Highly transparent polymer light-emitting

diode using modified aluminum-doped zinc

oxide top electrode
Cite as: Appl. Phys. Lett. 100, 133306 (2012); https://doi.org/10.1063/1.3698340
Submitted: 12 January 2012 • Accepted: 11 March 2012 • Published Online: 29 March 2012

Sung Heum Park, Byoung Hoon Lee, Jong Moon Shin, et al.

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Appl. Phys. Lett. 100, 133306 (2012); https://doi.org/10.1063/1.3698340 100, 133306

© 2012 American Institute of Physics.

 APPLIED PHYSICS LETTERS 100, 133306 (2012)

Highly transparent polymer light-emitting diode using modified

aluminum-doped zinc oxide top electrode
Sung Heum Park,1,a) Byoung Hoon Lee,2 Jong Moon Shin,3 Se-Young Jeong,3
Suhee Song,4 Hongsuk Suh,4 and Kwanghee Lee2,b)
1
Department of Physics, Pukyong National University, Busan 609-735, Korea
2
Heeger Center for Advanced Materials, School of Materials Science and Engineering, Gwangju Institute of
Science and Technology (GIST), Gwangju 500-712, Korea
3
Department of Nano-Science and Technology, Pusan National University, Busan 609-735, Korea
4
Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University,
Busan 609-735, Korea

(Received 12 January 2012; accepted 11 March 2012; published online 29 March 2012)
We report a novel approach that leads to a significant improvement in the performance of
transparent polymer light-emitting diodes (TPLEDs). By introducing a solution-based titanium
oxide (TiOx) layer, we have demonstrated that the device performance of TPLEDs using
aluminum-doped zinc oxide (AZO) top electrodes is enhanced. The TiOx layer lowers the energy
barrier between the luminescent polymer and the AZO top electrode by modifying the WF of the
top AZO electrodes. Moreover, the TiOx layer prevents the damage caused by UV radiation and by
C 2012 American Institute of Physics.
highly energetic ions generated during the AZO sputtering. V
[http://dx.doi.org/10.1063/1.3698340]

