Journal of the Korean Physical Society, Vol. 55, No. 1, July 2009, pp.

327330
Stable Eciency Roll-o in Solution-processed Phosphorescent Green
Organic Light-emitting Diodes
Jung Joo Park, Seong Taek Lee, Tae Jin Park, Woo Sik Jeon, Jin Jang and Jang Hyuk Kwon

Department of Information Display, Kyung Hee University, Seoul 130-701

Ramchandra Pode
Department of Physics, Kyung Hee University, Seoul 130-701
(Received 26 August 2008)
Using a mixed host system of hole transport, 4,4,4-tris(N-carbazolyl)triphenylamine (TCTA),
and electron transport, 1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBI), materials, we report
stable eciency roll-o in solution-processed phosphorescent green organic light-emitting diodes.
Maximum current and power eciencies of 28.2 cd/A and 13.2 lm/W, respectively, were achieved.
The current eciency was over 90% of the maximum value at a luminance of 20,000 cd/m
2
in this
device, which is very high compared to values reported earlier for any solution-processed triplet
devices.
PACS numbers: 78.60.Fi
Keywords: Eciency roll-o, Phosphorescent OLEDs, Solution process
I. INTRODUCTION
High-eciency phosphorescent organic light-emitting
diodes (PHOLEDs) have generated intense academic and
commercial interest as these devices theoretically oer
a maximum internal quantum eciency of 100% and
accordingly, a high external quantum eciency. The
upper limit on the internal quantum eciency of 25%
with uorescent dyes as the emissive layer, wherein only
the singlet states of the organic molecule contribute to
the light emission, is surmounted in phosphorescent dyes
that can harvest both singlet and triplet excitons gen-
erated by electron injection [13]. However, their per-
formance suers at high driving current densities ex-
ceeding 1 mA/cm
2
, resulting in a reduced quantum ef-
ciency at high current density. Triplet-triplet annihi-
lation originating from the long lifetime of the triplet
excited state [4, 5] electric-eld-induced dissociation of
excitons [6] and triplet-polaron annihilation [7] are re-
sponsible for this roll-o of the current eciency at high
current density. In most PHOLEDs, triplet-triplet an-
nihilation is considered to be the main cause of the re-
duced current eciency at high brightness. Several stud-
ies have been done on the origin and the improvement of
the eciency roll-o in PHOLEDs, and mixed emissive
hosts and multilayer device structures have been sug-

E-mail: jhkwon@khu.ac.kr; Fax: +82-2-961-9154

gested for stable quantum eciency roll-o OLEDs [8
11]. For instance, with TCTA:Ir(ppy)
3
/BPhen:Ir(ppy)
3
emissive hosts where TCTA and BPhen are 4,44-
tris(N-carbazolyl)-triphenylamine and 4,7-diphenyl-1,10-
phenanthroline, respectively, a peak external quantum
eciency (EQE) of 12.6% (corresponding to a cur-
rent eciency of 44.3 cd/A) was reported in mul-
tilayer PHOLEDs [8]. Recently, a 10% roll-o of
the current eciency at a luminance of 20,000 cd/m
2
in an Ir(ppy)
3
doped multilayer device system with
a TCTA:TPBI mixed host (TPBI is 1,3,5-tris(N-
phenylbenzimidizol-2yl)benzene) was presented [10].
Although a multilayer architecture in PHOLEDs com-
prised of electron/hole injection and transport layers is
commonly used to achieve better OLED performance,
complex design architecture of phosphorescent OLEDs
is undesirable from a manufacturing perspective. On
the other hand, solution-processible OLEDs are attract-
ing much attention as potential candidates for at-panel
displays and solid-state lighting, owing to their easy pro-
cessing and low manufacturing cost [12, 13]. However,
this method has serious limitations due to the unavail-
ability of good soluble small molecule and polymer ma-
terials and to the relatively poor device performance in
eciency and lifetime. Many eorts have been made
to improve the device performance of solution-processed
OLEDs. In this work, we report stable eciency roll-o
devices with a mixed emissive host in solution-processed
phosphorescent green OLEDs.
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-328- Journal of the Korean Physical Society, Vol. 55, No. 1, July 2009
Fig. 1. The device structure and energy levels of used
materials.
II. EXPERIMENTS AND DISCUSSION
A mixed host system of a hole transport, TCTA,
and electron transport, TPBI, materials with 2-(4-
biphenyllyl)-5-(4-tert-butylphenyllyl)-1,3,4-oxadiazol
(Ir(mppy)
3
) dopant was employed as an emitting layer
(EML) for stable eciency roll-o devices. The device
conguration used in this study was indium tin oxide
(ITO, 150 nm)/ Poly(3,4-ethylenedioxythiophene)-
poly(4-stylenesurfonate) (PEDOT:PSS, 40 nm)/ TCTA
(40 nm)/ emissive layer (EML, 40 nm)/TPBI (20 or
30 nm)/LiF (1 nm)/Al (100 nm). The PEDOT:PSS,
Baytron P VP AI4083, was purchased from H. C. Starck.
Fig. 1 shows the device structure with the energy levels
of the materials used. TCTA has an appropriate HOMO
(highest occupied molecular orbital) level for hole
injection while TPBI has a LUMO (lowest unoccupied
molecular orbital) level for ecient electron injection.
The combination of hole- and electron-transport-type
host materials can be benecial to control holes and
electrons in the EML to achieve stable eciency in
PHOLEDs at high current densities.
To fabricate OLED devices, we cleaned ITO-coated
glass substrates having a sheet resistance of 12 / with
isopropyl alcohol and acetone, successively, in an ultra-
sonic bath and later rinsed them in deionized water.
The cleaned ITO-coated glass substrates were treated
with UV-ozone for 15 min just prior to use. The 40-
nm-thick layer of PEDOT:PSS was prepared by using a
spin-coating method and dried at 120

