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Mo-doped GZO film used as anode or cathode

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Article in Journal of Materials Chemistry C November 2015

DOI: 10.1039/C5TC02637G

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Journal of
Materials Chemistry C
PAPER

Mo-doped GZO films used as anodes or cathodes

for highly ecient flexible blue, green and red
Cite this: J. Mater. Chem. C, 2015,
3, 12048 phosphorescent organic light-emitting diodes
Chih-Hao Chang,* Jun-Lin Huang and Szu-Wei Wu

Received 24th August 2015,
Accepted 26th October 2015
DOI: 10.1039/c5tc02637g
www.rsc.org/MaterialsC
We propose a novel transparent conductive oxide constructed by doping molybdenum into gallium zinc
oxide (GZO). The molybdenum doped GZO (MGZO) on a glass substrate possesses a high average
transmittance of 92% in the visible wavelength range, a high work function of 5.08 eV, a low sheet
resistance of 37.2 O sq 1, and an adequate mobility of 2.92 cm2 V 1 s 1. Furthermore, the MGZO films on a
PET substrate retained a low electrical sheet resistance after 1000 outward bending cycles. By using MGZO
films as anodes in conventional blue, green, and red phosphorescent organic light-emitting diodes (OLEDs)
on a PET substrate, low turn-on voltages ranging from 2.7 V to 3.1 V could be obtained. Moreover, the EL
eciencies of the conventional blue, green, and red OLEDs, respectively, reached 21.3%, 17.9%, and 8.9%. In
addition, flexible MGZO films were further examined as cathodes in blue (green and red) inverted OLEDs,
and gave satisfactory performance including a high eciency of 16.5% (17.5% and 8.5%) and an acceptable
turn-on voltage of 3.6 V (3.1 V and 3.4 V). These superior characteristics make MGZO films high-potential
candidates as transparent electrodes for future applications in flexible optoelectronics.

Introduction
Organic light-emitting diodes (OLEDs) are an emerging tech-
nology that allows for the creation of beautiful displays and
ecient lighting panels. Thin and light OLED panels are
potentially flexible/bendable, allowing for integration into
clothing, backpacks, wallpapers or other curved surfaces. Flexible
OLED panels oer several additional advantages over glass-based
displays: they are lighter, thinner and much more durable. In
particular, fueled by the growing demand for health care devices
and services, comfortable wearable devices equipped with curved
OLED displays have been developed to provide immediately
visible health-related information. However, the first challenge
for the creation of flexible optoelectronics is related to the
properties of indium tin oxide (ITO) in transparent electrodes.
ITO is brittle, making it unsuitable for use with flexible sub-
strates.1 Previous studies have explored the use of alternative
materials better suited for flexible applications including gallium
doped zinc oxide (GZO) based transparent conducting oxides
(TCOs), silver wires, carbon nanotubes and even graphene.25
Among these candidates, the high chemical stability and low cost
Department of Photonics Engineering, Yuan Ze University, Chung-Li, Taiwan 32003.
E-mail: chc@saturn.yzu.edu.tw; Fax: +886 3 4638800, ext. 7517;
Tel: +886 3 4514281
Electronic supplementary information (ESI) available. See DOI: 10.1039/
c5tc02637g
of GZO makes it the most promising TCO material because it can
be immediately applied in existing production processes. More-
over, GZO consists of closed GaO and ZnO bonds with respec-
tive lengths of 1.92 and 1.97 , which could reduce the
incidence of crystal defects resulting from lattice strain. In
addition, the smooth GZO surface contributed by the surfactant
effect of Ga doping in ZnO is beneficial for the development of
various optoelectronic devices, particularly OLED applications.6
Furthermore, some GZO-based TCOs have been shown to have
optoelectronic properties comparable to those of ITO.7 We have
demonstrated that Ga-doped TiZnO (GTZO) thin films possess
high transmittance, low resistance, and high carrier mobility.8
These excellent optoelectronic properties make GTZO films suit-
able alternatives for use as anodes in OLED applications. Simpli-
fied tri-layer blue, green, and red phosphorescent OLEDs with the
GTZO anodes exhibited high performance with respective max-
imum efficiencies of 19.0%, 14.5%, and 9.1%, representing an
improvement over ITO-based OLEDs. However, the GTZO films
inherit the drawback of GZO with a low work function of 4.6 eV,
which is similar to that of ITO (i.e. 4.7 eV). A high energy barrier
between the anode and organic hole transporting layers will lead
to higher driving voltages in OLEDs with GTZO anodes.
In this study, we develop a new TCO through doping a small
amount of molybdenum into GZO to simultaneously increase
the conductivity and modify the work function. We speculate
that the Mo6+ substitution for Zn2+ ions in GZO films will
behave as a donor providing an extra four free electrons, thus

