soreni- denceof the maximum luminancJand currentdensity by brrding to emPtysiteson the QD surface. (Fig.ad). The currentdensityand crosslinked QD-LED can fi.oti -a colleagua,adsorptionof organic molecules cause in detailfor the 210 surface maximum luminance gndually increasedwith temPeratue uPto throughthe formationof mrcroscopic lwelsto realign energy in "C, as enpected.neyond 210;C, the maximum luminance for the the change, Specificaff, dipoii at the QD-JurfactantinterfacerE. current density T$ treld increased in lwel is prirnarity determinedby the binding funaionality QD-LED; decreases spite of en'ergy A is caused by degradation of the QDs, which is corroborated by the and the QD surface' Uet"Ln the an&or groupof the crosslinker -been beyond210'Cii for observed anchor rapid decrease PL intensity for QD fiIms --:4d ercPerimentally Iarqer energyshift has A distinctive featureof our crosslinkedQD-LEDs is the sigrrficantly For dectronegativitiesrt. this reason'the amine siups tnitti-tri$rer and in our low turn-on voltage, which improves Power efficiency' At-a video as Lou'p i, a good-candidat. the anchorof the crosslinker device is with l'7-diaminoheptane brightness of 500;d m-2, the operating t"-lgg:-9f the &p.ii..nittt. QD layer was crosslinked on the f.S-V, which is much lower than that for QD-LEDs with organic by follotned thermal.ti"*ti"g. The effectsof-the crosslinker (-10.5V) (ref. ll). Becauseof the low operating voltage' burd of the QD layer were studied using UPS analpis' ETLs valence at the maximum power efficiency is as high as.2'4llmW-r with different -t.gS We pregaredfive QD films on silicon substrates lm W-r at 1,000cd m-2' In addition,the lumi100cd m-2 ana without any -p9l!.t!Fm9ll an QD film manipulatic'ns: as-coated value of 2'53cdA-' at 4V and (2), (fl), ; aD flm that wascrosslinked a crosslinladfrlm annealbd nous efficiency has a maxirnum range of and a QD film ,.rnul* greater than 2 cd A-t over a wide luminance .t bo oi 180 for 30 min (B and f4, respectively), "C in Fig. 5. The lifetime of the QD-LED is (f5)' The UPSresults 30-4,000;d m-2, as shown 180'C for 30 min without crosslink
'18.000 2.O

at annealed

PUBL|cAT|oN IM.nature.com,/natUrephotoniG oNL|NE PHoToN|cs,qDVANcE NATURE |

Tabhl I lontsdon.pdentfd
QD ftlm

rcsufts fo" QD filrns from He ll ultraniolet photodectron sPectroscopy.

cutoff, Secondary
*4.6 (eV)

Vahnce band edge, E"*oo (eV)

lonization potential* (eV)

Conesponding dskes in Fig 4

1 Sample 2 Sample 3 Sample 4 Sample

(fl) As-coated (f2) Crosslinked at 80 Crosslinked,/annealed "C (f3) at 180'C Crosslinked./annealed (14) at Annealed l80 "C (f5)
'lmizdril pdelni., - 4O.Bl cV - (6'*6 - 8".*).

36.59 35.77 35.90

5f,.)f

2.63
1.21 1.33 0.96 2.70

36.67

6.85 6.25 6.23 6.23 6.84

a t.zoo
E E
o 6 {VV

E 800
o 6
c J

16,000

(
E

:tr r4,ooo '-.-.-.__--.=--:*a

J 1?nnn

1.200 .1.2 l .\t z 1,000: l-10 i

N

800 : ;08 5. J !
a_---a.--

u.l

E = 10.000 E

.*Q,

t\ \,. r,
a l

Ann ! LnA I < i g 400 I i0a i

. ^ ^

! a,ooo E 6 o.ooo
al'

.a

\ . \ \ . \
l5O 180 210 24O 27O (oC) Annealing temPerature

::'
=

lWW

;
=

tsW-a w
^ .