C for 20 min on
a hot plate to remove the solvent. Subsequently, a 0.5%
TCTA solution in toluene was spin coated and dried at
180

C for 20 min on a hot plate to give the 30-nm-
thick interlayer. On top of this interlayer, an emitting
material solution of the TCTA:TPBI mixed host (1:1)
and the dopant, tris(2-(4-toltyl)phenylpyridine) iridium
(Ir(mppy)
3
), in chlorobenzene was spin coated to give
a smooth amorphous EML lm without any crystalliza-
tion. More details on spin coating the EML on top of
an organic soluble interlayer are described in our earlier
study [14]. A series of devices with 7, 10, 13, and 15%
dopant concentrations was fabricated to investigate the
doping concentration eects. The spin-coated substrates
Fig. 2. Electroluminescence characteristics of fabricated
OLEDs with a 20-nm-thick ETL (doping concentrations: 7,
10, 13, and 15%): (a) I V and L V characteristics and
(b) eciency-brightness curves.
were then baked on a hot plate at 120

C for 60 min to
remove the remaining solvent, if any. The spin coating
and baking processes were carried out in a nitrogen at-
mosphere in a glove box to prevent degradations caused
by oxygen and moisture. An electron transport layer of
TPBI (30 nm) was deposited on top of the EML in an
organic chamber by using vacuum thermal evaporation
at a base pressure of 10
7
Torr while LiF (1 nm) and
Al (100 nm) were deposited in a metal chamber without
breaking the vacuum of the system. The emission area
of the devices was 2 mm 2 mm. The current density
- voltage (I-V) and the luminance - voltage (L-V) char-
acteristics of the devices were measured with a Keithley
238 source measurement unit and a Minolta CS-100A
system. Electroluminescence (EL) spectra and CIE co-
ordinate were obtained using a Photo-research PR-650
spectroradiometer.
All fabricated devices showed clean emission peaks
in the green region with CIE coordinates (0.31, 0.61)
at 1,000 cd/m
2
, indicating that the excitons were well-
localized within the emitting-layer without leakages of
charges. Fig. 2 (a) shows the brightness and the cur-
rent density versus the driving voltage of OLEDs (20-nm-
thick ETL) fabricated with 7, 10, 13, and 15% dopant
doping concentrations. The luminance and the power
Stable Eciency Roll-o in Solution-processed Phosphorescent Jung Joo Park et al. -329-
eciency as functions of brightness are shown in Fig.
2 (b). As the doping concentration increases, better
I V L characteristics with higher current density
and brightness at a given driving voltage are obtained.
The best characteristic is achieved with 13% doping con-
centration. When the doping concentration is over 13%,
the current density and the brightness at a given driving
voltage decrease. At a voltage of 7 V, current density
values of 27.1, 25.8, 59.4, and 43.9 mA/cm
2
were ob-
served in devices with 7, 10, 13, and 15% doping concen-
trations, respectively. Brightness of 4904, 5238, 13810,
and 9560 cd/m
2
were obtained at a driving voltage of
7 V. Further, the device with a 13% doping concentra-
tion showed the best EL eciency performance. In the
device with 13% doping concentration, a driving volt-
age of 5.6 V and current and power eciencies of 18.5
cd/A and 10.4 lm/W at a luminance of 1,000 cd/m
2
were
achieved, respectively. Maximum current and power e-
ciencies of 23.8 cd/A and 11.7 lm/W, respectively, were
measured in this device. The current eciency value
of 18.5 cd/A at a luminance of 1000 cd/m
2
increases
gradually to reach a maximum value of 23.8 cd/A at a
luminance of 9,327 cd/m
2
, and shows good stability at
high brightnesses exceeding 10,000 cd/m
2
in the device
with 13% doping concentration. A similar trend in e-
ciency, increasing at high driving current density, is ob-
served in other devices. The current eciencies of these
devices were very stable and their current eciency val-
ues at 10,000 cd/m
2
, compared to those at a luminance
of 1,000 cd/m
2
, were reduced by 14.8, 13.5, 12.8, and
11.8%, respectively, for devices with 7, 10, 13, and 15%
doping concentrations. This result shows that the high-
est stable eciency characteristics are observed at high
brightness in solution-processed PHOLEDs.
Recently, we investigated solution-processed phos-
