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JOURNAL OF DISPLAY TECHNOLOGY 1
Improving the Performance of a Hybrid
Inorganic-Organic Light-Emitting Diode Through
Structure Optimization
R. Acharya and X. A. Cao
AbstractSignicant performance enhancement of a green hy-
brid inorganic-organic light-emitting diode (HyLED) based on a
simplied WO /organic layer structure has been achieved through
structure optimization. A 2050 nm as-deposited WO layer al-
lowed for facile hole injection and transport. In the meantime, it
had high transparency and good robustness required for efcient
and reliable operation of the HyLED. Inserting a 30 nm undoped
4,4 -N,N -dicarbazolebiphenyl (CBP) layer between the WO and
emitting layer resulted in a broadened exciton generation zone and
improved the brightness by 87.4% at 20 mA/cm . At this injection
level, the optimized HyLED reached a luminance of 11642 cd/m
and a current efciency of 58.2 cd/A, and exhibited good reliability
under constant-current stressing.
Index TermsElectroluminescence, hybrid junctions, light-
emitting diodes (LEDs), organic compounds.
I. INTRODUCTION
O
VER the past two decades, organic light-emitting diodes
(OLEDs) have undergone a phenomenal development ef-
fort and their performance has met many of the targets nec-
essary for full-color displays. However, they have yet to de-
liver the desired efciency and stability required for general
illumination [1]. State-of-the-art short-wavelength phosphores-
cent OLEDs suffer signicantly from unbalanced charge injec-
tion due to poor injection of holes [2][10]. This is because
the commonly used hole-injecting electrode, indium tin oxide
(ITO), has a work function 4.7 eV, which is much lower than
the highest occupied molecular orbital (HOMO) of typical hole
transport layer (HTL). A large voltage drop at the ITO/HTL in-
terface is needed to overcome the energy barrier during device
operation, generating a lot of joule heat, which accelerates the
crystallization of organic materials and thus device degradation
[3]. Considerable efforts have been devoted to the modication
of the ITO/HTL interface for enhanced hole injection. Athin or-
ganic interlayer, which has a HOMO between the Fermi level of
ITO and HOMO of the HTL, is often inserted between the ITO
anode and HTL as a hole injection layer (HIL) [5], [6]. Its ad-
dition thus creates a ladder-like energy structure that facilitates
Manuscript received November 28, 2012; revised February 22, 2013; ac-
cepted March 27, 2013.
The authors are with Department of Computer Science and Electrical En-
gineering, West Virginia University, Morgantown, WV 26506 USA (e-mail:
xacao@mail.wvu.edu).
Color versions of one or more of the gures are available online at http://
ieeexplore.ieee.org.
Digital Object Identier 10.1109/JDT.2013.2256106
hole injection. From the durability point of view, it is more de-
sirable to use an inorganic HIL which is more physically stable
than an organic HIL. Various insulating or semiconducting inor-
ganic materials, including MoO and WO , have been adopted
as the HIL in OLEDs [7][11]. The inorganic HIL creates band
bending and effectively displaces the Fermi level of ITO down-
ward. The injection of holes is thus better balanced with that
of electrons, giving rise to improved device performance. It has
been found that the optimal thicknesses of the inorganic HILs
are on the order of sub-nanometers or a few nanometers [9]. It
is a tremendous challenge to deposit such a thin lm on a large
substrate to form a uniform and robust interlayer. Additionally,
the HIL also adds substantially to the complexity of the device
structure and manufacturing process.
It would be desirable to develop OLEDs with a robust
single-layer HTL which also enables efcient hole injection
from the ITO anode. WO has great stability, high transparency
in the visible region, and a large work function of 6.3 eV
[10][12]. It has proven to be an effective material for the HIL
in OLEDs [9][11]. Moreover, WO deposited by evaporation
is p-type doped due to the presence of different oxide states
and impurities [12], [13], making it a good candidate as the
HTL material as well [12], [14]. Our recent work demon-
strated such a dual function of WO (hole injection and hole
transport) in high-brightness hybrid inorganic-organic LEDs
(HyLEDs), allowing for a signicant simplication of the
device structure and processing [14]. Compared to OLEDs with
a N,N-bis-(1-naphthyl)-N,N -diphenyl-1,1 -biphenyl-4,4 -di-
amine (NPB) HTL, the HyLEDs with a WO HTL had a 57%
higher current efciency at 20 mA/cm and a 7 times longer
lifetime under 20 mA/cm stressing.