12048 | J. Mater. Chem. C, 2015, 3, 12048--12055 This journal is The Royal Society of Chemistry 2015
Paper Journal of Materials Chemistry C

increasing thin-film conductivity.9 In addition, the high work

function of molybdenum oxide (MoO3) (i.e. 5.3 eV) could
increase the work function of GZO (i.e. 4.6 eV) to ensure that
the energy levels match, thus improving carrier injection into
organic layers.10 Moreover, the price of molybdenum metal is
much lower than that of indium, creating favorable conditions
for the commercialization of this newly developed TCO. For
reference, indium, gallium and molybdenum are, respectively,
priced at about $ 370, 205, and 19.7 US dollars per Kg, which
were according to the information exposed on the website on
Sep. 30, 2015. Last but not least, the fabrication of this TCO
could use existing RF sputter techniques, allowing for seamless
integration into current mass production processes. Based on
these advantages, we seek to develop Mo-doped GZO (MGZO)
films for flexible OLED applications.
On the other hand, in addition to conventional bottom-
emitting OLEDs, we also examine the ecacy of MGZO films as
cathodes in inverted OLEDs (IOLEDs). IOLEDs have several
advantages including their easy integration with n-channel thin
film transistors (TFTs), mitigation of eciency roll-o, longer
lifetime, etc.11 The latter is due to the fact that water and oxygen
sensitive electron injection materials reside beneath the organic
and metal layers. In general, a thin metal layer is usually used as
the cathode in IOLEDs to decrease the energy barrier between the
cathode and organic layers and thus provide sucient electron
injection, but spectral variations in dierent viewing angles
resulting from the microcavity eect make it unsuitable for use
in display applications. Based on our previous study, transparent
conductive oxide could be used as a transparent cathode to
prevent the microcavity eect in IOLEDs.12 We demonstrated that
an eective electron injection layer providing interfacial dipoles
could be inserted between the cathode and organic layers to
decrease the injection barrier and thus increase electron injection.

Results and discussion

(i) Electrical and optical properties of MGZO films on the
glass substrate
Fig. 1(a) shows the electrical resistivity (r), mobility (m), and
carrier concentration (n) of the MGZO films (120 nm) coated on
the glass substrate at dierent post-annealing temperatures.
As annealing temperature increased from 250 to 450 1C, the
resistivity of the MGZO films decreased from 7.18  10 3 to
4.46  10 4 O cm. Furthermore, the lowest sheet resistance of
37.2 O square 1 was obtained, indicating that higher annealing
temperatures improved the crystallinity of the films and decreased
the surface roughness.13 One reason for this is that annealing
treatment produces more oxygen vacancies, thus increasing the
carrier concentration.14 Another reason is that increased annealing
temperatures result in more Zn2+ sites being replaced by the Mo6+
or Ga3+ ions.15 The highest carrier concentration of 6.13 
1021 cm 3 was recorded at an annealing temperature of 350 1C,
which accompanied a low mobility of 2.06 cm2 V 1 s 1. More-
over, a slightly lower carrier concentration of 4.79  1021 cm 3
and a higher mobility of 2.92 cm2 V 1 s 1 were measured at an
Fig. 1 (a) Hall electrical resistivity (r), mobility (m), and carrier concen-
tration (n) of the MGZO films (120 nm) as a function of annealing
temperature. (b) Optical transmittance of MGZO films prepared at various
annealing temperatures. Inset: The photoluminescent spectra of MGZO
films at various annealing temperatures. (c) XRD patterns of MGZO films
deposited at various annealing temperatures.
annealing temperature of 450 1C. Obviously, the higher carrier
concentration of the MGZO films (41021 cm 3) over that of
typical ZnO films was attributed to the additional free electrons
provided by the substitution of Mo6+ into Ga3+ or Zn2+ sites,
producing more excess electrons in the MGZO films.16 On the
other hand, the work function of MGZO films on the glass
substrate was evaluated at 5.08 eV, confirming our initial
assumption.
Fig. 1(b) shows an average high transmittance of 92% in
the 350800 nm wavelength region, which indicates superior