0.001

4 6 8 (V) Voltage

4,000 80 Noanneal

Lo.o

characteristics efiiciency-voltage and luminance-voltage luminous performance elLEth. a-c,currentdensity-voltage, of Fgue 4 | Eestrolunrinescence (samnle crosslinked annealed 80 or 180"C' at and l), after crosslinked spin-coatins the with eD lor theeD-LEDs different manipulations: QD layer and luminance (sample d, Maximum 4). crosslinking io|' (samples and 2 3),andannealeJJilEi-oc 30 minwithout nitrogen for respectively,30 minunder the after pLintensity QDfilmsas a tunction annealing temperature crosslinking QD layer of for (g and bias v) Jorthe QD-tEDs the at density fixed current

r r S U g

'\l

\,
F
i

9
E

f' i
I

.-'i-r
? J

t00

lo2

103

104

Luminance(cd m-2)

of as efficiency a {unction quantum and efficiency power external efficiency, a, imageof QD-LEDs, Luminous and Fi$re 5 I Efficiency elecboluminescerre driveTheupper matrix arny lor theactive with TFT an using a-Si backplane a 320 x 240 pixel 4-inch crosslinked QD-LED image a of b, luminance.Display pixel. bar' scale 100pm' each rightinset shows at under operation 500 cdm-2 andthe lower from of is inset animage lightemission all pixels right
ONLINEPUBLIcATIoN lM.nature.comlnaturephotonrcs PHOTONICS ADVANCE NATURE I

50.5h at the initial luminance of 1,000cd m-2 (see Supplementary Fig. S5). We harrc also constructed a display dwice using the crossf"t ea Qp-l,lO using an a-Si thin-fiIm transistor (TFT) backPlane as an activernatrix &ive (Fig. 5b). The device has uniform brightnes with lessthan 5% variation over a 4-inch display area. In conclusion,this work demonstratesthat a high-perfonnance colloidal QD-LED can be achievedusing specific crosslinking and thermal annealingof the QD layer and the useof a sol-gel processed TiO, electrorrtransport layer. Controlling the energy levelsof the QD layer through surface manipulation provides a useful way to solve the problem of large potential barriers between the valence level of comrnonly used colloidal QDs and the ITO work function; this provides more flexibility when developing the device structure and materials.These results bring us one step closer to developing colloidal QD-LEDs suitable for application in high-performance' Iarge-areacommercial devices such as flat panel easy-to-fabricate, displaysand illumination sources.