In this work, we conduct a series of experiments to optimize
the design of a green phosphorescent HyLED based on a sim-
plied WO /organic layer structure. The layer structure of the
device is shown in Fig. 1(a). Since electron injection from the
LiF/Al electrode is not much an issue, the current study focuses
on the optimization of the critical components on the anode side,
including (i) the ITO/WO interface; (ii) the WO layer; and
(iii) The WO /emitting layer (EML) interface, in order to de-
velop HyLEDs with a low operation voltage, a high luminous
efciency, and good operational durability.
II. DEVICE DESIGN AND FABRICATION
Green phosphorescent HyLEDs with various layer struc-
tures were fabricated on glass substrates with pre-patterned
ITO (sheet resistance 15 ). The substrates were rst
1551-319X/$31.00 2013 IEEE
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2 JOURNAL OF DISPLAY TECHNOLOGY
Fig. 1. (a) Layer structure and (b) energy diagram of a HyLED with a WO
HTL. The arrows in (a) indicate the three critical components to be optimized
in this work.
cleaned with solvents and deionized water, and subjected to
different surface modications. They were then transferred to
a thermal evaporation system, where WO , organic materials,
and Al were deposited at a pre-calibrated rate 0.1 nm/s. The
standard device structure, as shown in Fig. 1(a), consisted
of a 35 nm WO layer, a 20 nm undoped 4,4 -N,N -dicar-
bazolebiphenyl (CBP) layer, a 30 nm CBP doped with 7 wt.%
fac-tris(2-phenylpyridinato-N,C2 ) iridium (III) Ir ppy as
the EML, and a 45 nm 1,3,5-tris(2-N-phenylbenzimidazolyl)
benzene (TPBi) electron transport layer. Finally, a 0.5 nm
LiF/120 nm Al cathode was deposited through a shadow mask,
which dened the active area of the HyLEDs to be 0.1 cm .
All the device structures were deposited without breaking the
vacuum.
To modify the ITO/WO interface for enhanced hole injec-
tion, the ITO surface was exposed to O or Cl plasma for
5 min, and some O plasma-treated samples were further coated
with 210 nm of MoO . The treatment by O and
Cl plasma induces an In-X or Sn-X ( O,Cl) dipole layer
which may signicantly raise the work function of ITO [2], [3].
The MoO layer has a work function between those of ITO and
WO . It can sustain a voltage drop and effectively elevate the
work function of ITO [7], [8]. To optimize the WO layer, we
varied its thickness in the range of 550 nm. We expect that
a thin layer can reduce light absorption and series resistance,
but may not have sufcient robustness to ensure durable op-
eration of the HyLED. Finally, the WO EML interface was
modied by inserting an undoped CBP layer. As seen from the
HyLED energy diagram shown in Fig. 1(b), there is no elec-
tron blocking at the WO EML interface. We have found that
adding a 20 nm electron blocking layer of 4,4 ,4 ,-tris(N-car-
bazolyl) triphenylamine (TCTA) led to a remarkable increase
in the operation voltage by 3.6 V. Instead, an additional un-
doped CBP layer was inserted to capture over-injected electrons
and broaden the exciton generation zone. Performance enhance-
ment of the HyLED is thus expected. To determine the optimal
thickness of the undoped CBP layer, the thickness was varied
from 0 to 30 nm.
All the HyLEDs were encapsulated with glass lids in a
-lled glovebox and their electrical and optical character-
istics were measured in air at room temperature. To evaluate
the device reliability, as-fabricated devices were stressed at a
constant current density of 20 mA/cm , and their luminance
Fig. 2. Resistivity and transmittance at 520 nm of a 100 nm WO lm as a
function of the annealing temperature. The annealing was conducted in air for
20 min.
and voltages were recorded every 10 s. To characterize WO
deposited by thermal evaporation, 100 nm WO lms were
deposited on bare glass and the thickness was conrmed by
prolometry. The samples were annealed at 250550 C in
air for 20 min, and their transparency and resistivity were
measured. In addition, a structure of ITO/WO (100 nm)/ZnO
(100 nm)/Al was fabricated for electrical characterization of
the ITO/WO interface.
III. RESULTS AND DISCUSSION
The as-deposited WO lms (100 nm thick) were semicon-
ducting and transparent, with a resistivity of cm,
and a transmittance of 0.9 at 520 nm. The resistivity and trans-
parency at 520 nm of the lms annealed at different temper-
atures are shown in Fig. 2. The resistivity increases with the
annealing temperature, peaks at 3.6 10 cm after 450 C
annealing, and then exhibits a sharp decrease after annealing at
550 C. The transmittance is nearly constant when the annealing
temperature is below 450 C, but decreases substantially after
550 C annealing. These behaviors can be attributed to the re-
moval of oxygen vacancies and crystallization of WO during
annealing in air [9]. The results conrm that as-deposited WO
is highly transparent to visible light, and has a good conductivity
necessary for facile charge transport in OLEDs.
