Lumlnescent Materla|s For Phosphor~Converted LEDs
Tbonas ju¨ste|
Inorganlc Llght-Emlttlng Dlodes (LEDsj
Tho hist piactical inoiganic soniconductoi LEDs woio concoivod at Toxas Instiu-
nonts in 1961 ly Baiid and Pitnan. Thoso dovicos onittod in tho noai inliaiod
locauso tho natoiial usod was InGaP with a land gap ol 1.37 oV. Ono yoai latoi, tho
hist LEDintho visillo was luilt ly Holonyak ot al. Thoy usod a dilloiont conposition,
viz. GaAsP, to laliicato a dovico onitting iod light. Fionthat tino on, tho uso ol noio
iohnod piocossing and othoi natoiials (o.g., AlGaAs¡ lod to tho dovolopnont ol tho
connon LED, nainly usod in indicatoi lights.
Foi sovoial docados, LEDs woio not attiactivo loi illunination puiposos, nainly loi
two ioasons. Fiistly, tho optical output powoi (i.o. tho lunon packago, dohning tho
anount ol light onittod liona singlo LED¡ was laiily linitod, sinco tho packaging and
tho natoiials in uso did not allow high cuiiont donsitios in tho snall chips. Sinco tho
olhcioncy was lai loss than 100 %, a gioat doal ol hoat would havo loon gonoiatod,
dostioying tho soniconductoi chip. Socondly and noio inpoitantly, no olhciont lluo-
onitting soniconductoi natoiial was availallo. Foi sovoial yoais soniconductois
containing gioup II and gioup VI olononts, o.g., ZnSSo]ZnTo woio iosoaichod as
possillo candidatos loi lluo LEDs with linitod succoss. Howovoi, in 1993 Nakanuia
ot al. achiovodtho lioakthioughloi solid-stato lightingly pioving tho succosslul uso ol
InGaN as a natoiial in LEDs j1|. Sinco tho natoiial is chonically voiy stallo, it is
dilhcult to achiovo high-quality opitaxial layois loi high-olhcioncy LED opoiation, lut,
on tho othoi hand, tho high stalility allows voiy high cuiiont donsitios without
disintogiation ol tho LED natoiial. Thoioloio tho lunon packago can lo incioasod to
valuos iolovant loi lighting applications (Fig. 7.1¡. Moio inpoitant, howovoi, is tho
insonsitivity ol InGaNto dolocts. Althoughtho doloct donsity inconnonInGaNLEDs
is nuch highoi than would lo accoptallo inothoi natoiial conlinations, o.g., AlGaAs
(10 cn vs. 10 cn ¡, tho low suilaco ioconlination volocity ol InGaN allows
olhciont LEDs tolo luilt liondoloct-iich layois. Additionally, withtho advont ol liight
and stallo lluo and UV LEDs it locano possillo to gonoiato whito light lion solid-
stato dovicos, oithoi ly coloi convoisionol lluo LEDs using phosphois oi ly oxtoinally
nixing tho light lion lluo, gioon, and iod LEDs.
Lunincsccncc. Frcn 1nccry tc App|icuticns. Editod ly Coos Ronda
Copyiight 2008 WILEY-VCH Voilag GnlH & Co. KGaA, Woinhoin
ISBN: 978-3-527-31402-7
Tho piinciplo ol LEDs is oxplainod in nuch dotail in soniconductoi dovico
litoiatuio j13|. Hoio tho uso ol LEDs loi whito light gonoiation and tho iospoctivo
iolovant aspocts concoining luninoscont natoiials will lo discussod. Bocauso ol
tho inpoitanco ol coloi convoision in gonoiating whito light lion LEDs, tho natuio
ol tho phosphois usod is discussod in noio dotail.
whlte and Co|ored LEDs
Whito light is, gonoially spoaking, always a nixtuio ol sovoial puio colois. Tho
sinplost way to achiovo a light souico with a whito appoaianco is to conlino lluo with
yollow]oiango piinaiy light souicos (Fig. 7.2¡. Howovoi, only a voiy low coloi-
iondoiing indox (CRI¡ is oltainod, i.o. nany colois aio pooily iopioducod undoi
illunination ly such a light souico. Incioasing tho nunloi ol piinaiy colois ly
conlining, o.g., a iod, a gioon, and a lluo (RGB¡ LED innodiatoly onallos nuch
highoi CRI valuos to lo achiovod and honco a high-quality whito light souico. In tho
linit ol using nany dilloiont visillo LEDs, tho llack-lody iadiation spoctiun ol
5500 K (ossontially tho visillo spoctiun ol sunlight¡ is gonoiatod, which has, ly
dohnition, a CRI ol 100. Howovoi, locauso ol tho hnito sizo ol tho LED dios and thoii
packago, it is iathoi dilhcult to achiovo honogonoous nixing ol tho discioto LEDs, at
loast in a snall packago.
Tho najoi application ol coloiod LEDs as light souicos is thus not in tho aioa ol
gonoial lighting, lut in aioas whoio puio colois, o.g., as dopictod ly tho spoctia in
Fig. 7.3, havo to lo iopioducod, as in tialhc signals and autonotivo liako oi indicatoi
lights. In thoso application aioas, InGaN and AlGaInP LEDs havo laigoly ioplacod
hltoiod whito incandoscont light lulls locauso ol thoii highoi olhcioncy and longoi
Two najoi natoiials aio usod in coloiod LEDs: AlGaInP loi iod, oiango, and
yollow and InGaN loi gioon and lluo. Tho quatoinaiy nixtuio ol AlGaInP is tho
piino candidato loi a iod to yollow onission coloi. It is typically giown on GaAs
walois, sinco tho lattico natching ol sulstiato and opilayoi guaiantoos a snall
nunloi ol dolocts, ossontial loi high olhcioncy and long lilotino. Altoi doposition
Flg. 7.1 Classical 5-nn LFDs {leFt) and a high-power-illunination LFD
180 7 |un|nescent Mater|a|s jor PbospborConeerted |EDs
ol tho vaiious layois, tho waloi is londod to a GaP sulstiato, and tho oiiginal GaAs
sulstiato, which alsoils in tho spoctial iogion ol tho LED onission, is ionovod.
This incioasos tho olhcioncy, sinco, il tho sulstiato was alsoiling, hall ol tho light
would lo lost, i.o. all tho light onittod towaid tho sulstiato. Still, a lot ol light is
tiappod insido tho dio ly total intoinal ioßoction. Sinco tho ioliactivo indox ol tho
natoiial is gioatoi than ono, all light onittod at an anglo gioatoi than tho Biowstoi
anglo is ioßoctod lack into tho ciystal. Bocauso ol sono iosidual alsoiption, o.g., at
tho notal contacts oi tho chaigo tianspoiting layois, nultiplo intoinal ioßoctions
still dininish tho olhcioncy. By shaping tho soniconductoi chip in loin ol a
tiuncatodinvoitodpyianid (Fig. 7.4¡, tho highost olhcioncy ol a iod light souico was
achiovod ly an LED sono yoais ago j4|.
Flg. 7.2 Sunnary oF diFFerent concepts to generate white light by prinary
light sources.
700 650 600 550 500 450 400 350
Wavelength [nm]
increasing x
Flg. 7.3 1ypical spectra oF blue and green InGaN LFDs and oF a red
AlGaInP LFD {s =0.0 to ca. 0.45).
7.2 vb|te and Co|ored |EDs 181
This LED is ostinatod to havo closo to 100 % intoinal olhcioncy and an oxtoinal
olhcioncy ol alout 55 %, iosulting in a luninous olhcioncy ol 102 lnW . This valuo
dononstiatos tho potontial ol LED tochnology as tho lutuio light souico ol hist
choico, sinco this is tho nost olhciont iod-light souico availallo to dato.
Tho lunon packago ol AlGaInP LEDs is, howovoi, linitod locauso ol thoinal
quonching ol tho onission. Foi powoi donsitios loyond 0.1 Wcn , tho olhcioncy
and also tho lilotino ol AlGaInPLEDs diops signihcantly, sinco tho chip tonpoiatuio
incioasos. Moioovoi, tho olhcioncy diops tionondously with incioasing onoigy ol tho
onission land (Fig. 7.5¡.
Flg. 7.4 InGaP LFD shaped as truncated inverted pyranid For eF6cient
light extraction {Source: Lunileds).
Flg. 7.5 FF6ciency oF InGaN- and AlInGaP-based LFDs as a Function oF
enission wavelength at roon tenperature. v{) gives the eye-sensitivity
as a Function oF the wavelength {Source: Lunileds).
182 7 |un|nescent Mater|a|s jor PbospborConeerted |EDs
Foi tho highoi-onoigy onissionliongioonto lluo andloyond, InGaNhas locono
tho natoiial ol choico. Altoi sovoial yoais ol intonsivo iosoaich, it has locono
possillo to cioato woiking LEDs intho InGaNnatoiial syston. Tho najoi dilhculty to
ovoicono was tho piollon ol p-doping GaN. This is achiovod ly doping Mg into tho
InGaN lattico, which happons at tonpoiatuios alovo 1100 C in tho doposition
piocoss. By vaiying tho anount ol Inin tho conposition ol tho LED, tho onissioncan
lo tunod lion UV to gioon. Howovoi, locauso ol sogiogation ollocts and sulsoquont
dovolopnont ol lattico dolocts, tho olhcioncy diops with incioasing wavolongth, i.o.
loi high Incontonts. Conpaiing tho dilloiont classos ol natoiials, it tuins out that tho
doloct donsity ol InGaN LEDs is nuch highoi than would lo toloiallo in noio
convontional III-Vconpound soniconductois. This is nainly locauso ol tho lack ol a
lattico-natchod sulstiato natoiial. At tho piosont tino, nostly Al O (sapphiio¡, with
a lattico nisnatch ol appiox. 15 %, is loing usod. Cuiiont oxtoinal olhcioncios iango
lion 40 % loi lluo to 10 % loi gioon wavolongths, with olhcioncy hguios tonding to
incioaso continuously now valuos loing pullishod litoially wook ly wook. As a
sunnaiy, olhcioncy as a lunction ol wavolongth loi tho two-natoiial systons is
plottod in Fig. 7.5 togothoi with tho oyo-sonsitivity cuivo.
Phosphor-Converted LEDs
As nontionod alovo, conlining tho light ol sovoial coloiod LEDs can cioato whito
light. Tho uso ol sopaiato RGB LEDs pionisos high olhcioncios and ßoxillo, usoi-
contiollod coloi lut ioquiios conplicatod oloctionics, locauso tho anounts ol iod,
gioon, and lluo light nust lo caiolully contiollod sinco tho LED light output
(intonsity and coloi¡ vaiios with diivo cuiiont, tonpoiatuio, and tino (dovico agoing¡.
Honogonoous optical nixing ol tho light is also iathoi dilhcult. Bocauso ol tho high
satuiation ol tho piinaiy LED colois, displays with a laigo coloi ganut can lo nado.
This can lo oxploitod loi tho inpiovonont ol LCDs, sinco standaid lacklights loi
LCDs aio lasod on ßuoioscont lanps yiolding a snalloi coloi ganut.
Howovoi, tho nost connon nothod to achiovo whito onission lion LEDs to dato
is ly paitially convoiting lluo light lion tho InGaN soniconductoi to lowoi-onoigy
onission ly noans ol phosphois, which aio dopositod onto tho LED chip as a thin
layoi (Fig. 7.6¡.
Thoso phosphoi-convoitod LEDs (pcLEDs¡ display a coloi point which is hoavily
dopondont on tho typo, thicknoss, and packaging donsity ol tho phosphoi layoi. Tho
appliod phosphoi(s¡ nust show stiong alsoiption ol tho lluo light and a high
photochonical stalility duo to tho high oxcitation donsity, o.g., 30 Wcn loi 1 W
InGaN LED (chip aioa 1 nn , oxt. olhcioncy ca. 30 %¡. This valuo is alnost thioo
oidois ol nagnitudo highoi than tho oxcitation donsity oxpoiioncod ly phosphois in
ßuoioscont lanps, with nany consoquoncos loi tho chonical and physical piopoitios
ol applicallo phosphois. Consoquontly, LEDphosphois canonly lo activatod ly thoso
ions which show a high quantun olhcioncy, ovon at olovatod tonpoiatuios (up to
150200 C¡. Tho host lattico nust showhigh chonical and thoinal stalility in oidoi
7.3 Pbospbor-Coneerted |EDs 183
to suivivo tho LEDlilotino ol noio than10 000 hj10|. Moioovoi, tho phosphoi should
havo a shoit docay tino to avoid satuiation at high diivo lovols, sinco this will iosult in
a chango, i.o. a lluo-shilt, ol tho LED spoctiun with diiving conditions. Most
pioninont LED convoitoi natoiials aio thus activatod ly thoso ions iolying on
allowod 4l-5d tiansitions, i.o. Eu and Co , which aio dopod into iigid host latticos
(oxidos, nitiidos, and sulhdos¡.
Today, tho whito LED naikot is doninatod ly pcLEDs conpiising a lluo-
onitting InGaN soniconductoi (420480 nn¡ coatod with a Co -activatod phos-
phoi doiivod lion tho ninoial giossulai (Ca Al Si O ¡ ciystallizing in tho gainot
stiuctuio j2|. Tho ioplaconont ol Ca ly Y and ol Si ly Al yiolds Y Al O
(Yttiiun-Aluninun-Gainot YAG¡, which can oasily lo dopod ly Co and othoi
tiivalont iaio-oaith ions, o.g. Gd oi Tl . Tho nost widoly appliod phosphoi is
(Y,Gd¡ Al O :Co (YAG:Co¡ j1|, whoio tho olloctivo coloi tonpoiatuio ol tho onittod
light lion a pcLED doponds on tho optical thicknoss ol tho phosphoi layoi. By
incioasing tho layoi thicknoss tho coloi shilts lion lluish whito (cool whito¡ to
yollowish whito (wain whito¡ (Fig. 7.7¡.
Tho hist cool whito LEDs including YAG:Co as a phosphoi showod a luninous
olhcioncy ol alout 10 lnW j8|. This coiiosponds to a light output ol 0.7 ln at a
powoi consunption ol 70 nW. Piosontly, cool whito LEDs alioady showan olhcioncy
ol 30 lnW , i.o. a high-powoi 5-W LED yiolds up to 150 ln j9|.
A disadvantago ol tho application ol a singlo yollow phosphoi is that low coloi
tonpoiatuios (wain whito light¡ cannot lo achiovod with a high coloi iondoiing
locauso ol tho lack ol iod light in tho LED spoctiun j7|. In addition, tho coloi
iondoiing ol cool whito LEDs doponds ontho diiving conditions. Thoso piollons aio
solvod ly tiichionatic whito LEDs conpiising two phosphois, tho hist onitting
lotwoon 520 and 570 nn and tho socond onitting lotwoon 590 and 660 nn.