of from H. 4. Mattoussi, at al. Electroluminescence heterostructures Ipo$phenylenevinylene)and inorganicCdSenanocrysrds. Appl.Phyl8!' 7965-7974 0998\. fiom M. 5. Coe,S.,Woo, W.-K., Bawendi, & Bulovii, V. Electroluminescence Nature420, organicdevices. in of singlemonolayers nanocrystals molecular (2002). 800-803 nar-iniiared N., 6. Tessler, Medvedw,V., Kaze, M, Kan,S.& Banin,U. Efficient (2002)' 295' 1506-1508 light-emittingdiodes Science polymernanocrystal 7. Chaudhary, Ozkan,M. & Chan,W C' w. TrilayerhybridPolymer-quntm S., (2004). Appl. Phls.Lett. a4,2925-2927 dot light-eminingdiodes. V' M. S., 8. Coe-Sullivan, Steckel, S.,Woo, W.-K., Bawendi, G. & Bttlovi' I. during via orderedquantum-dotmonolayers phaseseparation Large-area Mater.15, lllT-1124 (2005). Adv. Funct. spir-casting. M. 9. Caruge, J.-M.,HalPen,J. E.,Bulovid,V. & Bawendi, G. NiO asan inorganic N4no Lelt 6' layerin quantumdot light-emittingdevices. hole-iransporting (2W3). 2991-2994 on 10.Mueller,A. H. et al.Multicolor light-emittingdiodesbascd semiconductor NanoLett. 5, in nanocrystals encapsulated GaN chargeinjectionlayers. (2005). 1039-r044 on diods based quantumdots. light-emitting I L Su, Q. et al. Bright,mu.lticolored (2007). 1,717-722 Photon. Nature M. 12.Caruge, M., HalPert,l. E.,wmd, V., Bulovit, V. & Bawendi, G Colloidal l. tlansPorllayers' charge Methods quantw-dot light-emittingdiode with metal-oxide nO thss ms fu* demed NaturePhoton.2, 247-250 (2008). QD-LED fabrication atrd chuacterization' A Patterned (BaltmnP VP reated.A HIL PEDOT:PSS rarious olwnts andthenUV-ozone M., using D. M., 13.Rcdecker, Bradley, D. C., lnbasekaran, Wu, W. W. & Woo' E. P 'C at ITO glasr and the fiIm thenbaked 200 Adv. was copolymers. Mater' ll, AI,1083) spinroatedonto thepatterned fluorene-triarylamine holetnrnsPort High mobi.lity for 5 min in a nitrogenglovebox after baking at t l0 "C for 5 min ia air. TFB 24r-246 (t999). (H.w. Sands as and nanocrystals their Corp.) HTLwasspi 14,Lim, l. et al. Prepantionof highly luminescent bor QDs (2007). layer Adv. Mater' 19,1927-1932 to application light-emittingdiodes. at cells polymerphotovoltaic ) wer for 15.Kim, I. Y. et al. New architecture high effrciency andcr Adv. Mater' lE, rpm for 30s, 2,000 titanium oxide asan opticalspacer' usingsolution-based a c9!di!p$.For QD mslinkin& 572-576(2006). qasheatedto 60 "C. QD film wrerhen dipped into the mechanism 16.Hikmet,R. A. M., Talapin,D. V. & Weller,H Studyof conduction and quantumdot composites. Appl Phys' md subequenthsalad in puremethmol for 5 min. After rinsingwith iraglqPeqa! l. in and electroluminercence CdSe/ZnS the 2 dryingwith a nitrcgenstream, 6lmswereannaled at 180"C for 30 min in a nitrogen 9 3 ,3 5 0 9 - 3 5 1(4 0 0 3 ) . (DuPonttyzol BTP)wa9dilq!ed.!o. !'t% t4b[anol 5 17.Kepler,R. G. et al. Electronand hole mobility in tris(8-hydroryquinolinolato$we lor A TiO, sol-gelprecurcr rPm tbr 30s andthen al was (1995). the Lett.66, 36I8-3620 ior spin-coating ETL.Spin-coating performed 2,000 NI,O8) aluminum.Appl.Phys' We conditions. deposited 18.Soreni-Harari, et al. Tunning energylevelin nanocrystal qu.ntum dots at anncaled 100'C for 30 min underambient subsquently M. NanoLett.8' 678-684(2008). aluminiumon top ofthe DTL usinga thermalevapontor.Finally,devica wereshielded manipulations. throughsurface V in M. with cnap$lationglass a nitrogenglovebor S., l. 19.Coe-sullivan Woo,W.-K.,Steckel, S.,Bawendi, & Bulovic, Tuningthe (l-V) (/-V), and luminance-voltate dwices' quantumdot light-emitting curcnt density-voltage EL spectra, performance hybrid organic/inorganic of coupledwith (2003). rvererecordcdusing a Topcon SR3sPectroradiometer charactcristics 123-130 Org.Electron.4, were an AdvantacR6243DCroltage and current source.All measulcments performedunder ambient conditions.The lifetimes of the QD-LEDs weretestedat Acknowledgements di*usion' S lu and room ternpcmturcuing a Mc&iencc Polarcnix Lifetime Tcst System. The authon thank l. Lrc, J.M. ke, l. Chmg and t. Songfor helpfi.rl

2'l 2008;accepted April2009; 5 ReceivedNovember published 24 online MaY2009 References

A. M. t. Crlvin, V. L, Schlanrp, C. & Alivisatos, P. Light-emittingdiodesmade polymer.Nature and nanocrystals a semiconduaing from cadmiumselenide (te94). 370,3s4-357 M. B. 2. Dabbousi, O., Barvendi, G., Onitsuka'O. & Rubner'M. F. AppLPhp. composites. quantum-dot/polymer from Etearolumrnescence CdSe (1995). Lett.66, l316-1318 in X Nt. 3. Schlamp, C., Peng, & AlMsatos,A. P. lmprcvedefficiencies light and core/shellt)'Penanocr)atals a eminingdiodesmadewith CdS(CdS) -5842(19971. 82' po\mer. /. Appl. Phys. 5837 semiconducting

H. lang for prcviding quantm dots and l. !V. Kim, Y. T. Chm, t.-Y. Kwon and Y G Leefor fabricatingthe QD-LED devicewith the a-Si TFT backplme.