This journal is The Royal Society of Chemistry 2015 J. Mater. Chem. C, 2015, 3, 12048--12055 | 12049
Journal of Materials Chemistry C
optical properties compared to those of typical ITO thin films.17
In addition, by considering an electron transition from valence
to conduction bands when a thin film absorbs a photon of
energy (hn), we could calculate the optical band gap (Eg) of the
MGZO films with different annealing temperatures. In general,
the absorption coefficient (a) and the optical band gap follow
the relationship (ahn)2 = (hn Eg),18 where h is the Planck
constant and Eg is the photon frequency. The Eg could be
deduced by extrapolating the linear portion of a plot of (ahn)2
against the (hn) axis. The optical band gaps of MGZO films with
different annealing temperatures were evaluated from the Tauc
plot and are summarized in Table 1. The optical band gaps of
MGZO were around 3.633.65 eV. The increased electron concen-
tration slightly shifts the Fermi level due to the so-called
BursteinMoss effect.19,20 The experiment results showed that
the highest optical band gap of MGZO (i.e. 3.65 eV) was recorded
at an annealing temperature of 350 1C. In addition, the absorp-
tion edge moved back to the longer wavelength region at a
higher annealing temperature of 450 1C. The slightly lower
carrier concentration was due to the mitigated BursteinMoss
effect. The inset of Fig. 1(b) shows the photoluminescent (PL)
spectra of MGZO films with various annealing temperatures.
The peaks at 382 and 529 nm are recognized as the near band
edge (NBE) emission and oxygen vacancies emission.21,22 These
enhanced peaks demonstrate that the annealing processes
helps to increase the carrier concentrations of MGZO films,
which agrees well with the Hall measurement results. Fig. 1(c)
shows the X-ray diffraction (XRD) patterns of MGZO films depos-
ited at various annealing temperatures. The films annealed at
350 1C exhibited a higher (002) peak compared to the films
annealed at 250 1C and 450 1C, presenting the optimized
Table 1 Electrical and optical properties, and figure of merit of the MGZO films coated on a glass substrate at dierent annealing temperatures
Annealing Avg. transmittance Optical band Work Resistivity Sheet resistance Carrier concentration Mobility
temp. (1C) (%) [380780 nm] gap (eV) function (eV) (10 4 O cm) (O sq 1)
RT 92.3 3.62 5.01 7.07
250 92.4 3.63 5.02 7.18
350 92.5 3.65 5.09 4.93
450 92.4 3.64 5.08 4.46
Fig. 2 AFM images of MGZO films on (a) glass and (b) PET substrates.
12050 | J. Mater. Chem. C, 2015, 3, 12048--12055
Paper
annealing temperature for crystallinity of MGZO films. These results
were consistent with the aforementioned electrical properties.
Table 1 summarizes the electrical and optical properties
of MGZO films with dierent annealing temperatures. Figure
of merit (FTC) was used to evaluate the performance of the
fabricated MGZO films, expressed as FTC = T10/RS, where T is
the average transmittance in the visible wavelength region
(380780 nm), and RS is the sheet resistance of the TCO films.23
From Table 1, the MGZO films annealed at 450 1C exhibit the
highest FTC of all films.
(ii) Surface morphology and mechanical properties of MGZO
films on the polyethylene terephthalate (PET) substrate
Encouraged by the performance of MGZO on the glass substrate,
we further examined the MGZO films on a highly transparent
polyethylene terephthalate (PET) substrate by RF sputtering.
However, because the decomposed temperature of the PET
substrate is less than 220 1C, we had to abandon the thermal
annealing process for the MGZO/PET substrate. AFM was used to
monitor the MGZO surface morphology on dierent substrates,
as shown in Fig. 2. Compared to the MGZO films on the glass
substrate, bypassing the annealing process led to a smaller grain
size and thereby a smoother surface.13,24 The respective arithmetic
average roughnesses (Ra) of MGZO/glass and MGZO/PET sub-
strates were about 1.67 nm and 0.39 nm which are considered
to not aect the sequential manufacturing processes. Further-
more, we further measured the surface morphology of glass and
PET substrates. The respective arithmetic average roughnesses of
glass and PET substrates were recorded to be 1.25 nm and
0.38 nm, indicating that the additional 120 nm-MGZO films
didnt alter the surface roughness significantly. However, omitting
Figure of merit
(10 21 cm 3) (cm2 V 1 s 1) FTC (10 3 O 1)
58.9 3.49 2.53 7.6
59.8 4.11 2.12 7.6
41.1 6.13 2.06 11.1
37.2 4.79 2.92 12.2
This journal is The Royal Society of Chemistry 2015
Paper
the annealing processes will result in fewer oxygen vacancies and
less crystallinity, thus leading to reduced conductivity of the