Interest in transparent polymer light-emitting diodes
(TPLEDs) as elements for displays has recently increased
owing to their potential application in new conceptual trans-
parent displays,1–3 light-emitting windows,4,5 transparent
electronic devices,6,7 etc. Metal oxide electrodes such as in-
dium tin oxide (ITO), indium zinc oxide (IZO), and
aluminum-doped zinc oxide (AZO) have been studied as
transparent electrodes deposited on the top of the lumines-
cent polymer layers by means of a radio-frequency (RF)
sputtering technique.8,9 However, such RF deposition proc-
esses cause serious damage to the polymer layer beneath.
The energetic ions damage the underlying luminescent poly-
mer layer during the electrode deposition, and this results in
degradation of the device performance.10 In addition, the
energy level mismatch between the conduction band edge of
the luminescent polymer and the work-functions (WFs) of
such top electrodes in TPLEDs creates a significant energy
barrier between them.
Several methods of addressing these problems have been
reported, including the use of an organic material layer
between the active layer and the top electrode (such as copper
phtalocyanine (CuPc) or bathocuproine (BCP) layers)
intended to prevent such damage11,12 and the replacement of
metal oxide electrodes with semi-transparent thin metals or
conducting polymers that do not require the RF sputtering
process.8,9 However, since small molecules such as CuPc or
BCP cannot be processed in a solution, this approach is not
compatible with the typical fabrication concept of polymer-
based electronic devices, which involves a printed coating
method.13,14 In addition, the TPLEDs using semi-transparent
metal and conducting polymer electrodes exhibit poor trans-
parency and performance owing to their low transmittances in
the visible range and their low electrical conductivities. More-
over, one of the main challenges, i.e., the problem of mis-
a)
Electronic mail: spark@pknu.ac.kr.
b)
Electronic mail: klee@gist.ac.kr.
matched energy levels between the luminescent polymer and
the top electrode, remains unsolved; consequently, high injec-
tion barriers for electrons are created in the interface between
the layers, resulting in a decrease in device performance.
In this work, we have successfully demonstrated a highly
transparent and efficient TPLED using a solution-based tita-
nium oxide (TiOx) layer on luminescent polymer. The deposi-
tion of TiOx on the luminescent polymer decreases the energy
level difference between the lowest unoccupied molecular or-
bital (LUMO) level of the luminescent polymer and the
Fermi-level of the top AZO electrode through modification of
the WF of the AZO electrode; this leads to a decrease in the
energy barrier between them. In addition, the inorganic TiOx
layer, with high optical density in the UV range, prevents the
damage caused by UV radiation and by highly energetic ions
generated during the AZO sputtering.
Figure 1 presents the device structure of the TPLED to-
gether with the molecular structures of the TiOx and poly-
fluorene (PFO) active materials. The TPLEDs were
fabricated in the conventional sandwich structure of glass
substrate/ITO/PFO polymer/TiOx/AZO. The transparent
ITO-coated glass substrates were cleaned using a routine
cleaning procedure, which included sonication in detergent
followed by repeated rinsing in water, ethyl alcohol, and ace-
tone; the ITO is used as a transparent bottom electrode in the
device. PFO, one of the outstanding luminescent polymers
for blue emission, was synthesized by our group15 and spin-
coated on top of the ITO as an active material in the TPLED.
The solution-based TiOx layer was spin-cast in air on top
of the PFO layer with a thickness of around 30 nm. The TiOx
films were prepared using a sol-gel processed TiOx precursor
solution.16,17 The sol-gel procedure for producing TiOx is as
follows; titanium(IV) isopropoxide (Ti[OCH(CH3)2]4, Aldrich,
99.999%, 10 ml) was prepared as a precursor and mixed with
2-methoxyethanol (CH3OCH2CH2OH, Aldrich, 99.9þ%,
50 ml) and ethanolamine (H2NCH2CH2OH, Aldrich, 99þ%,
5 ml) in a three-necked flask, each connected to a condenser,

0003-6951/2012/100(13)/133306/4/$30.00 100, 133306-1 C 2012 American Institute of Physics