Tho hist tiichionatic LED intioducod into tho naikot was lasod on a YAG:Co
pcLED, which conpiisos an additional iod phosphoi to achiovo illunination giado
wain whito LEDs with a high coloi iondoiing. Rod luninoscont natoiials usod in
conlination with tho yollowYAG:Co aio (Si Ca ¡S:Eu j5| and (Si Ca ¡ Si N :Eu
Flg. 7.6 Principle oF color conversion in a phosphor-converted pcLFD.
184 7 |un|nescent Mater|a|s jor PbospborConeerted |EDs
j6|. Thoso iod-onhancod LEDs showhigh CRIs (alovo 90¡ loi lowcoloi tonpoiatuios
(lotwoon 2500 and 4000 K¡.
An ovon noio advancod appioach loi a tiichionatic light souico, howovoi, is tho
application ol a gioon- and a iod-onitting phosphoi. This concopt has tho advantago ol
onalling a high coloi iondoiing at all iolovant lighting coloi tonpoiatuios, i.o. lotwoon
2500 and8000 K. It was dononstiatodly OpstoltonandKoodanloi ßuoioscont lanps
intho 1970s, altoi tho thooiotical tioatnont ly Thointon, that an RGBlight souico can
sinultanoously yiold high coloi iondoiing and high luninous olhcioncy j9|.
A two-conponont phosphoi llond loi application in tiichionatic RGB LEDs was
hist pioposod ly Mu¨lloi and conpiisos SiGa S :Eu (535 nn¡ and SiS:Eu (610 nn¡
j7|, yiolding pcLEDs with a voiy high coloi quality at an ailitiaiy coloi tonpoiatuio
lotwoon 2500 and 8000 K (Fig. 7.8¡.
Tho nain diawlack ol tho alovo-nontionod phosphoi llond is tho sonsitivity ol
sulhdos to watoi, iosulting intho pioductionol H S. This volatilo and ioactivo pioduct
dillusos to othoi LED conpononts, o.g. to tho Ag niiioi, whoio it convoits Ag into
llack Ag S. Howovoi, this piollon can lo ciicunvontod ly tho application ol a donso
paiticlo coating piovonting tho dillusion ol watoi towaid tho phosphoi suilaco j11|.
Although this noasuio is sulhciont to oltain usallo LED phosphois with tho
conposition (Si Ca ¡S:Eu, tho thiogallatos such as SiGa S :Eu aio still not appliod
inLEDs, sinco thoy oxhilit pionouncod thoinal quonching. Tho luninosconco ol tho
gioon-onitting thiogallato is stiongly quonchod with incioasing tonpoiatuio, i.o. its
quantun olhcioncy is ioducod ly 50 % at 170 C.
Altoinativo gioon phosphois aio Eu -dopod oithosilicatos ol tho loinula
(Ba Si ¡ SiO :Eu, which woio invontod ly Baiiy alout 40 yoais ago j12|. Thoii
coloi point shows a tionondous iod shilt duo to tho ioplaconont ol Ba ly Si . A
luithoi iod-shilt ol tho coloi point can lo achiovod ly tho incoipoiation ol Ca into
tho lattico.
800 700 600 500 400
Wavelength (nm)
YAG:Ce layer
Flg. 7.7 Fnission spectra oF a white LFD conprising a 460 nn-enitting
blue InGaN chip and a phosphor as a Function oF the optical thickness oF
the ¥AG:Ce layer.
7.3 Pbospbor-Coneerted |EDs 185
Thoso alkalino oaith oithosilicatos havo loon clainod iocontly to convoit lluo
InGaN LEDs into whito pcLEDs at dilloiont coloi tonpoiatuios j13|. Tho nain
piollon with oithosilicatos is thoii stiong alkalino chaiactoi and thus ioactivity
towaids oloctiophilic attack, o.g. ly CO oi H , as a iosult ol tho iathoi high oloction
donsity ontho oxygonatons ol tho SiO gioups. Thoioloio, a stalility inpiovonont
noasuio, o.g. a paiticlo coating, is still nocossaiy.
Whilo (Ba,Si¡ SiO :Eu is considoiod as a potontial gioon-onitting LED phosphoi,
Paik dosciilod tho application ol tho conposition (Ba,Si,Ca¡ SiO :Eu, which onits at
570 nn(Fig. 7.9¡, to oltaina whito pcLEDlasod onjust a singlo phosphoi, i.o. sinilai
800 700 600 500 400
84 89
87 92
88 93
89 93
86 91
88 89
87 89
Wavelength (nm)
Flg. 7.8 Fnission spectra oF white trichronatic LFDs conprising
SrGa S :Fu and SrS:Fu. 1he R values nentioned are the CRIs For 8 and 14
reFerence colors, respectively {the naxinun CRI is 100 in both cases).
800 700 600 500 400
1,0 Ba2SiO4:Eu
Wavelength (nm)
Flg. 7.9 Fnission spectra oF selected conpositions oF the solid solution
{Ba Sr Ca ) SiO :Fu.
186 7 |un|nescent Mater|a|s jor PbospborConeerted |EDs
to tho YAG:Co LEDs. Anothoi possilility to achiovo a whito pcLED with a singlo
phosphoi is tho application ol SiLi SiO :Eu oi Tl Al O :Co (TAG:Co¡, which woio
clainod as LED phosphois a low yoais ago j14,15|.
In viow ol tho chonical ioactivity ol (Ba Si ¡ SiO :Eu, tho soaich loi luithoi
gioon-onitting phosphois applicallo in pcLEDs is ongoing. Sono intoiosting
candidatos aio Lu Al O :Co(LuAG:Co¡ and tho oxynitiidos SiSi N O :Eu and CaSi
N O :Eu j16|, which woio quito iocontly nontionod as LED phosphois. Fion a
chonist`s point ol viow, tho oxynitiido is a voiy intoiosting conpound, sinco this
natoiial loinally includos tiivalont N anions. On tho ono hand, tho nitiido anion
can undoigo thioo oi loui covalont londs iosulting in natoiials with a highoi
haidnoss, stalility, and donsity than olsoivod loi sinilai oxidos. On tho othoi hand,
tho stiongly covalont chaiactoi ol tho nitiido-notal londs iosults in a stiong
ioduction ol tho onoigy sopaiation lotwoon tho giound stato (4l ¡ and tho oxcitod
stato conhguiation (4l 5d ¡ ol Co and Eu . A iathoi snall sopaiation yiolds
phosphois with alsoiption lands in tho noai UVto gioon and onission lands in tho
gioon, yollow, oi ovon iod spoctial iango. As oxpoctod, tho conposition Si Si N :Eu,
sololy conpiising nitiido as an anion, is an oiango powdoi with a lioad onission
land aiound 610 nn j17|.
A tiichionatic LED on tho lasis ol Si Si N :Eu and SiSi N O :Eu shows high
coloi iondoiing at all iolovant coloi tonpoiatuios (Fig. 7.10¡, as alioady shown loi tho
sulhdo LED, lut with tho advantago ol a highoi lilotino and loss dopondonco ol tho
light output and coloi point on tho diivo conditions j18|.
Evon though this phosphoi conposition is a powoilul and pionising llond loi
pcLEDs, thoio aio noio potontial LEDphosphois, nainly lasod on nitiidos, SiONos,
oi SiAlONos as a host lattico. Ono ol tho iocontly dovolopod natoiials is CaAlSiN :Eu
j19|, which can lo appliod as a doop iod onittoi to luithoi inpiovo coloi iondoiing at
low coloi tonpoiatuios.
800 700 600 500 400
86 90
88 92
85 89
85 89
81 86
83 86
83 85
Wavelength (nm)
Flg. 7.10 Fnission spectra oF white trichronatic LFDs conprising
SrSi N O :Fu and S Si N :Fu.
7.3 Pbospbor-Coneerted |EDs 187
Future 1rends
A piactical olhcioncy taigot loi a phosphoi-convoitod LED light souico is alout
100 lnW , which is conpaiallo to high-ond whito ßuoioscont lanps. Inpioving
tho oxtoinal phosphoi quantun olhcioncy, stalility, linoaiity, and tonpoiatuio
poiloinanco aio tho nost inpoitant issuos to noot this taigot.
Tho inpiovonont ol tho intoinal quantun olhcioncy ol tho piosontly appliod
natoiials can itsoll haidly contiiluto to this goal, sinco LED phosphois, such as
YAG:Co, (Ca,Si¡S:Eu, oi (Ca,Si¡ Si N :Eu, aio alioady opoiating at tho physical linit
as lai as tho intoinal quantun olhcioncy is concoinod. Moio inpoitant is tho
inpiovonont ol tho so-callod LED packago gain, which dosciilos tho ovoiall
olhcioncy ol tho convoision ol photons onittod ly tho InGaN soniconductoi into
tho dosiiod LED spoctiun. Sinco light out-coupling lion tho phosphoi giains and
light scattoiing in tho convoision layoi signihcantly contiiluto to tho packago gain,
tho optinization ol tho paiticlo sizo distiilution and tho suilaco noiphology ol LED
phosphois will lo in tho locus ol lutuio R&D activitios.
A iocont dovolopnont, loi instanco, is tho onhanconont ol tho light out-coupling
olhcioncy ly tho applicationol a giainy coating to giadually natchtho ioliactivo indox
ol tho highly ioliactivo sulhdo and nitiido phosphois to tho packago natoiial j20|.
Fuithoi noasuios aio tho ioduction ol tho docay tino j21|, tho onhanconont ol tho
alsoiption ol LED phosphois to inpiovo thoii linoaiity with oxcitation donsity j21|,
and tho application ol iod lino onittois instoadol iodlioad-land onittois to onhanco
tho lunon oquivalont j22|.
Evon though cool and wain whito LEDs with a iathoi high coloi iondoiing aio
alioady on tho naikot, tho hnal goal is to pioduco LED light souicos with a coloi
quality closo to that ol a llack-lody iadiatoi at a tonpoiatuio ol 2500 to 6000 K. This
noans that upconing LEDs havo to natchtho spoctiunol incandoscont and halogon
lanps noio closoly. This ioquiios novol LED phosphois to hll up tho spoctial gaps in
tho onission spoctiun ol cuiiont whito pcLEDs. To this ond, nany novol nitiido and
oxynitiido host latticos dopod ly Eu and Co aio piosontly undoi dovolopnont,
sinco tho spoctia ol Eu and Co canoasily lo tunodly tho host lattico, and nany ol
tho luninoscont natoiials activatod ly thoso ions oxhilit high olhcioncy, stiong
alsoiption, shoit docay tino, and lioad onission lands.
Dospito tho succoss ol whito pcLEDs opoiating on tho lasis ol lluo InGaNdios, tho
convoisionol noai-UVLEDs (370420 nn¡ is anothoi appioachol lioad intoiost. Tho
nainioason is that noai-UVLEDs would allowtho application ol nany noio typos ol
luninoscont natoiials than thoso nontionod in Tallo 7.1.
In paiticulai, Eu dopod phosphois aio ol stiong intoiost loi tho application in
noai-UV LEDs, sinco thoy oxhilit a high lunon oquivalont, quantun olhcioncy, and
photostalility at tho sano tino. Moioovoi, lion a piactical point ol viowa ßuoioscont
light souico conpiising a iod lino onittoi onitting at 610615 nn is tho lost
conpioniso lotwoon luninous olhcacy and coloi iondoiing j9|.
A diawlack is, howovoi, tho woak alsoiption ol Eu in tho lluo and ovon in tho
noai UV. Tho nain stiatogy to solvo this piollon has locusod on natoiials that havo
188 7 |un|nescent Mater|a|s jor PbospborConeerted |EDs
lioad and intonso chaigo-tiansloi (CT¡ alsoiption lands in tho noai UV and aio
thoioloio capallo ol olhciontly alsoiling tho onission lion InGaN lasod LEDs.
Such natoiials includo oxysulhdos, vanadatos, nolyldatos, tungstatos, otc., whoio
tho oxygon to Eu chaigo-tiansloi land aio voiy intonso and lioad and tho position
is at iathoi low onoigy, as loi o.g. in Y O S:Eu oi Gd O S:Eu j23|.
A iocont idoa is to convoit noai-UV oi lluo light via tho 4l-4l tiansitions ol Eu
locatod at 394 ( F L ¡ and 465 nn ( F D ¡, which aio iathoi intonso in tungstatos
and nolyldatos. Following tho oxcitation piocoss, Eu iolaxos noniadiativoly to tho
D stato, which is tho onitting onoigy lovol. Foi instanco, tho conposition
NaY Eu (WO ¡(MoO ¡ shows a nuch highoi light output than Y O S:Eu loi
394 nn oxcitation. Thoso iosults lood tho hopo that an Eu phosphoi, which is
sulhciontly stiongly luninoscont undoi 394- and]oi 465-nnoxcitation, can lo lound
in tho lutuio. Tho highoi lunon oquivalont ol Eu (260300 lnW ¡ conpaiod to
Eu phosphois (Tallo 7.1¡ will contiiluto to a luithoi onhanconont ol tho luninous
olhcacy ol LEDs.
1ab. 7.1 Overview oF the spectral properties and problen
areas oF the nost inportant LFD phosphors.
Emlsslon pe
a| at ¡nmj
Lumen equlva|ent
(LEj ¡|m]w j
Prob|em areas
(Ba,Si¡ SiO :Eu Gioon 525 530 Stalility
Lu Al O :Co Gioon 530 465 Naiiow alsoiption land
SiSi N O :Eu Gioon 540 530 Synthosis
SiGa S :Eu Gioon 535 575 Thoinal quonching
Y Al O :Co Yollow 540 450 Naiiow alsoiption land
Tl Al O :Co Yollow 560 410 Naiiow alsoiption land
CaSi N O :Eu Yollow 565 485 Synthosis
(Y,Gd¡ Al O :Co Yollow 570 400 Naiiow alsoiption land
SiLi SiO :Eu Yollow]oiango 580 415 Stalility
Ca Si N :Eu Rod 610 270 Synthosis
Si Si N :Eu Rod 620 240 Synthosis
CaAlSiN :Eu Rod 650 150 Synthosis, LE
CaS:Eu Rod 650 85 Stalility, LE
1 Nakanuia, S. and Fasol, G. (1997¡ 1nc
B|uc Luscr Dicdc, Spiingoi,
Boilin,Nakanuia, S. (1997) MRS Bu||.,
2 Zukauskas, A., Shui, M. S., Caska, R.
(2002¡ !ntrcducticn tc Sc|id-Stutc
Lignting, John Wiloy & Sons, 122.