In order to shed light on the electrical property of the
ITO/WO interface, we fabricated a simple ITO/WO
(100 nm)/ZnO (100 nm)/Al structure, where ZnO was also
deposited by thermal evaporation and had a low resistivity of
1.8 10 cm. Its currentvoltage ( ) characteristics
are shown in Fig. 3. The linear relationship indicates the
ohmic nature of the ITO contact to WO . It is plausible that,
under a forward bias, holes may tunnel through the interfacial
barrier into the valence band via band gap states of WO .
Therefore, facile injection of holes from the ITO anode into
the WO HTL in the HyLEDs is expected. As seen from the
energy diagram in Fig. 1(b), holes can be injected directly
from the valance band of WO into the HOMO of CBP. In the
meantime, electrons face a small barrier of 0.2 eV as they are
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ACHARYA AND CAO: IMPROVING THE PERFORMANCE OF A HYBRID INORGANICORGANIC LED 3
Fig. 3. characteristics of an ITO/WO (100 nm)/ZnO (100 nm)/Al
structure.
injected from the cathode. Therefore, the injection of electrons
and holes in the HyLEDs is well balanced.
Fig. 4 compares the characteristics of HyLEDs with
ITO treated by different methods. The I-V curves of the de-
vices on ITO/glass with and without O plasma treatment are
almost identical, showing a turn-on voltage of 5 V. The de-
vices also have similar brightness under the same injection con-
dition. Even though Cl plasma treatment could raise the work
function of ITO by as much as 0.9 eV [3], it causes a minimal
reduction in the operation voltage. These results indicate that
the hole injection is not sensitive to changes of the ITO work
function. As seen in Fig. 4, adding a nanometer-thick (210 nm)
MoO results in an increase in the forward voltage by 1 V. In
typical OLEDs, such a MoO layer would act as a HIL and sus-
tain a voltage drop needed to reduce the hole injection barrier
[7], [8]. However, in the HyLEDs, the impact of the interfa-
cial energy barrier is small, as indicated by the data in Fig. 3.
Hence, the extra voltage drop across the MoO layer adds to
the operation voltage of the HyLEDs. These ndings suggest
that no additional surface modication of ITO is necessary to
enhance hole injection from ITO to WO . All the HyLEDs pre-
sented below were built on ITO/glass treated with a conven-
tional cleaning procedure, i.e., solvent rinse followed by 5 min
O plasma exposure.
Fig. 5 plots the luminancecurrentvoltage ( ) charac-
teristics of HyLEDs with a WO HTL whose thickness varies
from 5 to 50 nm. The operation voltages of the devices are very
similar at a given current density, indicating that the voltage
drop across the WO layer is quite small due to its good con-
ductivity. The HyLEDs with 2050 nm WO also have compa-
rable brightness, whereas the HyLEDwith 5 nmWO is slightly
( 6%) brighter mainly due to less light absorption by the thin
WO layer. The latter reaches the luminance level of 10 cd/m
at 16.5 mA/cm , and has a current efciency of 60.7 cd/A at
this current density.
The above results seem to suggest that the thickness of an
ideal WO HTL is on the order of a few nanometers. Such a thin
layer can act as an effective hole injection and transport layer,
while causing minimal absorption of visible light. However, an-
other critical design consideration is the impact of the WO
Fig. 4. characteristics of HyLEDs with different surface modications of
the ITO anode.
Fig. 5. characteristics of HyLEDs with a WO HTL whose thickness
is varied from 5 to 50 nm.
layer on the reliability of the HyLED, since the ITO/HTL inter-
face plays a critical role in device operation [3]. To evaluate the
reliability, all the HyLEDs were stressed in air at 20 mA/cm .
The dependence of their normalized luminance on the stressing
time is plotted in Fig. 6. The HyLEDs with 2050 nm WO
display relative slow degradation at a similar rate. Stressing for
15 h results in a decrease in luminance by 21%. Their half
life (dened as the time for the brightness to decline to 50% of
its initial value) is projected to be 52 h under this condition.