MGZO films. As a result, 120 nm-MGZO films based on the PET
substrate exhibited an adequate thin film sheet resistance of
89.1 O square 1. Fortunately, the sheet resistance of MGZO was
still within acceptable ranges for OLED applications. Moreover,
the average high optical transmittance of 92.3% in the wavelength
range between 380 and 780 nm was preserved.
In addition, the work function of MGZO films on a PET
substrate was evaluated to be 4.75 eV. Comparing to the work
function of MGZO films on a glass substrate, bypassing the
annealing process also led to a lower work function. Thus,
MGZO anodes without UV-ozone treatment were used to examine
the carrier injection in the conventional OLEDs. The outcomes
showed that the MGZO-based conventional OLEDs without
UV-ozone treatment possessed extremely low current density
and poor eciency. Therefore, we deduced that an increased
work function of MGZO could be obtained by employing the
UV-ozone treatment.25
Flexible electrodes require stable morphology and electri-
city after bending. Thus, we monitored the surface images and
electrical resistance of both MGZO and ITO films on the PET
substrate after repeated outward bending. The parameters
of bending radius and rate were, respectively, set at 8 mm
and 60 revolutions per min.26 Fig. 3(a) shows the bright-field
microscopy images of both tested films before and after
bending. Many channeling cracks appeared in the same
orientation on the ITO surface, while the MGZO films main-
tained a smooth surface after 1000 bending cycles. Fig. 3(b)
shows the normalized resistance change after repeated bend-
ing as a function of the number of cycles for MGZO and ITO
films. The electrical resistance of the ITO-based PET substrate
increased rapidly with bending iterations to about 60 times
the original value. In sharp contrast, the MGZO-based PET
substrate retained low electrical sheet resistance after bend-
ing. The aforementioned superior optoelectronic and mechan-
ical properties make MGZO films potential anodes for use in
flexible OLEDs.
Fig. 3 (a) Bright-field microscopy images of MGZO and ITO films on the PET substrate before or after repeated bending. (b) Normalized resistance vs.
bending cycles for MGZO and ITO films.
This journal is The Royal Society of Chemistry 2015
Journal of Materials Chemistry C
(iii) Conventional blue, green, and red phosphorescent
OLEDs with MGZO anodes
In this study, both ITO and MGZO anodes were used to
compare the performance of OLEDs with a simplified tri-layer
architecture based on the PET substrate. Iridium(III) FIrpic,
Ir(ppy)3, and Ir(piq)3 were, respectively, selected as the blue,
green, and red phosphorescent emitters because of their high
quantum yields.2729 To fulfill the requirement of hostguest
energy transfer, host and carrier transport materials with wide
triplet energy gap hosts and wide gaps should be adopted in the
architecture design. According to our previous studies, bipolar
3-bis(9-carbazolyl)benzene (mCP) possessing a wide-triplet energy
gap of 2.9 eV could effectively provide endothermic energy
transfer from the host to the blue, green, and red guests.30
Furthermore, 1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene (TmPyPB)
and di-[4-(N,N-ditolyl-amino)-phenyl] cyclohexane (TAPC) were,
respectively, selected as the electron-transport and electron
blocking layers due to their excellent carrier transport capabil-
ities and adequate energy gaps.31,32 Consequently, the tri-layer
architecture for blue, green, and red OLEDs consisted of PET
substrate/ITO (Device I) or MGZO (Device II) (120 nm)/TAPC
(30 nm)/mCP doped with 8 wt% phosphorescent emitter
(20 nm)/TmPyPB (50 nm)/LiF (0.5 nm)/Al (150 nm), where the
LiF and aluminum were, respectively, used as the electron-
injection layer and cathode. Fig. 4 shows a structural drawing of
the materials, the schematic structures, and the energy level
diagrams of the tested OLEDs.
The electroluminescence (EL) characteristics of the tested
conventional OLEDs with dierent anodes are collected in
Table 2 and are also shown in Fig. S1 in the ESI. All devices
exhibited similar EL spectra with pure dopant emissions,
demonstrating that the carrier recombination was well con-
fined within the EML and the exciton diusion to the adjacent
layers has been avoided. Moreover, although the tested blue,
green, and red devices used dierent anodes, the similar
spectral profiles illustrated the similar location of the carrier
recombination zone. The current densityvoltageluminance
( JVL) curves of OLEDs indicated that the devices with ITO
J. Mater. Chem. C, 2015, 3, 12048--12055 | 12051
Journal of Materials Chemistry C Paper