3 Szo, S. M. (1981¡ Pnysics cj
Scniccnductcr Dcviccs, John Wiloy &
4 Kianos, M. R. ct u|. (1999¡ App|. Pnys.
Lctt., 75, 2365.
5 Mu¨lloi-Mach, R., Mu¨lloi, G. O., Ju¨stol,
T., Schnidt, P. J. (2003¡ US Putcnt
Rejerences 189
2003]0006702,Mu¨lloi-Mach, R., Mu¨lloi,
G. O., Kianos, M., Tiottioi, T. (2002¡
!EEE ]. Sc|. 1cp. Quunt. E|cctr., 8, 339.
6 Yanada, M., Naitou, T., Izuno, K.,
Tanaki, H., Muiazaki, Y., Kanoshina,
M., Mukai, T. (2003¡ ]pn. ]. App|.
Pnys., 42, L20.
7 Mu¨lloi-Mach, R. and Mu¨lloi, G. O.
(2000¡ Prcc. SP!E, 3938, 30.
8 Bando, K. (1998¡ Synp. Prcc. cj tnc 8tn
!nt. Synp. cn tnc Sci. µ 1ccn. cj Lignt
Scurccs, 80.
9 Thointon, W. A. (1971¡ ]. Opt. Scc.
Ancr., 61, 1155,Koodan, M. and
Opstolton, J. J. (1971) Lignting Rcscurcn
und 1ccnnc|cgy, 3, 205;Veislegen,
1. M. P. 1., Raoielovic, D., VienLen,
I. !. (1974) ]. E|cctrccncn. Scc., 121,
10 Scott, K. (May]Juno 2002¡ 1nc Lignting
]curnu|, 34.
11 Ju¨stol, T., Mayi, W., Ronda, C. R.,
Schnidt, P. J. (2000¡ Ccrnun Putcnt
DE 10051242.
12 Baiiy, T. L. (1968¡ ]. E|cctrccncn. Scc.,
115, 1181.
13 Tasch, S., Pachloi, P., Roth, G., Tows,
W., Konploit, W., Staiick, D. (2000¡
Wcr|d Putcnt WO 02]054502.
14 Ju¨stol, T., Mayi, W., Schnidt, P. J.
(2004¡ Eurcpcun Putcnt EP
15 Ellons, A., Joinann, F., Zwaschka, F.,
Kunnoi, F. (2001¡ Wcr|d Putcnt WO
16 Fiodloi, T. and Joinann, F. (2004¡
Ccrnun Putcnt DE 102004051395.
17 Ho¨ppo, H., Lutz, H., Moiys, P.,
Schnick, W., Soilnoioi, A. (2000¡ ].
Pnys. Cncn. Sc|ids, 61, 2001.
18 Muolloi-Mach, R., Muolloi, G., Kianos,
M. R., Ho¨ppo, H. A., Stadloi, F., Ju¨stol,
T., Schnick, W., Schnidt, P. J. (2005¡
Pnys. Stut. Sc|. A, 202, 1727.
19 Uhoda, K., Takizawa, H., Endo, T.,
Yanano, H., Shinada, M., Wang, C.-
M., Mitono, M. (2000¡ ]. Lunin.,
87~89, 967,Ho¨ppo, H. A., Lutz, H.,
Moiys, P., Schnick, W., Soilnoioi, A.
(2000) ]. Pnys. Cncn. Sc|ids, 61, 2001.
20 Ju¨stol, T., Bochtol, H., Schnidt, P. J.
(2005¡ Eurcpcun Putcnt EP 05107759.
21 Sotlui, A. A., Shiang, J., Conanzo, H.
A., Bockoi, C. A., Duclos, S.,
Siivastava, A. M., Woavoi, S. (2005¡
Wcr|d Putcnt 2005]083036.
22 Radkov, E. V., Giigoiov, L. S., Sotlui,
A. A., Siivastava, A. M. (2006¡ US
Putcnt 2006]0169998.
23 Shionoya, M. and Yon, W. M. (1999¡
Pncspncr !undbcck, CRC Pioss.
24 Nooiaj, S., Kijina, N., Choothan,
A. K. (2004¡ Cncn. Pnys. Lctt.,
387, 2.
190 7 |un|nescent Mater|a|s jor PbospborConeerted |EDs
Organlc E|ectro|umlnescence
josepb j. Sb|ang and /n|| R. Dugga|
Oiganic oloctioluninosconco is an oxciting hold that oxists at tho intoisoction
lotwoon nany sciontihc disciplinos including synthotic and physical chonistiy
and soniconductoi and optical physics. Oiganic light-onitting dovicos (OLEDs¡
aio tho piactical nanilostation ol tho tionondous piogioss that has loon
achiovod in this hold, highly olhciont dovicos having loon dovolopod j1,2| and
succosslully onployod in connoicial pioducts j3|. Tho lasic sciontihc aioa is
now oxtionoly activo, with nany now pullications outlining now dovico and
natoiial aichitoctuios appoaiing oach nonth. Most ol tho piogioss to dato has
loon luolod loth ly advancos in tho lasic knowlodgo ol oloctionic piocossos in
oiganic natoiials j4,5| and an appliod intoiost in dovoloping ßat panol displays.
Moio iocontly, iosoaichois havo sot thoii sights on applying this tochnology loi
gonoial lighting, aigually tho nost donanding luninosconco application j6,7|.
Achioving this goal will ioquiio sulstantial inpiovononts to natoiials and dovico
aichitoctuios to incioaso olhcioncy, and tho sinultanoous dovolopnont ol a
high thioughput nanulactuiing inliastiuctuio to onallo high poiloinanco at low
In this chaptoi, tho lasic nochanisns lohind oiganic oloctioluninosconco will lo
dosciilod, and thon tho pioniso, challongos, and sono uniquo appioachos to
dovoloping this tochnology loi tho ultinato application ol gonoial lighting will lo
outlinod. Tho chaptoi logins with a dosciiption ol tho lundanontal physics ol OLED
dovicos and natoiials. Following this, Soction 8.2 piovidos noio dotail ly piosonting
a sonowhat histoiical ovoiviow ol tho najoi tionds and innovations in dovico and
natoiial dosign that havo onallod tho inpiossivo piogioss to dato. Soction 8.3
outlinos an oxanplo ol how thoso dilloiont olononts: physics, dovico dosign, and
natoiials can lo conlinod to nako a piactical, laigo-aioa illunination souico. This
oxanplo dononstiatos loththo possililitios inhoiont in this tochnology and tho aioas
whoio olloit noods to lo locusod in oidoi loi piogioss to continuo. Conclusions aio
piosontod in tho hnal soction.
Lunincsccncc. Frcn 1nccry tc App|icuticns. Editod ly Coos Ronda
Copyiight 2008 WILEY-VCH Voilag GnlH & Co. KGaA, Woinhoin
ISBN: 978-3-527-31402-7
OLED Fundamenta|s
An oiganic light-onitting dovico consists ol ono oi noio soniconducting oiganic
thin hlns sandwichod lotwoon two oloctiodos, ono ol which nust lo tianspaiont. A
sinplihod schonatic ol an OLED is shown in Fig. 8.1. In a typical dovico, indiun tin
oxido (ITO¡ is utilizod as a tianspaiont anodo oloctiodo and an ovapoiatod notal is
utilizod as tho cathodo. Tho OLED shown in Fig. 8.1 iopiosonts tho nost connon
''down-onitting`` dovico stiuctuio and is typically laliicatod ly soquontially doposit-
ing layois onto tho tianspaiont sulstiato. Typically, tho sulstiato is glass oi plastic that
has loon pio-coatod with ITO. Tho oiganic layois consist ol natoiials that tianspoit
chaigo and onit light. Thoso aio appliod via oithoi a solution-lasod oi a vapoi-lasod
coating piocoss. Tho nunloi and typo ol layois doponds upon tho choson natoiials
and laliication nothodology. Thoso layois, which dotoinino lundanontal OLED
piopoitios, lointho locus ol this chaptoi. An oloction-injocting cathodo is appliod on
top ol tho oiganic layois via thoinal ovapoiation. Typically this oloctiodo consists ol a
low woik lunction notal such as calciun oi a nagnosiun silvoi alloy. Finally, tho
ontiio packago is soalod to piovont ingioss ol watoi oi oxygon. Whonvoltago is appliod
lotwoon tho two oloctiodos, diodo-liko ioctihcation is olsoivod with appiociallo
cuiiont ßow occuiiing whon tho ITO anodo is liasod positivoly. Undoi this loiwaid
lias, light is gonoiatod and onittod into tho suiioundings thiough tho tianspaiont
sulstiato. On tho iight sido ol Fig. 8.1 is a connonly usod loin ol onoigy lovol
diagian loi tho dovico. Tho voitical axis is onoigy with tho onoigy ol a lioo oloction in
tho vacuun locatod at tho top ol tho axis and sot to a valuo ol zoio ly convontion.
Flg. 8.1 A schenatic drawing oF the layer structure oF a
sinple OLFD {leFt) and the corresponding energy level
diagran {right). 1he energy scale indicates binding energy
relative to the vacuunlevel. For this scale, the Free electron
in vacuun has the highest energy oF 0 and corresponds to
the top oF the scale.
192 8 Organ|c E|ectro|un|nescence
Eloctionic statos that woakly lind oloctions aio high on this axis, statos that havo voiy
high alhnity loi oloctions loing lowoi down on tho axis. Typically, tho nogativo sign is
not includod, so that a stato that is donotodas having anonoigy ol 6 oVis actually |cwcr
inonoigy iolativo to tho vacuunly 6 oV. Motal woik lunctions aio donotod ly a singlo
lioadlino to iopiosont thoii Foini lovol. Tho oiganic natoiials aio typically dosciilod
using two linos, tho uppoi ono coiiosponding to tho lowost unoccupiod noloculai
oilital (LUMO¡ and tho lowoi ono tho highost occupiod noloculai oilital (HOMO¡.
Thoso lovols coiiospond to tho conduction and valonco lands ol a covalont soni-
conductoi natoiial.
Qualitativoly, tho dovico physics ol an OLED is lost illustiatod ly oxanining tho
sinplost typo ol dovico stiuctuio ono which usos only a singlo oiganic layoi. Tho
opoiating piinciplos ol this singlo-layoi dovico aio shown in Fig. 8.2. Whon a
loiwaid lias is appliod, oloctions aio injoctod lion tho cathodo into tho LUMO ol
tho oiganic natoiial and holos aio injoctod lion tho anodo into tho HOMO ol tho
natoiial. Thus, tho oloctions nust ovoicono tho laiiioi lotwoon tho Foini lovol ol
tho top oloctiodo and tho LUMO lovol ol tho polynoi, whilo tho holos nust
ovoicono tho onoigy laiiioi lotwoon tho ITO Foini lovol and tho HOMO ol tho
polynoi. Altoi tho caiiiois aio injoctod, thoy diilt in tho piosonco ol tho oxtoinally
appliod oloctiic hold ly hopping lion noloculo to noloculo to tho opposito
oloctiodo. Il an oloction and a holo happon to noot, thoy nay conlino to loin
a noloculai oxcitod stato known as an oxciton that nay thon iadiativoly ioconlino
to gonoiato a photon.
Thoio aio hvo distinct stops in tho light onission piocoss: (1¡ chaigo injoction, (2¡
chaigo nigiation, (3¡ oxciton loination, (4¡ light onission, and (5¡ light oxtiaction.
To achiovo optinal OLED poiloinanco, oach stop nust opoiato at its naxinal
olhcioncy. Tho hist loui ol thoso stops aio illustiatod in Fig. 8.2. Whilo thoso stops
occui in tiaditional soniconductoi lasod LEDs (o.g., GaAs, GaN¡, oach stop is
Flg. 8.2 Diagran illustrating the physical processes
involved in electroluninescence Fron organic naterials.
8.2 O|ED |undanenta|s 193
signihcantly dilloiont in oiganic natoiials locauso tho oloctionic statos in oiganic
natoiials aio highly localizod and tho nolility ol tho chaigo caiiiois is oidois ol
nagnitudo lowoi j4|. Dovicos lasod upon oiganic soniconductois ioquiio a spocial
dosciiption ol tho physics ol opoiation which utilizos loth tho languago ol solid
stato physics, oiiginally dovolopod to dosciilo plano wavo-liko tianspoit statos, and
tho languago ol noloculai physics, dovolopod to dosciilo oloctionic piocossos in
localizod statos j5|.
Foi an oloctioluninoscont dovico, tho iadiant ''wall-plug`` olhcioncy ol tho light
souico (iadiant powoi out dividod ly oloctiical powoi in¡ is givon ly tho lollowing
 
EQE 1
Tho iatio is tho avoiago onoigy ol tho onittod photons in oloction volts (typically
2.4 oVloi a whito-light onittoi¡ dividod ly tho appliod dovico voltago. Bocauso ol tho
intiinsically lowconductivitios ol thoso natoiials, tho injoction and diilt ol caiiiois
ioquiio high oloctiic holds ( 0.1 MVcn ¡, and achioving low-voltago opoiation
thus linits tho thicknoss ol tho oiganic layois to a low hundiod nn. Tho oloction
(holo¡ injoction and tianspoit piocossos aio illustiatod as stops 1a (1l¡ and 2a (2l¡ in
Fig. 8.2. Tho socond toin, tho oxtoinal quantun olhcioncy (EQE¡, is tho iatio ol tho
nunloi ol photons onittod into tho anliont dividod ly tho nunloi ol oloctions
injoctod into tho dovico. Wo can luithoi doconposo tho dovico EQE into sovoial
EQE  


Tho hist two olhcioncy toins coiiospond to tho ionaining piocossos dopictod in
Fig. 8.2. Thus,  , is tho liaction ol oloctions and holos that noot at a
paiticulai sito within tho dovico to loin a potontially onissivo stato oi oxciton.