V
133306-2 Park et al.
FIG. 1. Device structures of the transparent polymer light emitting diode
(TPLED) together with the molecular structure of TiOx and the PFO
material.
thermometer, and argon gas inlet/outlet. Then, the mixed solu-
tion was heated to 80  C for 2 h in a silicon oil bath under mag-
netic stirring, followed by heating to 120  C for 1 h. The two-
step heating process (80  C and 120  C) was then repeated. The
typical TiOx precursor solution was prepared in isopropyl
alcohol.
The use of TiOx is crucial for achieving a high-
performance TPLED. The TiOx layer serves five important
functions. First, the TiOx layer functions as a protecting ma-
terial. Given that TiOx is based on stable inorganic materials
(see Figure 1) and exhibits extremely high optical density in
the UV range, the TiOx layer can reduce damage to the
Appl. Phys. Lett. 100, 133306 (2012)
underlying active material caused by UV radiation and the
highly energetic ions generated during RF sputtering for the
AZO top electrode. Second, the TiOx layer reduces the
energy barrier for electron injection via modification of WF
for AZO.18,19 Third, TiOx functions as an electron transport
layer due to its high electron mobility.16 Fourth, the TiOx
functions as a hole-blocking layer because the top of the va-
lence band of TiOx is sufficiently electronegative to block
holes.17,20 Finally, the TiOx layer functions as a passivation
layer that prevents penetration by O2 and H2O into the active
layer and significantly increases the lifetime of device when
exposed to air.21
AZO top electrodes were deposited using an RF sputter-
ing technique on top of the TiOx layer. Argon and oxygen
were used as the process gas and reactive gas, respectively.
When the target was being prepared, metallic zinc with alu-
minum content of 2 wt. % was applied. AZO electrode thin
films with low electrical resistivity of 20 X/h were depos-
ited by an RF sputtering technique. Unlike the more com-
monly used ITO, AZO is a nontoxic, inexpensive, and
abundant material.22,23
The most important requirement for TPLEDs is the
transparency of all components in the visible range. Figures
2(a)–2(d) show the transmittances of each component: ITO,
AZO, PFO, and TiOx, respectively. The ITO and the AZO
film exhibits similar transmittance spectra with average opti-
cal transmittance in the visible range (400  800 nm) of
above 85%. When we measure their transmittances to
2500 nm as shown in the insets of Figures 2(a) and 2(b), re-
markable Drude-peaks related to free electrons in the infra-
red range are observed in both films. The PFO film exhibits a
relatively high band gap of 2.75 eV, with high transmit-
tance of 80% in the visible range. Earlier work has demon-
strated that the PFO produces blue emission for pure
materials without a keto-defect site at 9-position.24,25 A rela-
tively large Stokes’ shift between absorption and emission
FIG. 2. Transmittance spectrum of the
(a) ITO, (b) AZO, (c) PFO, and (d) TiOx
layer.
133306-3 Park et al.
for PFO allows the film be transparent in the visible range
with a visible emission. The TiOx layer is also transparent in
the visible range, with transmittance above 90%.
Although the device can be fabricated easily, as described
above, one issue must still be addressed for production of an
efficient TPLED. Since a conventional AZO top electrode
exhibits a WF that is almost the same as that of the ITO bot-
tom electrode (4.8 eV), it is difficult to match the charge va-
lence between holes injected from the ITO and electrons
injected from the AZO, when AZO is used as a cathode. This
means that the energy difference between the highest occu-
pied molecular orbital (HOMO) level of the PFO and the
AZO work function is much larger than the energy difference
between the LUMO level and the ITO work function, and
consequently, a high energy barrier for electron injection
occurs at the interface of the PFO and the AZO.
The introduction of TiOx before AZO deposition in this
process provides a good solution to this issue. Since TiOx is
an n-doped semiconductor, the introduction of a TiOx layer
onto the metallic AZO can raise the WF of the AZO as a
results of the generation of a Schottky barrier at the interface
Appl. Phys. Lett. 100, 133306 (2012)
FIG. 3. Energy level diagram of the
TPLED with and without the TiOx layer.
(b) WF values for ITO, AZO, and AZO/
TiOx measured by the Kelvin probe
method.
between the metallic AZO and the semiconducting TiOx; con-
sequently, the energy barrier between the PF and the AZO
electrode decreases. In addition, earlier ultraviolet photoelec-
tron spectroscopy (UPS) studies demonstrated that insertion
of the TiOx layer between the conjugated polymer layer and
metal electrode can alter the WF of the electrode due to the
existence of a strong interfacial dipole at the surface of the
TiOx and electrodes.18,19 Figures 3(a) and 3(b) present energy
level diagrams for the TPLED with and without, respectively,
the TiOx layer. Although the pristine TPLED without the
TiOx layer exhibits a highly symmetric band structure, modi-