phorescent green OLEDs with a mixed host sys-
tem of poly(N-vinylcarbazole) (PVK) and 4,4-N,N-
dicarbazolebiphenyl (CBP) by utilizing similar device
structures to those of this study [14]. Although excellent
maximum current and power eciencies of 27.2 cd/A and
17.8 lm/W, respectively, were demonstrated, the devices
showed relatively large eciency roll-o at high bright-
ness and the current eciency of those devices was only
66% of the maximum current eciency at 10,000 cd/m
2
The hole-electron balance and the distribution of recom-
bination zone in the light-emitting layer were critical to
eciency roll-o in PHOLEDs [10]. PVK was described
as an unipolar hole transporter while CBP was recog-
nized to have a bipolar transport character. As a result,
relatively poor eciency roll-o characteristics were eas-
ily expected in PVK:CBP mixed host PHOLEDs. On
the other hand, in the TCTA:TPBI mixed host system,
the combination of the hole-transport character of TCTA
and the electron-transport property of TPBI can con-
tribute to controlling the holes and the electrons in the
light-emitting layer and can result in stable eciency
roll-o PHOLEDs. In addition to this well-balanced
hole-electron characteristic in the light-emitting layers
Fig. 3. Electroluminescence characteristics of fabricated
OLEDs with 13% dopant concentration (ETL thicknesses:
20 and 30 nm): (a) I V and L V characteristics and (b)
eciency-brightness curves.
based on the charge transporting properties of host ma-
terials, the stable eciency roll-o of the TCTA:TPBI
mixed host system can be explained by the low charge
injection barriers in our devices. As shown in Fig. 1, we
utilized TCTA as a HTL and TPBI as an ETL to com-
prise the mixed host EML system. As a result, holes are
injected from the HOMO of HTL to the HOMO of TCTA
of the mixed host EML, and electrons are injected from
the LUMO of ETL to the LUMO of TPBI of the mixed
host EML without barriers to a give high probability of
a hole-electron balance in the light-emitting layer. The
appropriate HOMO energy level of TCTA for hole injec-
tion and the LUMO energy level of TPBI for ecient
electron injection contribute to a certain degree to good
hole-electron balance in the light-emitting layer.
As shown in Fig. 3, we achieved a better eciency
characteristic with a thicker ETL thickness of 30 nm,
even though relatively deteriorated I V L charac-
teristics with a lower current density and brightness at
a given driving voltage were observed compared to the
device with a 20-nm-thick ETL. The operating voltage
of 6.1 V for 1,000 cd/m
2
in the device with a 30-nm-
thick ETL is 0.5 V higher than that of the device with a
20-nm-thick ETL, but the dierences in operating volt-
age tend to decrease at higher brightness. In the de-
-330- Journal of the Korean Physical Society, Vol. 55, No. 1, July 2009
vice with a 30-nm-thick ETL, current and power e-
ciencies of 22.3 cd/A and 11.5 lm/W, respectively, were
attained at a luminance of 1,000 cd/m
2
. Maximum cur-
rent and power eciencies of 28.2 cd/A and 13.2 lm/W,
respectively, were achieved in this device. The current
eciency of this device was over 90% of the maximum
current eciency at 20,000 cd/m
2
. This value is bet-
ter than eciency roll-o value reported in any other
solution-processed triplet devices, and it was possible to
get stable eciency values from 1,000 to 20,000 cd/m
2
in this device.
III. CONCLUSION
In conclusion, we have presented stable eciency roll-
o in solution-processed phosphorescent green OLEDs
based on small molecular materials The current e-
ciency was stable and could be maintained at over 90%
of the maximum current eciency at 20,000 cd/m
2
,
which is the highest eciency roll-o value in solution-
processed PHOLEDs. This stable eciency roll-o is at-
tributed to the well-balanced hole-electron characteristic
in the light-emitting layer arising from a combination of
the hole-transport character of TCTA and the electron-
transport property of TPBI in the mixed host system.
ACKNOWLEDGMENTS
The authors thank the Ministry of Commerce, Indus-
try, and Energy of Korea for nancially supporting of
this work.
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