Eloctions oi holos that do not noot lut iathoi nigiato to tho opposito oloctiodo aio
lost and ioduco this toin lolow unity. Tho noxt toin  is tho photoluninoscont
olhcioncy ol tho oxciton stato. It ioßocts tho lact that tho oxcitonnay iolax thoinally to
pioduco hoat iathoi than iadiativoly to pioduco light. To avoid lossos duo to this toin,
tho iato ol iadiativo piocossos, k , nust lo nuch highoi than tho iato ol tho
noniadiativo piocoss, k , so that tho iatio:


 k
is noaily unity. In oiganic natoiials, this toin is typically ''spin dopondont``, as an
oloctionanda holo, oach with spin ½, canlointwo typos ol oxcitons ''singlot`` witha
spin-stato ol 0 oi ''tiiplot`` with a spin stato ol 1. In gonoial, thoso statos havo dilloiont
iadiativo and noniadiativo iatos. Fig. 8.3 illustiatos tho dilloiont pathways that can
occui in tho piosonco ol nultiplo spin statos. A noio conploto oquation loi  is
194 8 Organ|c E|ectro|un|nescence

 fs
S rad
S rad
 k
S nr
1 fs
T rad
T rad
 k
T nr
Tho hist toinontho iight hand sido coiiosponds tosinglot onission, tho socondtoin
coiiosponds to tiiplot onission. Hoio, l is tho liactionol singlots loinodand is givon
ly a sinilai typo ol iato oxpiossion:
fs 
f S
f S
 3k
f T
1 
 5
Hoio wo havo dohnod k and k as tho iato ol loination ol singlot (S1¡ and tiiplot
(T1¡ oxcitons lion an initially sopaiatod oloction holo paii, thoso iatos aio sonsitivo to
tho dotails ol tho chaigo ioconlination piocoss.  , ''tho intoisyston ciossing
quantun yiold``j8| iolois to tho liaction ol tho initially loinod S1 statos that non-
iadiativoly convoit to T1 statos and is dotoininod ly tho associatod iato constant k
as lollows:


S rad
 k
S nr
 k
In nost highly ßuoioscont oiganic natoiials, tho coupling lotwoon tho spin and
spatial dogioos ol lioodon is snall, and  is noai zoio. In thooiy, wo should also
considoi a iovoiso piocoss, i.o. tiiplots that latoi loin singlots, lut in alnost all
oiganic natoiials tho T1 stato is 0.251.0 oV lowoi in onoigy than tho S1 stato. As
this is signihcantly gioatoi than tho anliont thoinal onoigy (kT¡, onco tho tiiplot
Flg. 8.3 Fnergy level and kinetic diagran oF the charge
reconbination process.
8.2 O|ED |undanenta|s 195
stato is loinod on a paiticulai noloculo, it will not latoi loin an oxcitod singlot
stato without additional onoigy input. This dillois lion tho caso ol inoiganic
oloctioluninoscont onittois, which havo nuch snalloi oxciton linding onoigios
loi loth singlot and tiiplot oxcitons. Tho lactoi ol 3 in tho dononinatoi conos lion
spin statistics: thoio aio 3 conlinations ol two spins ol 1]2 that can yiold a tiiplot
and only ono that can yiold a singlot. Thus, assuning that k and k aio oqual,
thon tho ''statistical`` linit ol singlots and tiiplots is oltainod, and 25 % ol tho
oxcitons that aio loinod aio singlot and 75 % ol tho oxcitons that aio loinod aio
Whothoi tho statistical linit (ls 0.25¡ is oloyod in all oiganic oloctioluninoscont
natoiials is tho suljoct ol sono contiovoisy, as tho dotails ol tho chaigo ioconlina-
tion nochanisn undoi oloctiical injoction conditions aio haid to piolo. In tho
sinplost nochanisn, an oloction and holo collido and loin a highly oxcitod oxciton
that is oithoi singlot (25 % ol tho tino¡ oi tiiplot (75 % ol tho tino¡. Thoso highly
oxcitod statos thon iapidly iolax to tho oithoi S1 oi T1 loloio any intoisyston ciossing
can occui. This nochanisn loads to singlot and tiiplot loination iatos that aio sololy
govoinod ly initial chaigo ioconlination iatos, i.o. tho ''statistical linit``. In an
altoinativo nochanisn, chaigo ioconlination occuis thiough nultiplo intoinodiato
statos lollowing loination ol tho initial chaigo paii, and thus k and k aio actually
tho pioduct ol sovoial iato constants j9|. Hoio, k and k can lo nonoqual whon
two conditions aio not: (a¡ thoio aio dilloiont onoigy laiiiois to tho loination ol S1
and T1 lion ono oi noio ol thoso intoinodiato statos and (l¡ thoio is a piocoss
whoioly tho chaigo paiis can intoichango thoii spin oiiontation whilo in thoso
intoinodiato statos j10|. In this caso, tho liaction ol singlots loinod can dilloi gioatly
lion tho statistical linit. Noto that this altoinativo nochanisn is lut ono ol sovoial
othoi piocossos that also nay lo occuiiing in tho dovico, such as tiiplot-tiiplot
annihilation, that can load to valuos ol l 0.25 j11|. Each ol thoso nochanisns,
howovoi, doponds upon tho oxact dotails ol intoinoloculai chaigo tiansloi piocossos,
which aio haid to dosciilo thooiotically, ovon whon tho niciostiuctuio is woll known
j12|. Thus, caiolul oxpoiinontal noasuiononts aio nocossaiy to dotoinino which
nochanisns aio opoiativo.
Expoiinontally, nost noasuiononts ol tho singlot tiiplot iatio aio sonowhat
indiioct and usually ioquiio additional nodoling. Cuiiontly, howovoi, thoio appoais
to lo consonsus that loi snall noloculos (1000 anu¡ tho statistical linit soons to
hold, lut that in polynoi natoiials it nay oi nay not. Foi polynois, sono thooiotical
calculations j13| and indiioct oxpoiinontal iosults j14,15| suggost that, doponding on
natoiial, ks canlo gioatoi than0.25, whilo othoi iosults suggost that l is tho sano loi
polynois and snall noloculos.
Tho distinction lotwoonsinglots and tiiplots is inpoitant locauso tho giound stato
ol nost oiganic onissivo noloculos has singlot spin, and thus iadiativo onission
lionsinglot oxcitod statos is spinallowod whilo onission liontiiplot oxcitod statos is
loinally spin loiliddon. In nost oiganic natoiials, singlot tiansitions havo typical
valuos loi k on tho oidoi ol 10 s . In contiast, k is on tho oidoi ol 10 s,
which is only conpotitivo with noniadiativo iolaxation at lowtonpoiatuios (100 K¡.
Honco, loi thoso natoiials, only singlot onission is olsoivod at ioon tonpoiatuio,
196 8 Organ|c E|ectro|un|nescence
and tho socond toin in Eq. (4¡ nakos only a nogligillo contiilution to tho total
Tho hnal toin,  , is tho olhcioncy ol coupling tho light gonoiatod in tho high
indox polynoi layois (ioliactivo indox, n 1.52.0¡ out ol tho dovico and into tho
anliont (n1¡. Typically, intoinal ioßoction linits this toin to lotwoon 0.2 and 0.4
j16|. A nunloi ol schonos oxist loi incioasing this output coupling olhcioncy. Ono
nothod iolios on nodihcation ol tho onission layois to adjust tho physical optics ol
tho optical niciocavity loinod lotwoon tho two oloctiodos. This appioach nodihos
tho angulai dopondonco ol tho onission piohlo ol tho light-onitting layois so that
nost ol it is not intoinally ioßoctod. Tho optical niciocavity is dosignodto onsuio that
light is onittod in tho loiwaid diioction at anglos lolow tho ciitical anglo ol tho
intoilaco j17|. A vaiiant ol this solution is to placo a voiy low-indox aoiogol (n 1.01¡
noxt to tho thin cavity. Ina conplonontaiy appioach, tho OLEDsulstiato is nodihod
so as to outcouplo light that would noinally lo tiappod via intoinal ioßoction. Foi
oxanplo, ono solution, nost applicallo to point souicos, is to uso a shapod sulstiato,
and it has loon dononstiatod that coitain lons-liko shapos will iosult in alnost
conploto light oxtiaction j18,19|. In addition, tho sulstiato itsoll can lo physically
toxtuiod j20| oi nodihod to scattoi light volunotiically j21|. Both niciocavity and
sulstiato nodihcation ollocts can lo nodolod, and it is possillo to oltain a conploto
dosciiption ol light oxtiaction lion tho dovico. Thoso calculations indicatod that
undoi tho coiioct conditions tho ovoiall oxtiaction olhcioncy can lo quito high, and
valuos loi  aio potontially 0.6 j21|.
key OLED 1rends and Innovatlons
In oidoi to achiovo optinal poiloinanco, oach ol tho physical piocossos dosciilod
alovo nust opoiato at naxinal olhcioncy. Histoiically, thoio havo loontwo schools ol
thought on howto achiovo this goal. Ono is to utilizo nultiplo oiganic layois, oach ol
whichis optinizod loi a distinct lunction. This appioach has typically utilizod''snall-
noloculo`` natoiials that aio appliod as thin hlns ly noans ol thoinal ovapoiation.
Tho socond school ol thought has loon to nininizo tho nunloi ol oiganic layois
nocossaiy ly luilding as nuch lunctionality as possillo into a singlo oi at nost a low
natoiials. This appioach has typically utilizod polynoiic natoiials that aio appliod as
thin hlns via solution piocossing nothods such as spin coating. In tho lollowing
soctions, tho histoiical tionds and cuiiont natoiials and dovico stiuctuios loi thoso
two appioachos aio dosciilod in noio dotail.
E|ectro|umlnescence From vapor-deposlted Organlc Fl|ms
Eloctioluninosconco lion oiganic natoiial was hist olsoivod in tho 1960s using
anthiacono ciystals j22,23| (soo stiuctuial loinulao in Fig. 8.4¡. Howovoi, tho
olhcioncy ol light gonoiation was low (0.01¡ j24|. Inpiovononts in olhcioncy
8.3 key O|ED Trends and |nnoeat|ons 197
woio nado whonthinhlns ol anoiphous oiganic natoiials woio utilizod iathoi than
singlo ciystals j24,25|, lut tho nost dianatic lioakthiough occuiiod whon dovicos
containing two dilloiont stackod oiganic layois woio utilizod j24|. Tho two layois in
this caso consistod ol a di-tiiphonyl anino into which holos aio injoctod and
aluninun tiis-quinolato (Alq ¡ into which oloctions aio injoctod. Tho dovico stiuc-
tuio loi this OLED and tho iolovant onoigy lovols loi oach dovico layoi aio shown in
Fig. 8.5. Tho inpoitant loatuio is that tho onoigy lovols ol tho two oiganic layois aio
ollsot so that noithoi oloctions noi holos can oasily tiansit lionono sido ol tho dovico
to tho othoi. Thus, oxcitonloination and onission aio loicod to occui at tho intoilaco
lotwoon tho holo-tianspoiting layoi (HTL, dianino¡ and tho oloction-tianspoiting
layoi (ETL, Alq ¡. Thoso dovicos oxhilitod EQEvaluos ol 1 % and a luninous olhcacy
ol 1.5 lunons]watt (LPW¡, which is sulstantially highoi than that ol tho piovious
singlo-layoi dovicos. Tho iolativo oaso ly which two highly dissinilai natoiials aio
layoiod atop ono anothoi illustiatos an additional chaiactoiistic ol oiganic natoiials:
tho lack ol dangling londs andintoilaco suilaco statos. Ingonoial, thoio is no covalont
chonical lond lotwoon adjacont noloculos, and thus no chonical londs aio
disiuptod at tho intoilaco lotwoon ono natoiial and anothoi. In contiast to inoiganic
soniconductoi natoiials, it is iolativoly oasy to loin nany layois ol dissinilai
natoiials thoio is no ''lattico natching`` piollon.
Flg. 8.4 Sone oF the naterials used in vapor-processed
devices, including naterials that are connonly used as
host naterials {leFt) and typical singlet Fuorescent and
triplet phosphorescent enissive dopants {right).
198 8 Organ|c E|ectro|un|nescence
Tho onission olhcioncy ol tho dovico stiuctuio dopictod in Fig. 8.5 is linitod ly
tho low photoluninosconco olhcioncy ol Alq Howovoi, it was latoi shown that
this linitation could lo ovoicono thiough co-doposition ol snall quantitios ol
voiy high-PL olhcioncy natoiials in tho tianspoit layois noai tho HTL]ETL
intoilaco j26|. By co-doposition ol a highly ßuoioscont dopant at low concontia-
tions ( 1 %¡, such as Counaiin 540 (lluo-gioon onission¡ oi DCM1 (iod
onission¡ into an ETL host, tho dovico olhcioncy could lo gioatly incioasod
(ly a lactoi ol 2.5¡ and tho onission coloi tunod. In thoso diluto guost-host
systons, il tho dopant is choson coiioctly, all onoigy is tiansloiiod liontho host to
dopant. Onco on tho dopant, it doos not iotuin to tho host. Thus, tho only
iostiiction on this nothod is that tho onoigy ol tho onissivo dopant (usually a
singlot¡ nust lo lowoi than tho singlot lovol ol tho host to piovont lack onoigy
tiansloi lion tho dopant to tho host.
In thoso two-layoi dovicos, 6 V8 V is ioquiiod to ioach signihcant liightnoss
( 1001000 cd n ¡. Thoso high opoiating voltagos ioßoct tho dilhculty in chaigo
injoction lion tho oloctiodos. Thoso dilhcultios aio causod ly tho nogligillo intiinsic
chaigo concontiation in tho oiganic natoiial and an onoigy lovol nisnatch with tho
oloctiodo Foini lovol. Tho voltago chaiactoiistics ol tho dovico can lo inpiovod ly
cioating noio chaigo caiiiois noai tho oloctiodo ly doping tho HTL (oi ETL¡ with
dopants that act to p-dopo (n-dopo¡ oi paitially oxidizo (ioduco¡ tho iogion ol tho
OLED layoi noai tho anodo (cathodo¡. Thoio aio now sovoial vapoi phaso ioutos to
chaigo doping that iosult in dosiiallo chaigo injoction chaiactoiistics and ioducod
opoiational voltago j2729|.
Flg. 8.5 Device structure {leFt) and energy level diagran
{right) oF a bilayer OLFD device prepared by vapor
deposition. 1he energy levels For the diagrans were taken
Fron inFornation obtained Fron ReFs. [26| and [36|.
8.3 key O|ED Trends and |nnoeat|ons 199
A luithoi iohnonont to tho two-layoi dovico stiuctuio is to insoit lotwoon tho ETL
and HTL a thiid distinct onission layoi that luithoi conhnos chaigo caiiiois and
oxcitons j30|. This appioach can lo oxtondod and nultiplo onission layois dopositod,
oach ol which possossos a dilloiont onission coloi. Using this idoa, a ''whito light ``
OLEDthat conlinod a lluo, gioon, and iodonittoi ina singlo, nany-layoi dovico was
dononstiatod j31|. Nunoious vaiiants ol tho gonoial dosign ol nultilayois to loico
chaigo conhnonont and lavoiallo luninoscont olhcioncy havo loon nado, and
cuiiontly a laigo vaiioty ol dopants and chaigo-tianspoiting host natoiials aio in
oxistonco j32|. Howovoi, whilo tho uso ol highly ßuoioscont dyos and sophisticatod
dovico aichitoctuios incioasos EL olhcioncy loi snall-noloculo OLEDs, only thoso
oxcitons that load to tho loination ol an onissivo stato with a high ioontonpoiatuio
quantun yiold aio haivostod. Excludod aio nost tiiplot oxcitons, as thoii slow
iadiativo iatos load to voiy snall ioon tonpoiatuio quantun yiolds. Sinco in tho
''statistical`` linit dosciilodoailioi, thoso tiiplot oxcitons conpiiso 75 %ol all oxcitons
loinod, this would potontially linit dovicos lasod uponoiganic oloctioluninosconco
to low powoi olhcioncios.