Fig. 4 (a) Chemical structures of the organic materials; (b) the schematic architecture of the tested flexible OLEDs with ITO and MGZO electrodes;
(c) the energy level diagram of the tested flexible OLEDs with MGZO electrodes.

Table 2 EL characteristics of blue, green, and red phosphorescent conventional and inverted OLEDs with MGZO or ITO electrodes on the PET
substrates

Flexible device IB IIB IIIB IG IIG IIIG IR IIR IIIR

Dopant FIrpic Ir(ppy)3 Ir(piq)3
Anode ITO MGZO Al ITO MGZO Al ITO MGZO Al
Cathode Al Al MGZO Al Al MGZO Al Al MGZO
a a a a a a a a
External quantum 20.0 21.3 16.5 19.1 17.9 17.9 10.2 8.9 8.9a
eciency (%) 18.0b 19.0b 16.5b 19.1b 17.6b 17.2b 6.6b 5.7b 6.7b
Luminance eciency (cd A ) 45.5a
1
47.5 a
39.2 a
67.9a 63.7 a
62.9 a
7.1a 6.0a 6.3a
41.1b 42.4b 39.2b 67.9b 62.8b 60.6b 4.7b 3.9b 4.8b
1
Power eciency (lm W ) 46.6a 49.2 a
31.7 a
65.3a 71.5 a
65.8 a
7.5a 6.7a 6.6a
32.2b 33.3b 23.7b 53.3b 62.6b 41.3b 3.3b 2.6b 2.3b
Turn on voltage (V) 3.1c 3.1c 3.6c 3.1c 2.7c 3.1c 3.1c 3.0c 3.4c
CIE 1931 coordinates (0.17, 0.40)b (0.16, 0.39)b (0.18, 0.40)b (0.32, 0.62)b (0.32, 0.62)b (0.34, 0.61)b (0.68, 0.32)b (0.68, 0.31)b (0.68, 0.32)b
(0.17, 0.40)d (0.16, 0.39)d (0.19, 0.42)d (0.32, 0.62)d (0.32, 0.62)d (0.34, 0.61)d (0.68, 0.32)d (0.68, 0.31)d (0.68, 0.32)d