However, the HyLED with 5 nm WO exhibits a considerably
faster drop in the light intensity. After 15 h stressing, the lu-
minance decreases by 33%. The fast luminance decay was ac-
companied by a rapid increase in its operation voltage. The es-
timated half life of this device is only about 30 h. In our pre-
vious study, it was found that HyLEDs with a 35 nm WO
HTL were much more durable than all-organic OLEDs under
the same current stressing due to the facts that the joule heat gen-
eration at the HTL/ITO interface is greatly reduced and WO
is more thermally stable than organic materials [14]. However,
nanometer-thick WO may not form a uniform and robust in-
terlayer which can effectively prevent the interfacial reactions
between ITOand organic materials. Therefore, a relatively thick
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4 JOURNAL OF DISPLAY TECHNOLOGY
Fig. 6. Evolution of the normalized luminance of HyLEDs with a 550 nm
WO HTL under constant-current stressing at 20 mA/cm .
Fig. 7. characteristics of HyLEDs with an undoped CBP inserted be-
tween the WO HTL and CBP Ir ppy EML. The thickness of the undoped
CBP layer is varied from 030 nm.
WO HTL should be adopted to ensure efcient and reliable op-
eration of the HyLED.
Finally, the inuence of an additional undoped CBP layer
inserted between the WO and EML on the performance of
the HyLED was studied. Both the HyLEDs with and without
an undoped CBP showed typical green electroluminescence of
Ir ppy with a peak wavelength of 517 nm. Fig. 7 compares
the characteristics of the HyLEDs with 030 nm un-
doped CBP and a 35 nm WO HTL. As expected, adding an
undoped CBP leads to signicant performance enhancement.
At a given current, the luminance increases as the undoped
CBP grows thicker, and tends to saturate at 2030 nm. At
20 mA/cm , the brightness of the baseline HyLED (without
undoped CBP) is 6212 cd/m . It is increased to 8578 cd/m ,
10713 cd/m , and 11642 cd/m for HyLEDs with 10 nm,
20 nm, and 30 nm undoped CBP, respectively. The external
quantum efciency and current efciency of the device with
30 nm undoped CBP are 14.2% and 58.2 cd/A, respectively,
which are 87.4% higher than those of the baseline HyLED. A
comparative study showed that such high efciencies could not
be achieved by simply increasing the thickness of the EML.
The performance enhancement is explained as follows. The
undoped CBP captures over-injected electrons and meanwhile
acts as a reasonable hole transport layer, leading to a broadened
exciton generation zone. Excitons generated in the undoped
CBP layer can diffuse or transfer energy to the CBP:Ir ppy
EML, contributing to the light emission. As seen in Fig. 7,
the operation voltage also increases with the thickness of the
undoped layer. It is 1.1 V higher in the HyLED with 30 nm
CBP at 20 mA/cm . This additional voltage is applied across
the undoped CBP, driving charge transport in this layer. The
above results show that, even though an inserted undoped
CBP layer results in a small increase in the operation voltage,
it greatly improves the brightness, current efciency as well
as luminous efciency of the baseline HyLED. The optimal
thickness is determined to be 30 nm. Within this distance,
carriers can drift through the layer under a relatively low bias,
while the majority of the excitons generated in this layer can
reach the EML via diffusion or energy transfer.
IV. CONCLUSION
In summary, structure optimization of a green phosphores-
cent HyLED based on a simplied WO /organic layer structure
has been performed to achieve efcient and reliable operation of
the device. It has been found that ohmic injection of holes can
be obtained at the ITO/WO interface, whereas surface mod-
ication of ITO had little impact on the HyLED characteris-
tics. A 2050 nm as-deposited WO layer has critical attributes
for hole transport, including high transparency, low resistivity,
and good physical stability. Inserting a 2030 nm undoped CBP
layer between the WO and CBP Ir ppy EML signicantly
enhanced the HyLED performance. The device with an opti-
mized structure reached a brightness of 11642 cd/m and a cur-
rent efciency of 58.2 cd/A at 20 mA/cm . This simplied hy-
brid structure represents a viable design for low-cost high-ef-
ciency RGB and white OLEDs suitable for color displays and
solid-state lighting.
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R. Acharya is currently a graduate student in the Department of Computer Sci-
ence and Electrical Engineering, West Virginia University, where his research
focuses on the fabrication and characterization of high-efciency organic and
hybrid structure light-emitting diodes.
Xian-An Cao received the Ph.D. degree in materials science and engineering
from the University of Florida in 2000.
He is currently an Associate Professor with the Department of Computer
Science and Electrical Engineering, West Virginia University. Prior to this, he
worked at GE Global Research Center as a research scientist for ve years. His
research interests lie in developing integrated optoelectronics based on wide
bandgap semiconductors, organic materials, nanocrystals, and hybrid materials,
for energy and sensing applications. He has published over 100 journal papers
and 2 book chapters, and holds 12 patents.