Sono oiganic natoiials, howovoi, oxhilit liight onission at ioon tonpoiatuio
lion tiiplot oxcitons. In thoso natoiials, tho singlot and tiiplot statos aio nixod, and
honco tho oxcitod tiiplot statos shaio sono singlot chaiactoi and havo nuch lastoi
iatos ol iadiativo docay to tho giound stato than a puio tiiplot stato. Foi instanco,
incoipoiating a hoavy notal aton, such as iiidiun, in an oigano-notallic noloculo
incioasos tho spin-oilit coupling that nixos singlot and tiiplot oxcitod statos j8|. Foi
sono Ii-containing noloculos, this nixtuio ol singlot and tiiplot statos incioasos tho
iato ol iadiativo onission to 10 s , and allows loi olhciont, phosphoioscont,
iadiativo docay ol tiiplot oxcitons j33|.
An oaily dononstiation ol a phosphoioscont OLED was nado ly Baldo ot al. and
involvod doping a platinun poiphyiin (PtOEP¡ phosphoioscont onittoi into a
standaid Alq host natoiial j34|. In this woik thoy showod that tho sinultanoous
uso ol loth a ßuoioscont (DCM2¡ and a phosphoioscont onittoi iosultod in a dovico
that oxhilitod onission lion loth tho ßuoioscont and phosphoioscont dopants.
Whon conpaiod to a sinilai dovico that was not dopod with PtOEP, tho intonsity ol
tho ßuoioscont onission was unchangod. This iosult indicatos that tho phosphoi-
oscont onittoi is allo to nako uso ol a dilloiont sot ol oxcitod statos in tho host
natoiial (i.o. tho tiiplot statos¡ than tho ßuoioscont onittoi. Onco again, onoigy
tiansloi nust lo lavoiallo lion tho host to onissivo dopant, and in this caso this
ioquiios that tho tiiplot onoigy ol tho dopant lo lowoi that tho tiiplot onoigy ol tho
host. Tho low tiiplot onoigy ol tho Alq host ( 1.9 oV¡ piovonts any othoi coloi than
doopiod lionloing oltainod using tiiplot onission, lut tho sano gioup voiy quickly
usod a dilloiont sot ol host natoiials and dopants to oltain loth lluo j35| and gioon
j36| onission. Foi oxanplo, tho host natoiial CBP has a highoi tiiplot onoigy lovol
(2.6 oV¡ and can lo usod to nako olhciont gioon (2.4 oV¡ onitting dovicos lasod upon
tho phosphoioscont iiidiun conplox Ii(ppy ¡ j37|.
Much woik has locusod on dovoloping and onploying phosphoioscont iiidiun
conploxos, and now gioon-onitting OLEDs havo loon dononstiatod which oxhilit a
''wall-plug`` olhcioncy ol 17 % at a piactical display liightnoss ol 100 cd n j38|. Tho
200 8 Organ|c E|ectro|un|nescence
dovico stiuctuio loi tho nost olhciont ol thoso dovicos to dato is dopictod in Fig. 8.6
and iopiosonts poihaps tho ultinato dovolopnont ol tho tochnology onallod ly oiganic
vapoi doposition. It consists ol no lowoi than 6 oiganic layois, oach ol which having a
spocihc lunction. Thus, adjacont to tho ITO stiuctuio, thoio is a p-dopod oiganic layoi
that pionotos holoinjoction. Sinco dopingsonotinos quonchos luninoscont olhcioncy,
thodopodlayoiisthonlollowodlya''lulloi`` layoi, whichtianspoitschaigoawayliontho
dopod layoi to tho onission zono. This layoi also piovonts oloctions lion ioaching
tho anodo. Tho noxt two layois constituto tho dosiiod onission zono loi this dovico
stiuctuio and consist ol two dilloiont host natoiials dopod with tho phosphoioscont
onittoi (Ii(ppy¡ ¡. Tho hist host natoiial, TCTA, is a holo tianspoit natoiial, whilo tho
noxt host, TAZ, is an oloction tianspoit natoiial with a doop HOMO lovol. This dosign
onsuios that holos luildupat thoTCTA]TAZintoilaco, whichloicos chaigos tonoot and
loinoxcitons withintho dosiiod zono. Tho noxt two layois aio anoloction-tianspoiting
lulloi layoi and an ''n-dopod`` layoi that pionotos tho injoction ol oloctions into tho
dovico. In addition, tho natoiials aio aiiangod so that tiiplots, whon loinod on tho
onission zono, do not nigiato to tho oloctiodo, lut aio iathoi loicod to ioconlino at
tho gioon onission sito.
Dotailod calculations ol tho light outcoupling olhcioncy loi tho gioon-onitting
phosphoioscont OLEDshown inFig. 8.6 indicato that noaily 100 %intoinal quantun
olhcioncy was achiovod. Achioving this lovol ol poiloinanco in tho lluo spoctial
iango has piovon noio challonging j35,39|. A koy issuo has loon tho dilhculty in
hnding host natoiials with good injoction and chaigo tianspoit piopoitios that also
satisly tho ioquiionont ol having tiiplot lovols alovo thoso ol lluo phosphoioscont
dopants. Additionally, in contiast to gioon oi iod onittois, it has loon dilhcult to hnd
puio lluo phosphoioscont onittois with adoquato stalility undoi opoiating condi-
tions j40,41|.
Flg. 8.6 Device structure {leFt) and energy level
diagran {right) oF an OLFD device with six
active organic layers prepared by vapor
deposition. 1he green arrows indicate the layers
Fron which enission is expected to take place.
1he prinary conponents oF each layer are given
beneath the diagran. Iey dopants are also
shown enclosed by parentheses.
8.3 key O|ED Trends and |nnoeat|ons 201
E|ectro|umlnescence From So|utlon-Deposlted Organlc Fl|ms
In gonoial, vapoi doposition piocossos, whilo olloiing oxquisito contiol ovoi tho hln
thicknoss, conposition, and nultilayoi oidoiing, ioquiio iolativoly sophisticatod
high-vacuun piocossing tochniquos. In addition, thoio aio linits on tho noloculai
woight ol a natoiial that nay lo piocossod using vapoi doposition nothods. Thoso
noloculai woight iostiictions linit tho dogioo ol conjugation and chonical lunc-
tionally that canlo luilt into a singlo noloculo. Whilo this linitation canlo ovoicono
thiough tho uso ol conplicatod nultilayoi aichitoctuios, uso ol thoso aichitoctuios
tonds to incioaso piocossing costs. Tho uso ol solution-piocossallo natoiials holds
pioniso loi ovoiconing thoso issuos. Contiollod piinting ol oiganic layois lion a
solution ol oloctio-activo natoiial can lo oxtionoly last potontially at a thioughput
and cost stiuctuio akin to that ol nowspapoi pioduction. Solution piocossing also
allows sono contiol ovoi tho hnal noiphology ol tho layoi thiough judicious choico
ol piocossing conditions j4244|. In addition, solution piocossing allows tho uso ol
high-noloculai-woight oligonois oi polynois that incoipoiato nultiplo typos ol
lunctional gioups, thoioly oxpanding tho availallo natoiial dosign options.
Tho advantagos ol solution piocossing aio ollsot ly tho dilhculty in loining
conplicatod nultilayoi stiuctuios, and thus solution-piocossod OLEDs ioquiio
natoiials that aio allo to poiloinwoll in sinplo stiuctuios. In addition, tho synthosis
and isolation ol highly puio polynoi natoiials is an ait loin in itsoll and ioquiios
noio donanding synthosis than tho isolation ol a noloculai spocios. Foi oxanplo, a
chonical ioaction that loads to tho loination ol an undosiiallo lypioduct 1 % ol tho
tino can usually lo puiihod quito oasily at tho noloculai lovol, lut can lo inpossillo
to sopaiato il tho lypioduct is incoipoiatod into a long-chain polynoi. Thus,
considoiallo natoiial dosign and dovolopnont olloit is ioquiiod to onginooi tho
piopoitios ol an OLED dovico nado using solution-lasod piocossing. As a conso-
quonco, solution-piocossod OLEDs havo nostly inpiovod as a iosult ol natoiials
dovolopnont, and not thiough incioasing dovico aichitoctuio sophistication. Tho
discussion in this soction will niiioi this tiond, and will piinaiily locus on sono ol
tho dilloiont stiands ol natoiials dovolopnont that havo onallod thoso poiloinanco
Sono ol tho hist solution-dopositod OLEDs woio lasod upon tho woll-known
polynoi polyvinyl cailazolo j25|, PVK (noto: stiuctuios loi this soction aio givon in
Figs. 8.8 and 8.9¡. This polynoi, which oxhilits a noai-UV]lluo luninosconco, also
has considoiallo chaigo nolility, paiticulaily loi holos j5|. In a soiios ol papois,
pullishod in tho oaily 1980s, Paitiidgo dononstiatod that thiough chonical oxida-
tion oi ioduction, loth oloctions and holos could lo injoctod into tho polynoi
natoiial. In addition, Paitiidgo showod that ly doping tho PVK with a luninoscont
dopant, tho onission coloi could lo ioadily tunod. Whilo thoso dovicos woio quito
thick ly today`s standaids (ianging lion 0.5 n to sovoial n in thicknoss¡ and
opoiatod at high voltago, thoy anticipatod nany loatuios that chaiactoiizo piosont day
vapoi-dopositod OLEDs, i.o. sopaiato holo and oloction injoction layois and a coloi-
tunallo dopant in an onissivo layoi. Thoso olononts aio all illustiatod in Fig. 8.7.
202 8 Organ|c E|ectro|un|nescence
As with vapoi-dopositod OLEDs, thoso polynoi-lasod dovicos woio laliicatod
staiting with a glass plato coatod with at tianspaiont conductoi. Tho noxt layoi that
was dopositod was a solution ol PVK and SlCl . Hoio tho SlCl acts as loth an
oxidizing agont to p-dopo tho PVK and, sinco PVK tonds to cioss-link whon oxidizod,
as a ciosslinking agont. Tho noxt layoi that was dopositod (again lion solution¡ was a
nixtuio ol PVK and a luninoscont dopant such as poiylono oi aciidino oiango.
Finally, a layoi ol cosiun notal was dopositod on top. Following cosiun doposition,
Flg. 8.7 Schenatic illustration oF a solution-processed OLFD
nade using PvI as the prinary electroactive conponent
{6gure taken Fron the United States Patent [45|).
Dopant+Host Dendrimer
Conjugated Polymer
(alternating co-polymer)
Acridine Orange
Flg. 8.8 Sone oF the naterials used in solution-processed
devices. Linear polyners are denoted by the brackets and
asterisks on each side oF the repeat unit.
8.3 key O|ED Trends and |nnoeat|ons 203
tho PVK hln was olsoivod to daikon, suggosting n-doping thiough tho loination ol
cailazolo anions. Instoad ol diioctly ioducing tho polynoi, it was also dononstiatod
that oloctiontianspoit could lo lacilitatodly inclusion ol a dopant noloculo (typically
a di- oi tii-cyanolonzono doiivativo¡ that acts as an oloction accoptoi in PVK at
sulhciont concontiation to piovido a low-onoigy hopping pathway. Thus, instoad ol
having to injoct oloctions diioctly into PVK, tho oloctions could lo injoctod into tho
noio oasily ioducod dopant noloculos, olininating tho nood loi highly ioactivo
cathodos such as cosiun.
Paitiidgo`s woik, which was actually patontod in tho 1970s j45|, dononstiatod an
inpoitant advantago ol solution-piocossing loi OLEDs tho alility to nix a vaiioty ol
iolativoly conplox noloculai stiuctuios togothoi in solution to loin a thin hln
dosignod loi nultiplo lunctions. Howovoi, luithoi woik in this aioa did not pick up
until tho two-layoi lioakthiough in vapoi-dopositod OLEDs was iopoitod in tho lato
1980s. Rosoaichois thon inpiovod Paitiidgo`s oiiginal PVKsyston ly applying noio
olloctivo dopants loi oloction tianspoit and luninosconco j46|. Moio iocontly, altoi
tho intioduction ol phosphoioscont OLEDs, tho uso ol PVK has accoloiatod, sinco its
iolativoly high tiiplot lovol nakos it an attiactivo solution-piocossallo host syston.
Rocont iosults utilizing PVK co-dopod with loth tiiplot onittois and chaigo-tians-
poiting snall noloculos dononstiatod that voiy high poiloinanco can lo oltainod
using this lasic dosign and host natoiial j47,48|.
Rosoaich in solution-piocossallo OLEDs accoloiatod gioatly in tho oaily 1990s,
whon it was discovoiod that iolativoly olhciont singlo-layoi dovicos could lo nado
using conjugatod polynois. Conjugatod polynois aio uniquo in that thoy havo
altoinating singlo and doullo londs along tho polynoi lacklono that iosult in
oxtondod oloctionic statos ovoi nultiplo polynoi iopoat units j49|. In dovicos, thin
hlns ol conjugatod polynois lohavo sinilaily to thin hlns ol snall noloculos in that
chaigo injoction is linitod ly tho onoigy lovol nisnatch with tho oloctiodos and is
inpiovodly chaigo doping, and in that chaigo tianspoit is linitod ly chaigo hopping
lotwoon polynoi chain sognonts. Howovoi, in addition, tho oxtondod statos onallo
noio olloctivo chaigo notion along tho chainaxis and, as discussod oailioi, accoiding
to sono thooiotical nodols, tho potontial loi a highoi iatio ol singlot to tiiplot
loination undoi dovico-opoiating conditions.
Tho hist dononstiation ol a conjugatod polynoi in an OLED utilizod phonylono
vinylono (PPV¡, which is highly luninoscont in thin-hln loinovon in tho alsonco ol
additional dopants j50|. Tho hist dovico had a voiy sinplo stiuctuio consisting ol a
plato ol ITO-coatod glass as tianspaiont anodo, tho polynoi layoi (70-nn thicknoss¡,
and a top vapoi-dopositod aluninun layoi. Puio PPV doos not dissolvo in nost
solvonts, so tho thin hln was loinod ly hist dopositing polynoi piocuisois lion
solution and thon polynoiizing tho iosulting hln in situ via hoat tioatnont. Soon
altoi this dononstiation, solullo vaiiants ol PPV, such as MEH-PPV, woio utilizod, so
that tho hnal natoiials could lo solution dopositod into a thin hln in ono stop j51|.