Max. luminance (cd m 2) [V] 41 352 [8.2] 30 048 [11.6] 15 918 [19.0] 66 079 [9.0] 42 807 [16.4] 33 630 [19.0] 5417 [8.0] 3700 [14.4] 3058 [16.0]
a b 2 2 c 2 d 3 2
Maximum eciency. Recorded at 10 cd m . Turn-on voltage measured at 1 cd m . Measured at 10 cd m .

anodes had higher current densities than those of the devices
with MGZO anodes, resulting from the higher mobility and
lower sheet resistance of the ITO films. Nevertheless, devices
with MGZO anodes exhibited lower turn-on voltages than those
of ITO-based OLEDs, representing that a lower energy barrier
between the anode and organic layers could be obtained due to
the efficacy of the higher work function of the MGZO films.
Therefore, we deduced that an increased work function of
MGZO could be obtained by employing the UV-ozone treat-
ment, as shown in Fig. 4(c). Moreover, the MGZO-based blue
(green and red) OLEDs exhibited an EL efficiency of 21.3%
(17.9% and 8.9%), while the control blue (green and red)
devices with the ITO anodes exhibited an efficiency of 20.0%
(19.1% and 10.2%). It worth to noting that Device IIB with a
simplified tri-layer architecture reached an internal quantum
efficiency of nearly 100% according to the assumption of 20%
out-coupling efficiency, which might result from the suitable
hostguest system and adequate carrier injection from the
MGZO anode.33 To evaluate the performance of the developed
MGZO films, we compared the articles published during 2007
2014 which addressed flexible anodes for bottom-emitting
OLED applications (see Table S1 in the ESI). The outcomes
indicated that the performance of the MGZO-based OLEDs were
not inferior to those of other previously-reported flexible
anodes in terms of both efficiency and turn-on voltages. Over-
all, these comparable results indicate that the bending durable