fying the TPLED by inserting the TiOx layer can break the
symmetry of its energy band structure and lower the energy
barrier for electron injection from the AZO.
Figure 3(c) shows the WF values for AZO films with
and without the TiOx layer, directly measured by the Kelvin-
probe method. While the untreated AZO film without the
TiOx layer exhibits a WF almost the same as that of the ITO
(i.e., 4.8 eV), the AZO film significantly changes its work
function, from 4.8 eV to 4.5 eV, when TiOx is introduced.
This clearly indicates that the TiOx layer breaks the
FIG. 4. (a) Current density-voltage and
(b) brightness-voltage characteristics for
devices with and without the TiOx layer.
133306-4 Park et al.
symmetric band structure of component of the TPLED and
serves as an electron injection layer. In addition, the TiOx
layer functions as a hole blocking layer (HBL) in the device
on account of its deep HOMO energy level, i.e., 8.0 eV.17,20
The device with the structure of glass substrate/ITO/
PFO/TiOx/AZO operates well as a transparent device with
emission from the PFO. Figure 4(a) shows photographs of
the TPLED with the TiOx layer and the AZO electrode in
front of a red flower-shaped mirror. The TPLED consists of
four pixels, as shown in the sketched pixel structure. When
we turn on one of the pixels in the device by applying a for-
ward bias, the TPLED emits light through the transparent top
AZO and the bottom ITO at the same time. Note the light
image reflected from the mirror together with the light image
from the top electrode. In particular, the TPLED is highly
transparent in the visible range, with average transmittance
of 90% from 450 nm to 800 nm. Refer to the image of three
pixels marked “off” in Figure 4(a) and the photograph of the
film of ITO/PFO/TiOx/AZO on the Pukyong National Uni-
versity letters in Figure 4(b).
Figure 4(c) shows the current density versus voltage
(J-V) and the brightness versus voltage (L-V) characteristics
of the devices with and without the TiOx layer. These J-V
and L-V curves exhibit typical characteristics of polymer
light-emitting diodes.13,14,26 When the TiOx layer was
inserted between the polymer and the AZO anode, we
observed a significant increase in current density as com-
pared to the conventional device without the TiOx layer; for
instance, the current density of the conventional device is
about 20 mA/cm2 at 25 V, whereas the TiOx device exhibits
100 mA/cm2, a five-fold increase, at the same voltage.
Because the TiOx layer reduces the barrier for electron injec-
tion by altering the WF of AZO, the increase in current den-
sity within the device with TiOx layer is easily understood
by the reduced contact resistance due to the reduced energy
barrier. The L-V curves also demonstrate the significantly
enhanced device properties of the TiOx devices as shown in
Figure 4(c). For the TiOx devices, the brightness dramati-
cally increases compared to the conventional device. As a
consequence, the luminous efficiency of the TiOx device is
almost 50% higher than that of the conventional device as
shown in Figure 4(d). Because the TiOx layer serves as an
electron injection layer and hole-blocking layer, the increase
in luminous efficiency of the device with the TiOx layer is
also attributed to the enhanced charge balance matching
between the holes and electrons in the active layer. The over-
all results clearly demonstrate that the TPLED with the TiOx
layer exhibits a device performance superior to that of the
TPLED without the TiOx layer. Since the inorganic TiOx
layer is more stable than organic polymers and exhibits
strong absorption peaks in the UV range, as demonstrated in
Figure 2(d), we are confident that the TiOx layer prevents the
damage caused by UV radiation and by highly energetic ions
generated during the AZO sputtering.
In conclusion, we have successfully demonstrated a
TPLED using AZO as a transparent top electrode and
solution-processed TiOx as an electron transporting and pro-
tecting material. The TiOx layer in the TPLED lowers the
energy barrier between the luminescent polymer and the
Appl. Phys. Lett. 100, 133306 (2012)
AZO top electrode by modifying the WF of the top AZO
electrodes. Moreover, the TiOx layer prevents the damage
caused by UV radiation and by highly energetic ions gener-
ated during the AZO sputtering, and thereby preserves the in-
tegrity of the luminescent polymers in TPLEDs using AZO
top electrodes. We believe that the TiOx layer is a promising
candidate material for preventing the damage caused by UV
radiation and by highly energetic ions generated during the
AZO sputtering.
This work was supported by Basic Science Research
Program through the National Research Foundation of Korea
(NRF) funded by the Ministry of Education, Science, and
Technology (C-D-2011-0251). The work in GIST was sup-
ported by the National Research Foundation of Korea (NRF)
grant funded by the Korea Government (MEST) (No.
20090093869) and the World-Class University Program
funded by the Ministry of Education, Science, and Technol-
ogy through the NRF (R31-10026).
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