Also soon thoioaltoi, it was lound that tho iopoatalility and stalility ol PPV-lasod
dovicos could lo onhancod ly dopositing a highly p-dopod conjugatod polynoi such
as PEDOT:PSS (a poly(3,4-othylonodioxythiophono¡poly(styionosullonato¡ llond¡ oi
polyanilino lotwoon tho ITO and tho light-onitting polynoi j52,53|. At piosont, this
204 8 Organ|c E|ectro|un|nescence
lasic conhguiation ol a highly dopod conjugatod polynoi layoi lollowod ly an
undopod light-onitting polynoi layoi is still tho nost populai solution-piocossallo
dovico conhguiation.
Vaiious nodihcations ol tho lasic PPVstiuctuio havo loon nado to onallo tuning
ol tho onission coloi lion gioon to iod lut not lluo j54|. On tho othoi hand, light-
onitting polynois woio dovolopod lasod on tho lasic polyßuoiono stiuctuio which
aio tunallo in coloi ovoi tho wholo visillo iango. Tho polyßuoiono syston has
onallod incioasing natoiial dosign sophistication thiough tho uso ol tho Suzuki
ioaction j55|. This ioaction poinits a wido vaiioty ol AB-typo iogulai altoinating
polynois to lo ioadily piopaiodinhighnoloculai woight. This piovidos anadditional
dogioo ol stiuctuial contiol and polynoi dosign ßoxilility and has lod to sono
natoiials that canlo tunodto havo oxcollont spocihc piopoitios. Exanplos includo tho
ßuoiono-tii-aiyl anino co-polynois which woio onginooiod to havo voiy high holo
nolilitios. This polyßuoiono syston was aggiossivoly oxaninod ly tho Dow Cho-
nical conpany in tho lato 1990s and has iosultod in a suito ol lull-coloi-onissivo
natoiials j56| (iod, lluo, gioon¡ and a soiios ol holo tianspoit natoiials j57|. Thoso
natoiials havo loon shown to yiold voiy high poiloinanco, with EQEs gioatoi than
8 % at voiy low opoiating voltagos j58|.
Ono ol tho dosignphilosophios that has poivadod tho light-onitting polynoi hold
has loon tho dosiio to pioduco highly olhciont dovicos using only a singlo oiganic
thin hln layoi. Pait ol tho ioason loi this philosophy has loon tho dosiio loi sinplo,
low-cost laliication piocossos. Howovoi, anothoi ioason has loon tho piactical
considoiation that it is dilhcult to nako nultilayoi dovicos via solution piocossing,
locauso tho solvont ioquiiod to doposit a top layoi olton dissolvos an undoilying
layoi. As tho dosign sophistication ol polynois has incioasod, it has now locono
possillo to dosign polynois that aio not dissolvod ly connon solvonts, this loing
achiovod oithoi thiough a ciosslinking stiatogy j59| oi thiough judicious lunctio-
nalization. Thus, olloits aio undoi way to apply sono ol tho lossons loainod lion
nultilayoi vapoi-dopositod OLED tochnology to inpiovo solution-piocossod
dovicos. An oxanplo is tho uso ol a layoi ol a tii-aiylanino-ßuoiono copolynoi
undoi an onissivo ßuoiono copolynoi j60|. This nultilayoi appioach lod to an
incioaso in loth olhcioncy and lilo iolativo to a singlo layoi dovico with tho sano
onissivo copolynoi.
Tho PPV and polyßuoiono conjugatod polynoi systons oxhilit iolativoly low
onoigy tiiplot statos. This chaiactoiistic nakos thon unsuitallo loi uso as host
natoiials loi gioon- and lluo-onitting phosphoioscont natoiials. Thus, whilo
natoiials lasod upon polyßuoiono (tiiplot onoigy ol 2.15 V j61|¡ havo loon usod
to piopaio polynois andoligonois with iodtiiplot onissivo dopants j62|, thoio aio no
oxanplos which succosslully uso polyßuoiono oi othoi conjugatod linoai polynois as
hosts loi gioon oi lluo phosphoioscont natoiials. Sooningly, tho only way to achiovo
voiy high olhcioncios with such linoai conjugatod polynois is to dosign a stiuctuio
which loicos all ioconlination ovonts to load to singlot statos, which is a daunting
task lion loth a thooiotical and a chonical synthosis point ol viow.
An altoinativo appioach to olhciont light gonoiation is to dosign othoi classos ol
solution-piocossallo natoiials that will suppoit onission lion lluo oi gioon
8.3 key O|ED Trends and |nnoeat|ons 205
tiiplot statos. Ono oxanplo is tho uso ol highly stiuctuiod non-linoai noloculos
such as dondiinois j63|. Thoso noloculos aio intoinodiato in noloculai woight
lotwoon polynois and vapoi-dopositod noloculos and loatuio an onissivo coio
chonically londod to a chaigo-tianspoiting dondiinoi stiuctuio. Sinco tho contial
onitting spocios is lully suiioundod, thoso noloculos aio lully thioo-dinonsional
stiuctuios, in contiast to noio connonly usod ''ono-dinonsional`` polynois. Tho
thicknoss ol tho layoi that suiiounds tho onissivo coio is dotoininod ly tho
''gonoiation`` ol tho dondiinoi and can lo also tunod. Tho dondiinoi noloculo
can lo thought ol as oithoi a phosphoioscont noloculo with a voiy laigo ligand, as
shown ly tho ''hist-gonoiation`` lluo-onitting spocios shown in Fig. 8.8 (G1-Fii¡
oi as voiy laigo chaigo tianspoiting natoiials with a luninoscont coio as shown in
Fig. 8.9. Thus, thoso natoiials can lo usod oithoi noat oi co-dopositod as a dopant
in anothoi layoi. Rocont studios havo shown that OLED dovicos incoipoiating
phosphoioscont Ii coios can lo nado in a vaiioty ol colois and havo EQE
olhcioncios conpaiallo to vapoi-dopositod OLED stiuctuios j64|. Thoso systons
piovido loi an ovon laigoi dogioo ol noloculai onginooiing than nodihcation ol
linoai polynois whilo still iotaining tho oaso ol piocossing that is achiovod via
solution piocossing.
It should lo notod that this tioatnont has only touchod on sono ol tho najoi
natoiial classos. Many noio typos ol solution-piocossallo natoiials havo loon
Flg. 8.9 Structural Fornula oF a second-generation green-enitting dendriner.
206 8 Organ|c E|ectro|un|nescence
synthosizod, and now natoiials aio appoaiing daily. Matoiial dovolopnont in this
hold is still in its inlancy, and thoio aio an inhnito vaiioty ol chonically accossillo
stiuctuios that can lo piopaiod in sulhciont puiity and quantity. Ono should thus
oxpoct that thoso natoiials will continuo to natuio and load to solution-piocossod
dovicos with ovoi gioatoi poiloinanco.
Prospects For Cenera| I||umlnatlon
Most ol tho olloit oxpondodto dato ondovoloping OLEDtochnology has loon ainod at
dovoloping an OLED-lasod display. Piogioss in this ondoavoi has loon considoiallo.
OLED displays loi snall-loinat applications aio now connoicially availallo. It is
gonoially agioodthat OLEDdisplays havo supoiioi display chaiactoiistics, o.g., viowing
anglo, liightnoss, and olhcioncy, to thoso ol convontional liquid-ciystal display (LCD¡
tochnology j3|. Howovoi, OLEDs still iopiosont onlyasnall liactionol tho total availallo
ßat-panol display naikot. Fuithoi adoption ol OLED displays ioquiios continuod
tochnology dovolopnont to onallo intogiation with high-poiloinanco and laigo-aioa
activo natiix lackplanos, and nany conpanios aio puisuing thoso goals.
Staiting in ca. 2000, tochnology oiganizations aiound tho woild havo staitod to
oxploio tho possilility ol dovoloping OLEDs loi lighting, iathoi than display,
applications. Ono ioason loi this intoiost is tho tionondous iato ol incioaso in
olhcioncy that has loonachiovod ovoi tho last docado. As dosciilod intho last soction,
gioon-onitting OLEDs havo piogiossod lion 1 LPW to 100 LPW at liightnoss
lovols adoquato loi displays. Asinilai iato ol piogioss in naking illunination-quality
light would inply that OLEDs havo tho potontial to not only suipass incandoscont
lighting souicos, which havo anolhcacy ol 15 LPWand a lilotino ol 1000 h, lut ovon
ßuoioscont lighting souicos, which havo an olhcacy ol 100 LPW and a lilotino ol
20 000 h.
An oqually inpoitant attiiluto ol OLED tochnology is tho potontial loi low cost.
Eloctiic lighting tochnology has oxistod loi ca. 100 yoais and, in this tino, optiniza-
tion ol nass pioduction nothods has lod to a highly alloidallo tochnology that is, at
loast in tho dovolopod woild, takon loi giantod as a low cost nocossity. Thoso
poicoptions inposo cost constiaints on any now lighting tochnology. OLEDs aio
potontially consistont with thoso constiaints lundanontally locauso tho oloctio-activo
oiganic natoiials do not nood to lo laliicatod into a singlo ciystal loin loi piopoi
dovico opoiation. Foi oxanplo, tho activo layois ol tho polynoi-lasod tochnologios
can lo dopositod with high thioughput ioll-to-ioll tochniquos such as giavuio oi
ßoxogiaphic piinting.
Anothoi inpoitant loatuio ol OLEDtochnology is tho potontial loi nowdovico loin
lactois. Eaily on, it was dononstiatod that OLEDs can lo laliicatod on ßoxillo plastic
sulstiatos j65|. This hist dononstiation was not piactical locauso tho plastic
sulstiato was not hoinotic onough to piotoct tho OLED lion noistuio and
oxygon-inducod dogiadation. Howovoi, noio iocontly, tianspaiont, ßoxillo, plastic
sulstiatos havo loon dononstiatod which piovido tho ioquiiod hoinoticity, and
8.4 Prospects jor Genera| |||un|nat|on 207
thoso havo loon succosslully utilizod as sulstiatos loi OLEDs j66,67|. Anochanically
ßoxillo OLED that onallos now loin lactois is not nocossaiily ioquiiod loi gonoial
illunination applications. Howovoi, this loatuio will likoly lo inpoitant in onalling
tho oaily connoicialization ol OLED lighting pioducts. In paiticulai, sinco it
piovidos a lunction that is not possillo today, it will onallo tho oaily adoption ol
OLED lighting ovon loloio tho tochnology is conpotitivo with convontional lighting
tochnology on a cost oi olhcioncy lasis.
A Flrst OLED Llghtlng Demonstratlon
In 2003, a koy nilostono was achiovod whon an OLED was dononstiatod that could
piovido light with a quality, quantity, and olhcioncy ona pai withwhat canlo achiovod
with tiaditional light souicos. Tho actual 2 lt 2 lt dononstiation dovico and sono
koy poiloinanco notiics aio shownin Fig. 8.10. Tho dononstiationdovico was nado
ly tiling togothoi 16 sopaiato 6 in 6 in lluo-onitting OLEDs, oach ol which was
nado on a glass sulstiato. Noto that tho olhcioncy, total lunon output, and lilotino
aio tho sano as would lo achiovod with an 80-W incandoscont lull. Foi lighting, tho
appiopiiato whito coloi is dotoininod ly tho coiiolatod coloi tonpoiatuio (CCT¡ ol
tho souico and should lo in a iango lotwoon 2800 K and 6000 K. Tho illunination
quality ol a givon light souico is typically noasuiod in toins ol tho coloi iondoiing
indox (CRI¡, which has a naxinun possillo quality valuo ol 100 and is typically
aiound 80 loi tho standaid ßuoioscont lanps usod in nost nodoin connoicial
Flg. 8.10 2 Ft 2 Ft OLFD denonstration device and sone
key perFornance 6gures. 1he active layers oF the device
were prepared using solution processing. All the light
utilized For these pictures is generated by the OLFD.
208 8 Organ|c E|ectro|un|nescence
luildings. Boththo CCTand CRI canoasily lo calculatod liontho output spoctiunol
tho light souico j7,70|. Ono can soo that tho coloi tonpoiatuio loi tho dononstiation
dovico is appiopiiato loi lighting and that tho coloi iondoiing indox is slightly lottoi
than that ol standaid ßuoioscont lanps.
Tho dovico dopictod in Fig. 8.10 onployod solution-piocossod OLEDS and intio-
ducod thioo tochnology stiatogios dovolopod spocihcally loi OLED lighting down-
convoision loi whito light gonoiation j68|, scattoiing loi outcoupling olhcioncy
onhanconont j21|, and a scalallo nonolithic soiios aichitoctuio to onallo laigo-aioa
dovicos to lo pioducod j69|. In tho lollowing, a liiol dosciiption ol thoso tochnology
stiatogios is piovidod along with tho notivation loi thoii adoption. Downconverslon For whlte Llght Ceneratlon
Tho downconvoisionappioach consists ol optically coupling a lluo-onitting OLEDto
a phosphoi downconvoision layoi j68|. Tho downconvoision layois aio choson to
alsoil tho lluo OLED onission and thon io-onit at longoi wavolongths. Tho layois
aio dosignod such that tho unalsoilod lluo onission and tho longoi wavolongth
io-onission conlino to nako whito light. This appioach is attiactivo loi lighting
applications locauso only a singlo coloi OLED with a singlo onitting spocios is
ioquiiod. Fig. 8.11 dopicts an inplonontation ol this dovico aichitoctuio, consisting
ol a polynoi-lasod lluo-onitting OLEDand thioo downconvoisionlayois. Two ol tho
downconvoision layois utilizo poiylono-lasod dyos lion BASF AG ol Goinany with
high quantun olhcioncy (98 %¡, and ono ol tho layois consists ol inoiganic
Flg. 8.11 Schenatic oF a white-light OLFD nade using a
downconversion architecture. 1he source consists oF a blue
OLFD and three phosphor layers. At the lower leFt is shown
an actual neasured electroluninescence spectrun Fron a
blue device. 1he calculated white-light enission spectrun
Following transnission, absorption, and enission oF the
light through each layer is shown on the right.
8.4 Prospects jor Genera| |||un|nat|on 209
phosphoi paiticlos jY(Gd¡AG:Co| with a quantun olhcioncy ol 85 %. By indopon-
dontly vaiying tho thicknoss ol thoso downconvoision layois, tho conposito onission
spoctiun can lo vaiiod to naxinizo poiloinanco loi lighting (o.g., llack-lody
tonpoiatuio andcoloi iondoiing¡ whilo kooping tho piopoitios ol tho undoilying lluo
OLEDconstant. Anoxanplo spoctiunoptinizod loi gonoial lighting is shownontho
iight hand sido ol Fig. 8.11.