12052 | J. Mater. Chem. C, 2015, 3, 12048--12055 This journal is The Royal Society of Chemistry 2015
Paper
Fig. 5 (a) EL spectra of Devices IIB, IIG, IIR, IIIB, IIIG, and IIIR; (b) current densityvoltageluminance (JVL) curves; (c) external quantum efficiency vs.
luminance; (d) luminance efficiency vs. luminance; (e) photos of Devices IIIB, IIIG, and IIIR operating at 8 V.
MGZO films possess high potential for use in flexible displays
and lighting applications.
(iv) Inverted blue, green, and red phosphorescent OLEDs with
MGZO cathodes
In general, to avoid the microcavity eect in inverted OLEDs
(IOLEDs), it is preferable to use a TCO film and a metal layer,
respectively, as a transparent cathode and a reflective anode.
However, a high energy barrier formed at the interface between
the TCO cathode and the organic layer restricts the electron
injection to the lowest unoccupied molecular orbital (LUMO),
leading to a carrier imbalance as well as higher operation
voltages. Based on our previous study of IOLEDs, an eective
bi-layered electron injection layer (EIL) consisting of a Li2CO3
layer and a TmPyPB layer doped with Li2CO3 could help
mitigate the energy barrier and thus decrease the operation voltage
in IOLEDs.12 Therefore, we further examined the eectiveness of
the MGZO films as cathodes on the PET substrate following our
previous architecture. Consequently, the device architecture of the
flexible blue, green, and red IOLEDs, respectively, consisted of
This journal is The Royal Society of Chemistry 2015
Journal of Materials Chemistry C
PET/MGZO (120 nm)/Li2CO3 (5 nm)/TmPyPB: Li2CO3 20 wt%
(5 nm)/TmPyPB (50 nm)/mCP doped with 8 wt% phosphorescent
emitter (20 nm)/TAPC (30 nm)/HATCN (10 nm)/Al (150 nm), where
the HATCN and aluminum were used as the hole-injection layer
and anode, respectively (see Fig. 4(b)).
Fig. 5 and Table 2 compare the corresponding EL character-
istics of conventional OLEDs and inverted OLEDs based on the
MGZO/PET substrate (i.e., Devices II and III). From the EL
spectra shown in Fig. 5(a), the slight variation in the spectral
profiles was attributed to the eect of optical interference. No
other emission was observed, the carrier recombination zone
was located in the emitting layer (EML) and the exciton con-
finement was also restricted in the EML. In other words, the
opposite carriers could meet each other in the EML, indicating
that MGZO cathodes provided a balanced and adequate supply
of electrons comparing to the aluminum anode. Nevertheless,
because the MGZO films were exchanged from anodes to
cathodes, as expected, all IOLEDs showed inferior current
density than that of conventional OLEDs. Fortunately, blue,
green, and red IOLEDs gave respective turn-on voltages of 3.6 V,
J. Mater. Chem. C, 2015, 3, 12048--12055 | 12053
Journal of Materials Chemistry C
3.0 V, and 3.4 V, higher than those of flexible conventional
OLEDs (i.e. Device II) with accepted values of about 0.40.5 V. In
terms of driving voltages, transparent and flexible MGZO films
could be considered as alternate cathode materials for use in
IOLEDs.
As shown in Fig. 5(c), compared to Device IIB, the reduced
carrier injection from the MGZO cathode or aluminum anode
resulted in carrier imbalance and a higher turn-on voltage in
Device IIIB. Devices IIIG and IIIR showed a similar phenomena
of higher turn-on voltages. Fortunately, the eciencies of
Devices IIIG and IIIR were quite similar to those of Devices
IIG and IIR even though Device III harvested lower current
densities. This is likely attributable to the changed carrier
balance in the inverted OLEDs as compared to the conventional
OLEDs with MGZO anodes. Flexible green IOLEDs gave a
maximum luminance of 33 630 cd m 2 at 19.0 V, and peak EL
eciencies of up to 17.9%, 62.9 cd A 1, and 65.8 lm W 1. At a
practical brightness of 102 cd m 2, the eciencies remained
high at around 17.2%, 60.6 cd A 1, and 41.3 lm W 1. The
maximum eciencies of flexible red IOLEDs were recorded to
be 8.9%, 6.3 cd A 1 and 6.6 lm W 1. At a practical brightness
of 102 cd m 2, their eciencies were 6.7%, 4.8 cd A 1 and
2.3 lm W 1. These green and red IOLEDs based on the MGZO
cathodes showed adequate eciency levels, which implies that
the carrier balance could be achieved easily in this universal
architecture for various phosphorescent emitters. Furthermore,
the performance of our devices was considerably superior than
those of flexible IOLEDs discussed in previous articles.34,35
Overall, these results indicate that the bending durable MGZO