Authorcontributions
E.K.L.,w.-J.1.and B.LC. canied out the exPrimentand contributedto the writing K.-S.C., 'K.K' the of the paper. E.l. slrnthesized quantm dots. T -H.K., S.l.L' S.-,.K.,I Y.H' and B asisted with the qPriment and the deviceanalysis.,.M.K. conlributed to the Mitint of the paper and the proiect Plannint.

information Additional
this PaPerat M.natun.com/naturePhotonics' information accompanies Supplementary com/ is md Rcprints pmi$ion infotmation anilablconlincat http://npg.natw shouldbe for and rcprintsndpcmissions/. Correspondencc rcqucsts matcrials addrescd B.L.C. to

r ),)y

PUBLICATION ONLINE PHOfONCSADVANCE NATURE IM I

nature com,/nalurcphotonacs

3.9ev
E, = 4.56 eV

$=3.9eV

7.8 eV (a)
.t E (t o
t

lw =21.22eY

!i o t c o

c o e o o E
6

3.9oV

3.24 cV

o o c ul 1.5

20

1 5 1 0 5 BlndlngerErgy (eV) (b)

2,5 3.0 3.5 Energy(eV) (c)

4.5

Figure S1. Measurement of the enerry band of a TiO2 sol-gelfilm. a, Energyband diagramof a TiO2 film determined for for b, from UPS and UV-Vis absorptionmeasurements. UPS spectrum the TiO2 film. c, UV-Vis absorptionspectrum leveland3.24 is bandmaximum 7.8eV (= 21.22- (16.66- 3.24))belowthevacuum film. FromUPS,thevalence theTiO2 well with the work function on eV belowthe Fermilevel. The calculatedFermi-levelbased the UPSdata(4.56 eV) agrees of (4.55eV) measured previouslyby the Kelvin probemethod.Basedon the valenceband maximum and the bandgap the to the by TiO2 filn (3.9 eV) determined UV-Vis absorption, conductionband minimum of TiO2 was calculated be 3.9 eV belowthe vacuumlevel.

PHOTOI{tCS NATURE I m.nature.com,/naturephotonics

1.2 1.0 3

0.8

tri 0,6 ; c

3 0.4 o
0.2

10 35 34 33 Binding energy (eV)

(a)

= 6i
1ua

10

c = o

(b)

and thermallyor chemically on Figure52.He II UPSspectrafor variousQD fihnsspin-coated a Si substrate bandandsecondary of listedin Table1. a, UPSspectra QD films in thevalence to treatedaccording the procedures for band edge (dotted for Thevalues thevalence circle). region graph band edge ofthe valence b, cutoffregion. Expanded
each frlm are indicated with arrows.

PHOTONICS NATURE I www.nature.com,/naturephotonics

5
I

G .=

.g
J

o c o H

Irl

(nm) Wavelength
Figure 53. E1 spectra for QD-LEIh with normalized peak intensities at the maximum luminescent voltage,The The EL peak to of the insetshows CIE coordinates theemittedlight.The dottedline corresponds the NTSC color triangle' and peakswereobserved the EL peakpositiondid not position 6lg nm with FWHM = 35 nm. only the QD emission is the after cross-linkingand thermalannealing QD layer' change

PHOTONICS ilww.nature.com,haturephotonics NATURE I

s
( E =

ctt o

400

600

800

("C) Temperature
Cross-linked QDs' c' Figure S4. TGA for QD films. a, As-coatedQDs without crossJinkingor thermalannealing'b, 'C for 30 min. Weight lossoccurringat I < 500 oC is attributedto organiccomponents at Cross-linked eDs annealed 180 of components QD films.At Z< 500'C, a weight to of eD films while weightlossat 7> 500 "C is attributed theinorganic for of observedfor the non-annealed film while a weight decrease only l6.27Vowasobserved QD of decrease ?.g.O1Vowas of that indicates -l9vo (=3.8/20.07) them(3.87o) berween at g0 oc for 30 min (line c). The difference eD films annealed I 'C for 30 min after crosslinking of wereremovedduring thethermalannealat I 80 (surfactants cross-linkers) and organics the QD tilm.

NATURE PHOTONICS I M.nature com,/naturephotonics

1,000
(,{

E 8(x)
o 600 o c
G

!t () ---:-r - 50.5 hr \n- "

c
= J

E
2U) 0{0.01 100

0.1

10

(h) Time

is the of for Figure55. Lifetimecharacteristics QD-LED.At theinitialluminance I,000cd m'2, half-lifetime 50'5h (42 operation mA cm'') at roomtemPerature. current constant under

NATUREPHOTONICS m.nature.comlnaturephotonics I