Tho downconvoision aichitoctuio has sovoial loatuios that nako it attiactivo
loi lighting. To a hist appioxination, thoio should lo no coloi chango as tho
luninanco oi cuiiont donsity is vaiiod. Sinilaily, coloi shilts duo to dilloiontial
aging ol dilloiont coloi conpononts aio avoidod il ono onsuios that tho lilotino ol
tho down-convoision layois is sulstantially gioatoi than that ol tho undoilying
lluo OLED. This ioquiionont is not paiticulaily onoious, as inoiganic phosphoi
natoiials aio alioady dosignod to lo stallo ovoi tho lilotino ol ßuoioscont lanps, and
thoio aio a nunloi ol long-livod oiganic dyos that woio oiiginally dosignod loi
applications such as solai colloction. An addodlonoht ol this appioach is that a singlo
lluo OLEDdovico canlo utilizod loi a wido vaiioty ol applications ioquiiing dilloiont
coloi tonpoiatuios and]oi coloi iondoiing capalilitios ly sinply vaiying tho appliod
downconvoision layois. Finally, this aichitoctuio is iolativoly sinplo, ioquiiing tho
nanulactuio ol a singlo-coloi OLED lollowod ly tho application ol a sot ol phosphoi
layois ly noans ol a piinting oi lanination tochniquo. OLED pioduction costs aio
thus nininizod, and a wido vaiioty ol hnal whito colois can lo achiovod whilo only
having to naintain ono sot ol natoiials loi tho lluo OLED ''ongino`` and ono
pioduction lino.
Thoio aio two lossos associatod with any downconvoision appioach. Ono is tho
Stokos loss associatod with tho lact that highoi-onoigy photons aio convoitod to
lowoi-onoigy photons and tho othoi is sinply tho lact that tho quantun olhcioncy
loi downconvoision is typically loss than 100 %. It is inpoitant to ioalizo that tho
Stokos loss is not uniquo to tho downconvoision appioach. Although not oxplicitly
dohnod as a Stokos loss, any whito OLED that iuns oll ol a singlo voltago has this
typo ol loss locauso tho voltago noods to lo high onough to allow tho highost
onoigy (lluo¡ onission. This is a loss locauso, in piinciplo, tho lowoi onoigy
onission colois would ioquiio lowoi voltagos il opoiatod alono. Foi oui phosphoi
systonwo calculato that thoio is a alout a 20 % loss in onoigy olhcioncy duo to this
toin. Scatterlng For Outcoup|lng EFhclency Enhancement
As dosciilod in Soction 8.1, oloctioluninoscont dovicos aio linitod ly tho optical
oxtiaction olhcioncy,  , which is tho iatio ol tho light gonoiatod within tho dovico
to tho light onittod into tho anliont. Tho dononstiation lighting dovico utilizod light
scattoiing to incioaso this iatio. Tho light-scattoiing lunction was piovidod ly tho
Y(Gd¡AG:Co downconvoision layoi at tho top suilaco ol tho dovico. In lact, this layoi
incioasod tho light oxtiaction to tho point whoio tho onoigy olhcioncy ol tho dovico
with all tho downconvoision layois was actually highoi than tho onoigy olhcioncy ol
tho dovico without thon. To conhin this assignnont, a tapo ol non-alsoiling
scattoiing paiticlos in silicono was nado and appliod to a lluo OLEDdovico. Caio was
210 8 Organ|c E|ectro|un|nescence
takon to uso paiticlos with sinilai sizo and loading as thoso usod in tho YAG:Co layoi
ol a whito dovico. Tho iosulting lluo dovico showod a 27 % onhanconont in tho
noasuiod oxtoinal quantun olhcioncy iolativo to tho dovico without tho scattoiing
tapo. This 27 %incioaso ovoiconos tho 20 %loss intioducod ly downconvoision and
loads to a not incioaso in onoigy olhcioncy.
Light scattoiing onhancos outcoupling olhcioncy ly scattoiing a poicontago ol
tho light nodos that aio noinally tiappod in tho dovico to nodos that can oscapo
lion tho dovico. Tho potontial achiovallo onhanconont can lo accuiatoly calcu-
latod using a iadiativo tianspoit nothodology j21|. Such calculations suggost that
ono can utilizo voluno scattoiing to incioaso tho light output ly up to a lactoi ol 2.
Sinco scattoiing can lo acconplishod sinply ly applying ultia-low-cost natoiials
such as titaniun dioxido paiticlos, this appioach to incioasing output coupling
olhcioncy is uniquoly suitod to tho cost ioquiiononts ol gonoial lighting
applications. A Sca|ab|e Mono|lthlc Serles Archltecture
OLEDs aio cuiiont-diivon dovicos and, locauso ol thoii thin activo layois, aio
oxtionoly sonsitivo to dolocts that causo oloctiical shoits. Thoso two chaiactoiistics
aio tho koy linitations to laliicating laigo-aioa OLEDs, paiticulaily non-pixolatod
dovicos such as gonoial lighting dovicos. Cuiiont diiving inplios that, loi laigo-aioa
dovicos, thoio will lo a laigo olhcioncy loss and nonuniloinity in onission duo to tho
spioading iosistanco ol tho iolativoly iosistivo tianspaiont conductoi. Sinilaily, as
dovico aioa incioasos, thoio will lo an incioasod chanco ol an oloctiical shoit, which
will causo olhcioncy loss and nonuniloinity. In an olloit to ovoicono thoso issuos loi
tho dononstiation dovico, tho soiios aichitoctuio dopictod schonatically in Fig. 8.12
was utilizod j69|.
Tho aichitoctuio woiks ly dividing tho dosiiod laigo-aioa dovico into sopaiato
snalloi onitting olononts connoctod nonolithically in soiios. With this appioach,
tho ioquiiod cuiiont is contiollod ly tho individual olonont aioa iathoi than ly tho
total onitting aioa ol tho dovico. Tho individual olonont aioa can always lo choson to
nininizo cuiiont-spioading ollocts. Sinilaily, tho soiios connoction addiossos tho
oloctiical shoit issuo. Shoits still occui lut thoii dolotoiious olloct loconos isolatodto
Flg. 8.12 Schenatic side view representation oF the series-
connected architecture used in the denonstration device
shown in Fig. 8.10.
8.4 Prospects jor Genera| |||un|nat|on 211
tho paiticulai olonont alloctod, whilo tho ioquiiod cuiiont continuos to ßowthiough
tho iost ol tho dovico. This nininizos tho olhcioncy loss that occuis duo to shoits
without ioquiiing any activo contiol olononts.
Tho dononstiation dovico shown in Fig. 8.10 was nado ly tiling togothoi 16
sopaiato 6 in 6 in lluo-onitting OLEDs, oach ol which was nado on a glass
sulstiato using tho nonolithic soiios aichitoctuio. Tho total aioa ol oach 6 in 6 in
6 in dovico was dividod into 144 1.2-cn onitting olononts consisting ol 12 iows
connoctod oloctiically in paiallol, whoio oach iow containod 12 olononts connoctod
in soiios, as dopictod in Fig. 8.12. In oidoi to nako whito dovicos, downconvoision
layois woio optically couplod to tho output sido ol tho 6-in lluo OLEDs, as dopictod in
Fig. 8.11.
EFhclency Cha||enge For Cenera| I||umlnatlon
Tho hist OLED lighting dononstiation dosciilod alovo nicoly illustiatos what tho
ultinato goal nust lo in oidoi to onallo gonoial illunination applications. Tho
koy point to noto is that, in oidoi to gonoiato a lunon output iolovant loi lighting,
a iolativoly laigo (4 lt ¡ suilaco aioa was onployod. This is in contiast to an
incandoscont lull, which gonoiatos tho sano lunon output lion a nuch snalloi
aioa. Tho ioquiiod OLED aioa could lo docioasod ly incioasing tho input powoi
and honco output liightnoss, lut thoio is a tiadooll lotwoon liightnoss and
opoiating lilo which nakos it unlikoly that tho aioa could shiink to that ol an
incandoscont lull. This illustiatos tho lact that OLEDs aio ly natuio a dilluso light
souico. Cuiiontly, tho pionioi dilluso light souico is tho ßuoioscont lull. Honco,
in oidoi to locono a conpotitivo light souico loi gonoial illunination, OLED
tochnology nust natch tho poiloinanco and cost that is achiovallo with ßuoi-
oscont tochnology.
Tho olhcioncy ol a high-poiloinanco ßuoioscont lull ol 100 LPWcoiiosponds to a
wall-plug olhcioncy ol 28 %. This is noio than6 tinos highoi thanthat attainod in tho
dononstiation dovico. OLEDs nust lo allo to natch oi oxcood this valuo in oidoi to
displaco ßuoioscont tochnology on tho naikot. Tho olhcioncy ol tho OLED lighting
dononstiation was linitod ly tho poiloinanco ol tho undoilying lluo-onitting
OLED, sinco downconvoision was onployod to gonoiato tho iod and gioon coloi
conpononts ol tho whito light. Howovoi, it is in lact gonoially tiuo that tho olhcioncy
ol a whito-onitting OLED is linitod ly tho gonoiation olhcioncy ol tho lluo
conponont ol tho spoctiun iogaidloss ol tho dovico dosign utilizod. This stons
lion tho lact that illunination-quality whito light ioquiios no loss than a 25 %
contiilution oi woighting ol oach piinaiy coloi conponont (iod, gioon, oi lluo¡ j70|.
Whon whito light is gonoiatod ly a non-downconvoision nothod, o.g., ly nixing tho
light lionsopaiato iod, gioon, and lluo OLEDs, ono night oxpoct that tho naxinun
achiovallo olhcioncy would lo linitod ly tho coloi conponont which is gonoiatod
loast olhciontly. Howovoi, locauso tho iod and gioon coloi conpononts can altoi-
nativoly lo nado ly coupling tho appiopiiato downconvoision layoi to a lluo OLED
with ioasonallo olhcioncy, ono can always conponsato loi an inolhciont iod oi gioon
212 8 Organ|c E|ectro|un|nescence
dovico. Thus, to inpiovo tho poiloinanco ol whito-onitting OLEDs loi lighting, it is
ciitical to concontiato on onsuiing that tho lluo conponont ol tho hnal spoctiun is
gonoiatod as olhciontly as possillo.
Foi lluo ßuoioscont dovicos liko thoso usod to nako tho dononstiation dovico
shown in Fig. 8.10, it is possillo to opoiato OLEDs with 1000 cd n liightnoss at
3.23.3 V. Thus, tho piinaiy linitation ol thoso dovicos is thoii oxtoinal quantun
olhcioncy, which is cuiiontly 89 % loi lluo-polynoi OLED dovicos. At tho piosont
tino, oach ol tho appioachos to lluo-dovico laliication dosciilod in Soction 8.2
(dopod host, co-polynois, dondiinoi, and vapoi doposition¡ yiold voiy sinilai
valuos ol oxtoinal quantun olhcioncy loi lluo dovicos. Thoso olhcioncios aio listod
in Tallo 8.1.
All ol thoso dovicos woio noasuiod without tho uso ol additional scattoiing oi othoi
optical onhanconont tochniquos. Evonusing light onhanconont tochniquos, inoidoi
to ovoitako tho 28 % wall-plug olhcioncy ßuoioscont lanp, sulstantial tochnical
piogioss is ioquiiod.
In addition to olhcioncy, thoio aio two othoi koy challongos that nust lo ovoicono
to onallo OLEDs to displaco ßuoioscont tochnology loi gonoial lighting. Thoso aio
to achiovo an opoiating lilotino ol 20 000 h at a liightnoss ol 1000 cdn and to
achiovo a cost ol loss than S10 loi a dovico that pioducos 1000 lunons ol light. A
dotailod oxplanation loi thoso taigots has loon givon olsowhoio j7|. Foi tho puiposos
ol this chaptoi, tho koy point to onphasizo is that thoso paiallol challongos nust lo
takon into considoiation whon dosigning stiatogios to incioaso OLED olhcioncy loi
Oiganic natoiials, which havo loon tiaditionally viowod as ''solt``, nalloallo
insulatois, aio now loing succosslully utilizod loi oloctioluninoscont applications
ioquiiing thousands ol houis ol lilo, tiaditionally tho donain ol ''haid`` inoiganic
soniconductoi natoiials. Whilo tho lundanontal physical opoiation ol thoso
oiganic light-onitting dovicos can lo dosciilod using tho tiaditional tools ol
soniconductoi physics, thoio aio sovoial notallo dilloioncos in how chaigos novo
1ab. 8.1 Fxternal quantun eFFiciencies For various nethods
oF blue-device Fabrication.
System % EQE ReF.
PVKlluo phosphoioscont dopant 9 j47|
Bluo conjugatod polynoi 9 j58|
Bluo phosphoioscont dondiinoi 10.4 j64|
Vapoi-dopositod lluo 11.6 j39|
8.5 Conc|us|ons 213
and ioconlino, and thoso dilloioncos intioduco now challongos lut also now
dosign oppoitunitios.
Thoio aio two lasic OLED dosign paiadigns. Ono utilizos iolativoly sinplo
noloculai oiganic natoiials that aio vapoi piocossod into iolativoly sophisticatod
nultilayoi dovico aichitoctuios. Tho othoi paiadign utilizos highoi-noloculai-
woight and noio conplox oiganic natoiials lut nuch sinploi dovico aichitoc-
tuios. Thoso highoi-noloculai-woight natoiials cannot lo ovapoiatod, and so thoy
aio instoad piocossod lion solution using piinting tochniquos that should lo
scalallo to high thioughput and low cost. To dato, tho hist paiadign, vapoi
piocossing, has always lod in dovico poiloinanco. This is in pait locauso ol
tho iolativo oaso in cioating and tosting now dovico aichitoctuios in tho laloiatoiy.
It is haidoi to luild conplox dovico aichitoctuios at whin using solution piocos-
sing, lut tho oxtia noloculai dosignßoxilility that is possillo with high-noloculai-
woight chonical stiuctuios has to a laigo oxtont conponsatod loi this disadvan-
tago. Thus, tho poiloinanco ol solution-piocossod OLEDs has novoi laggod lai
lohind that ol vapoi-dopositod OLEDs. Both paiadigns ioly upon tho capalilitios
ol nodoin oiganic chonistiy to cioato a laigo vaiioty ol dilloiont oiganic
noloculos, and loth olloi tho potontial loi dovicos with incioasod olhcioncy
and lilotino.