films possess high potential for use as anodes or cathodes in
flexible OLED displays and lighting applications.
Experimental
Preparation of TCO films
The MGZO films were grown using a 3 in ZnO/Ga2O3/MoO3
(95/3/2 wt%, purity 99.99%) target. MGZO films were deposited
by RF magnetron sputtering on glass and PET substrates at
heating temperatures of 300 1C and 200 1C. The RF sputtering
power was kept at 100 W. The working pressure was maintained
at about 1.0  10 3 Torr with an argon gas flow of 30 standard
cubic centimeters per min (sccm). The thickness of the deposited
MGZO films was maintained at 120 nm which is the commonly
used thickness in OLED applications. MGZO films on the glass
substrate were then thermally post-annealed for 3 min in an
ambient nitrogen atmosphere at temperatures ranging from
250 to 450 1C in a rapid thermal annealing (RTA) system, while
the annealing process was abandoned in the case of MGZO
films on the PET substrate.
Electrical, photophysical, and surface morphology
measurements
Electrical resistivity, mobility, and carrier concentration were
measured by a Hall measurement system using the van der
Pauw configuration at room temperature. The PL spectra of
12054 | J. Mater. Chem. C, 2015, 3, 12048--12055
Paper
emitters were measured using a CCD spectrograph and the
325 nm line of a HeCd laser as the excitation source. Optical
transmission measurements were conducted using a Shimadzu
UV-1650PC spectrophotometer. Microscope images were taken
using an optical microscope (PoTop, HVC-300-CA). The work
function of MGZO films was measured by using a photoelectron
spectrometer (RIKEN KEIKI AC-2 LC1). The surface morphology
of the MGZO films on both glass and PET substrates was
monitored by atom force microscopy (AFM) (SEIKO, SPA400-
SPIWin). The microstructure of the MGZO films was character-
ized by X-ray diffraction.
OLED fabrication
Organic materials for the small molecules used were purchased
from Nichem and Lumtec. All organic compounds were sub-
jected to temperature-gradient sublimation under high vacuum
before use. The organic and metal layers were deposited by
vacuum evaporation in a vacuum chamber with a base pressure
of o10 6 Torr. Both MGZO and ITO films were chosen as the
transparent electrodes for OLED fabrication. The active area of
the devices was set to 2  2 mm2, as defined by the shadow
mask used for cathode deposition. The current densityvoltage
luminance characterization was measured using a Keithley 238
current source-measure unit and a Keithley 6485 picoammeter
equipped with a calibrated Si-photodiode. The electroluminescent
spectra of the devices were recorded using an Ocean Optics
spectrometer.
Conclusion
We investigate the development of high-quality MGZO films by
RF magnetron sputtering. A low sheet resistance of 37.2 O sq 1,
a high transmittance of 92% and a high work function of
5.08 eV were realized through doping molybdenum into GZO
films on a glass substrate. Furthermore, the MGZO films inherit
the mechanical strength of GZO and thus possessed high
stability of sheet resistance after regular bending on a PET
substrate. The superior characteristics of the resulting MGZO
films make them suitable for use in OLED applications. Simpli-
fied tri-layer blue, green, and red phosphorescent OLEDs were
used to examine both MGZO and ITO anodes on the flexible PET
substrate. Devices with MGZO anodes exhibited performance
comparable to those with ITO anodes. The EL eciency of the
flexible blue (green and red) phosphorescent OLEDs with MGZO
anodes was 21.3% (17.9% and 8.9%), which is comparable to
their ITO counterparts. In addition, low turn-on voltages ranging
from 2.7 V to 3.1 V were found in MGZO-based OLEDs. Further-
more, transparent MGZO films were also used as cathodes in
inverted OLEDs on a PET substrate. The resulting flexible blue,
green, and red IOLEDs exhibited respective peak EL eciencies
of up to 16.5%, 17.9%, and 8.9%. These outcomes show clear
advantages of using flexible MGZO films as anodes or cathodes
for higher eciency and lower operation voltages. Therefore,
these superior characteristics of the tailor-made MGZO films
point toward future applications in flexible optoelectronics.
This journal is The Royal Society of Chemistry 2015
Paper
Acknowledgements
The authors gratefully acknowledge financial support from the
Ministry of Science and Technology of Taiwan. (NSC 102-2221-
E-155-080-MY3 and MOST 104-2623-E-155-006-ET)
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