Rosoaichois aio putting incioasing olloit into dovoloping OLEDs loi tho
ultinato luninoscont application gonoial lighting. Ovoiall, thoio is good ioason
to lo optinistic that OLED-lasod gonoial lighting will locono a ioality. Tho hold
ol oiganic oloctioluninosconco has dononstiatod inciodillo piogioss in tho last
docado piogiossing lion voiy piinitivo dovicos to laigo, olhciont dononstiation
dovicos. Fuithoinoio, tho hold is ioally still in its inlancy with iogaid to undoi-
standing what typos ol noloculos should lo nado. Whilo tho dovico physics ol an
OLED is laigoly undoistood, tho iolationship lotwoon noloculai stiuctuio and tho
dotailod physics ol chaigo tianspoit, oxciton spin loination, and onoigy tiansloi
in anoiphous oiganic natoiials is not. As lasic iosoaich into tho lundanontal
physics and chonistiy ol oiganic natoiials continuos and locusod iosoaich on
dovoloping OLEDs loi gonoial lighting accoloiatos, it is likoly that tho oxponontial
iato ol piogioss soon in tho last docado will continuo into tho noxt. Il so, thon ly tho
ond ol tho noxt docado tho only lactoi that could possilly piovont tho laigo-scalo
adaptation ol an OLED-lasod lighting tochnology would lo cost. Givon tho lact
that, ovon today, OLEDs aio allo to lovoiago low-cost, high-thioughput tochnol-
ogios lion tho piinting industiy, it would lo suipiising il this huidlo could not lo
ovoicono as woll.
Tho authois aio giatolul loi tho suppoit ol tho Oiganics Eloctionics Advancod
Tochnology Piogian at GE Glolal Rosoaich, and wish to thank thoii colloaguos
involvod with tho piogian loi thoii nunoious tochnical contiilutions and insights.
214 8 Organ|c E|ectro|un|nescence
1 Fiiond, R. H., Gynoi, R. W., Holnos,
A. B., Buiioughos, J. H., Maiks, R. N.,
Taliani, C., Biadloy, D. D. C., Dos
Santos, D. A., Biodas, J. L., Logdlund,
M., Salanock, W. R. (1999¡ Nuturc,
397, 121.
2 Foiiost, S. R. (2000¡ !EEE ]curnu| cj
Sc|cctcd 1cpics in Quuntun E|cctrcnics,
6, 1072.
3 Wakinoto, T. (2005¡ Past, Piosont,
Futuio Diioctions ol Oiganic
Eloctioluninoscont Displays, in
Orgunic E|cctrc|unincsccncc, (od.
Z. H.Kalah¡, Tayloi & Fiancis
Gioup, Boca Raton, FL, 391.
4 Canploll, I. H. and Snith, D. (2001¡
Sc|id Stutc Pnys., 55, 1.
5 Popo, M. and Swonloig, C. (1982¡
E|cctrcnic Prcccsscs in Orgunic Crystu|s,
Oxloid Univoisity Pioss, Oxloid.
6 Boigh, A., Cialoid, G., Duggal, A.,
Haitz, R. (12]2001¡ Pnysics 1cduy, 54,
7 Duggal, A. R. (2005¡ Oiganic
Eloctioluninoscont Dovicos loi Solid
Stato Lighting, in Orgunic
E|cctrc|unincsccncc, (od. Z. H.Kalah¡,
Tayloi & Fiancis Gioup, Boca Raton,
FL, 437.
8 Tuiio, N. J. (1978¡ Mcdcrn Mc|ccu|ur
Pnctccncnistry, Bonjanin]Cunnings,
Monlo Paik.
9 Sogal, M., Baldo, M. A., Holnos, R. J.,
Foiiost, S. R., Soos, Z. G. (2003¡ Pnys.
Rcv. B, 68, 075211.
10 Loo, M.-K., Sogal, M., Soos, Z. G.,
Shinai, J., Baldo, M. A. (2005¡ Pnys.
Rcv. Lctt., 94, 137403.
11 Holliich, W. and Schnoidoi, W. G.
(1966¡ ]. Cncn. Pnys, 44, 2902.
12 Bio´das, J.-L., Coinil, J., Boljonno, D.,
Dos Santos, D. A., Shuai, Z. (1999¡
Acc. Cncn. Rcs., 32, 267.
13 Shuai, Z., Boljonno, D., Silloy, R. J.,
Bio´das, J. L. (2000¡ Pnys. Rcv. Lctt., 84,
14 Wilson, J. S., Dhoot, A. S., Sooloy, A.
J. A. B., Khan, M. S., Kohloi, A.,
Fiiond, R. H. (2001¡ Nuturc, 413, 828.
15 Wohlganannt, W., Tandon, K.,
Mazundai, S., Ranasosha, S.,
Vaidony, Z. H. (2001¡ Nuturc, 409,
16 Ziolaith, J. M. and McGohoo, M. D.
(2005¡ ]. App| Pnys, 97, 064502.
17 Bonisty, H., DoNovo, H., Woisluch, C.
(1998¡ !EEE ]. Quuntun E|cctrcn, 34,
18 Caii, W. N. (1966¡ !njrurcd Pnysics, 6, 1.
19 Madigan, C. F., Lu, M. H., Stuin, J.
C. (2000¡ App|. Pnys. Lctt., 76, 1650.
20 Mo¨lloi, S. and Foiiost, S. F. (2002¡ ].
App|. Pnys., 91, 3324.
21 Shiang, J. J. and Duggal, A. R. (2004¡
]. App|. Pnys., 95, 2880,Shiang, J. J.,
Faiicloth, T. J., Duggal, A. R. (2004) ].
App|. Pnys., 95, 2889.
22 Holliich, W. and Schnoidoi, W. G.
(1965¡ Pnys. Rcv. Lctt., 14, 229.
23 Mohl, W. and Funk, B.US 3 530 325.
24 Tang, C. W. and VanSlyko, S. A. (1987¡
App|. Pnys. Lctt., 51, 913.
25 Paitiidgo, R. H. (1983¡ Pc|yncr24,
733,Paitiidgo, R. H. (1983) Pc|yncr,
24, 739;Pailiioge, R. H. (1983)
Pc|yncr, 24, 748;Pailiioge, R. H.
(1983) Pc|yncr, 24, 755.
26 Tang, C. W., VanSlyko, S. A., Chon,
C. H. (1989¡ ]. App|. Pnys., 65, 3610.
27 Endo, J., Matsunoto, T., Kido, J.
(2002¡ ]pn. ]. App|. Pnys., 41, L358.
28 Zhou, X., Ploilloi, M., Blochwitz, J.,
Woinoi, A., Nollau, A., Fiitz, T., Loo,
K. (2001¡ App|. Pnys. Lctt., 78, 410.
29 Paithasaiathy, G., Shon, C., Kahn, A.,
Foiiost, S. R. (2001¡ ]. App|. Pnys., 89,
30 Adachi, C., Tokito, S., Tsutsui, T.,
Saito, S. (1988¡ ]up. ]. App|. Pnys., 27,
31 Kido, J., Ikoda, W., Kinuia, M., Nagai,
K. (1996¡ ]up. ]. App|. Pnys, 35, L394.
32 Shiiota, Y. (2000¡ ]. Mutcr. Cncn., 10, 1.
33 Lanansky, S., Djuiovich, P., Muiphy,
D., Aldol-Razzaq, F., Kwong, R.,
Tsyla, I., Boitz, M., Mui, B., Bau, R.,
Thonpson, M. E. (2001¡ !ncrg. Cncn.,
40, 1704.
34 Baldo, M. A., O`Biion, D. F., You, Y.,
Shoustikov, A., Silloy, S., Thonpson,
M. E., Foiiost, S. R. (1998¡ Nuturc,
395, 151.
Rejerences 215
35 Adachi, C., Kwong, R. C., Djuiovich,
P., Adanovich, V., Baldo, M. A.,
Thonpson, M. E., Foiiost, S. R. (2001¡
App|. Pnys. Lctt., 79, 2082.
36 Baldo, M. A., Lanansky, S., Buiiows,
P. E., Thonpson, M. E., Foiiost, S. R.
(1999¡ App|. Pnys. Lctt., 75, 4.
37 Baldo, M. A. and Foiiost, S. R. (2000¡
Pnys. Rcv. B, 62, 10958.
38 Ho, G., Ploilloi, M., Loo, K.,
Holnann, M., Biinstock, J., Pudzich,
R., Sallock, J. (2004¡ App|. Pnys. Lctt.,
85, 3911.
39 Holnos, R. J., D`Andiado, B. W.,
Foiiost, S. R., Ron, X., Li, J.,
Thonpson, M. E. (2003¡ App|. Pnys.
Lctt., 83, 3818.
40 Sajoto, T., Djuiovich, P. I.,
Tanayo, A., Yousuluddin, M., Bau, R.,
Thonpson, M. E., Holnos, R. J.,
Foiiost, S. R. (2005¡ !ncrg. Cncn., 44,
41 Schildknocht, C., Ginov, G.,
Kannoun, A., Riodl, T., Kowalsky, W.,
Johannos, H.-H., Lonnaitz, C., Kahlo,
K., Egon, M., Gonoi, T., Bold, M. N.,
Noid, S., Eik, P. (2005¡ Prcc. SP!E,
5937, 59370E.
42 Schwaitz, B. J. (2003¡ Annu. Rcv. Pnys.
Cncn., 54, 141.
43 Collison, C. J., Rothloig, L. J.,
Tioonanookain, V., Li, Y. (2001¡
Mucrcnc|ccu|cs, 34, 2346.
44 Schoil, U. and List, E.J.W. (2002¡ Adv.
Mutcr., 14, 477.
45 Paitiidgo, R. H. USP 3 995 299.
46 Kido, J., Shionoya, H., Nagai, K.
(1995¡ App|. Pnys. Lctt., 67, 2281.
47 Yang, X. H., Jaisoi, F., Klingoi, S.,
Nohoi, D. (2006¡ App|. Pnys. Lctt., 88,
48 Choulis, S. A., Mathai, M. K., Choong,
V.-E., So, F. (2006¡ App|. Pnys. Lctt., 88,
49 Hoogoi, A. J. (2002¡ Syntnctic Mctu|s,
125, 23.
50 Buiioughs, J. H., Biadloy, D. D. C.,
Biown, A. R., Maiks, R. N., Mackay,
K., Fiiond, R. H., Buins, P. L.,
Holnos, A. B. (1990¡ Nuturc, 347, 539.
51 Biaun, D. and Hoogoi, A. J. (1991¡
App|. Pnys. Lctt., 58, 1982.
52 Yang, Y. and Hoogoi, A. J. (1994¡ App|.
Pnys. Lctt., 64, 1245.
53 Caitoi, S. A., Angolopoulos, M., Kaig,
S., Biock, P. J., Scott, J. C. (1997¡ App|.
Pnys. Lctt., 70, 2067.
54 Bockoi, H., Spioitzoi, H., Kioudoi,
W., Klugo, E., Schonk, H., Paikoi,
I., Cao, Y. (2000¡ Adv. Mutcr., 12, 42.
55 Boinius, M., Inlasokaian, M., Woo, E.,
Wu, W., Wujkowski, L. (2000¡ ]. Mutcr.
Sci. Mutcr. E|cctrcnics, 11, 111.
56 Wu, W., Inlasokaian, M., Hudack, M.,
Wolsh, D., Yu, W., Chong, Y., Wang,
C., Kian, S., Tacoy, M., Boinius, M.,
Flotchoi, R., Kiszka, K., Mungoi, S.,
O`Biion, J. (2004¡ Micrcc|cctrcnics ].,
35, 343.
57 Rodockoi, M., Biadloy, D. D. C.,
Inlasokaian, M., Wu, W. W., Woo, E.
P. (1999¡ Adv. Mutcr., 11, 241.
58 Duggal, A. R., Shiang, J. J., Foust, D.
F., Tuinoi, L. G., Noalon, W. F.,
Boitscholloi, J. C. (2005¡ S!D 0S
Digcst, 28.
59 Mu¨lloi, C. D., Falcou, A., Rockoluss,
N., Rojahn, M., Wiodoihiin, V.,
Rudati, P., Fiohno, H., Nuykon, O.,
Bockoi, H., Mooiholz, K. (2003¡
Nuturc, 421, 829.
60 Kin, J. S., Fiiond, R. H., Giizzi, I.,
Buiioughs, J. H. (2005¡ App|. Pnys.
Lctt., 87, 023506.
61 Hoitol, D., Ba¨ssloi, H., Guontnoi, R.,
Schoil, U. (2001¡ ]. Cncn. Pnys., 115,
62 Sandoo, A. J., Willians, C. K., Evans,
N. R., Davios, J. E., Boothly, C. E.,
Kolhloi, A., Fiiond, R. H., Holnos, A.
B. (2004¡ ]. An. Cncn. Scc., 126,
63 Maikhan, J. P. J., Lo, S. C., Magonnis,
S. W., Buin, P. L., Sanuol, I. D. W.
(2002¡ App|. Pnys. Lctt., 80, 2645.
64 Lo, S.-C., Richaids, G. L., Maikhan, J.
P. J., Nandas, E. B., Shaina, S., Buin,
P. L., Sanuol, I.D.W. (2005¡ Adv.
Funct. Mutcr., 15, 1451.
65 Gustalsson, G., Cao, Y., Tioacy, G. M.,
Klavottoi, F., Colanoii, N., Hoogoi, A.
J. (1992¡ Nuturc, 357, 477.
66 Chwang, A., Rothnan, M. A., Mao, S.
Y., Howitt, R. H., Woavoi, M. S.,
Silvoinail, J. A., Rajan, K., Hack, M.,
Biown, J. J., Chu, X., Moio, L.,
Kiajowski, T., Ruthoiloid, N. (2003¡
App|. Pnys. Lctt., 83, 413.
216 8 Organ|c E|ectro|un|nescence
67 Yan, M., Kin, T. W., Eilat, A. G.,
Pollow, M., Foust, D. F., Liu, J.,
Schaopkons, M., Holloi, C. M.,
McConnoloo, P. A., Foist, T. P.,
Duggal, A. R. (2005¡ Prcc. !EEE, 93,
68 Duggal, A. R., Shiang, J. J., Holloi, C.
M., Foust, D. F. (2002¡ App|. Pnys. Lctt.,
80, 3470.
69 Duggal, A. R., Foust, D. F., Noalon, W.
F., Holloi, C. M. (2003¡ App|. Pnys.
Lctt., 82, 2580.
70 Ivoy, H. F. (1963¡ ]. Opt. Scc. An., 53,
1185, Thointon, W. A. (1971) ]. Opt.
Scc. An., 61, 1155;ZuLausLas, A.,
VaiceLausLas, R., !vanausLas, !.,
GasLa, R., Slui, M. S. (2002) App|.
Pnys. Lctt., 80, 234.
Rejerences 217


     

          

                                                         

    

                                                                                                                                                                                                                                                                                                    

Master your semester with Scribd & The New York Times

Special offer for students: Only $4.99/month.

Master your semester with Scribd & The New York Times

Cancel anytime.