MRS Advances © 2019 Materials Research Society

DOI: 10.1557/adv.2019.261

Highly-Efficient Solution-Processed Organic Light

Emitting Diodes with Blend V2O5-PEDOT:PSS
Hole-Injection/Hole-Transport Layer

Rohit Ashok Kumar Yadav, Mangey Ram Nagar, Deepak Kumar Dubey, Sujith Sudheendran
Swayamprabha, and Jwo-Huei Jou

Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu 30013,
Taiwan

ABSTRACT

Organic light-emitting diodes (OLEDs) have attracted huge concern because of their intrinsic
characteristics and ability to reach the pinnacle in the field of high-quality flat-panel displays
and energy-efficient solid-state lighting. High-efficiency is always a key crux for OLED
devices being energy-saving and longer life-span. OLEDs have encountered enormous
difficulties in meeting the requirements for large-sized devices due to a major limitation in
vacuum thermal evaporation technology. In multilayered OLED devices, the characteristics of
the charge injection/transport layer is a crucial factor for the operating-voltage, power-
efficiency and stability of the device. Transition metal oxides have shown great potential
owing to their wide range of possible energy level alignments, balanced charge injection, and
improvement of carrier mobilities. In this study, we report a solution-processed blend V2O5-
PEDOT:PSS hole-injection/hole-transport layer (HIL/HTL) for efficient orange
phosphorescent OLEDs. The electroluminescent characteristics of blend V2O5-PEDOT:PSS
based devices were studied with the structure ITO/V2O5-PEDOT:PSS/CBP:Ir(2-
phq)3/TPBi/LiF/Al. The V2O5-PEDOT:PSS based OLEDs displayed relatively higher device
performance and low roll-off than that of the counter PEDOT:PSS device in terms of a
maximum luminance of 17,670 cd m-2, power efficiency of 19.4 lm W-1, external quantum
efficiency of 8.7%, and more importantly, low turn-on voltage. These results demonstrate an
alternative approach based on metal oxide/organic blend HIL/HTL as a substitute of
PEDOT:PSS for high-efficiency solution process OLEDs.

1779
INTRODUCTION

In recent years, organic light emitting diodes (OLEDs) has surged into a mature
technology and have attracted significant attention due to their superior performance in
high-quality flat panel display and solid state lighting applications. Development of
energy-efficient and long-lifespan OLEDs have attracted enormous attention in the last
few years and become a front-line research field of academia as well as in industries.
Numerous tactics have been employed in material chemistry and device engineering
physics to enhance the OLEDs performance [1-4].
Solution-processing provides a low cost and low material utilization approach
to fabricate OLED devices. The charge carrier transporting materials with the possibility
of confinement of injected carriers within the emissive layer (EML) is highly important
to enable balanced carrier, electron and hole, to realize high-efficiency OLEDs. An
effective hole injection/transport material (HIM/HTM) must possess better hole mobility,
high-glass transition temperature, morphologically stable thin film formation during the
fabrication process, suitable frontier molecular orbital for hole injection and electron
blocking nature, and high triplet energy for blocking triplet exciton [5-7]. Poly(3,4-
ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) has been commonly used
in solution process OLED device fabrication as a hole injection/transport layer
(HIL/HTL). Unfortunately, PEDOT:PSS possess numerous drawbacks and degradation
mechanisms in OLED devices because of its low work function, unusual chemical
properties, being acidic, corrosive, and hygroscopic which severely limits the device
performance. Moreover, its inadequate ability to block electrons and excitons crossing
from an EML. As an alternative, transition metal oxides such as molybdenum oxide
(MoO3), tungsten oxide (WO3) and vanadium pentoxide (V2O5) with a high work
function and strong electron accepting affinity have been shown to be promising
substitute to PEDOT:PSS [8-9].
In the year 2015, Kim and group studied the V2O5 doping effect in PEDOT:PSS
as HIL and observed its impact on device characteristics. It states that the improvement
of the device performance is related to the improved conductivity due to the V2O5 doping
concentration in PEDOT:PSS. The best device, PEDOT:PSS:V2O5 showed the maximum
current and power efficiencies of 15.12 cd A-1 and 12.66 lm W-1, respectively [10]. More
recently, Zhang et al. developed solution processed V2O5 as an efficient and stable HIL,
the resultant film exhibited a high work function of 5.07 eV, high transparency of ~95%
and smooth surface morphology. The best device displayed maximum current efficiency
of 10.91 cd A-1, external quantum efficiency of 7.25% and luminance of 11,908 cd m2,
which is much better than the PEDOT:PSS based devices [11]. In the present study, we
reported solution-processed metal oxide-organic blend, V2O5-PEDOT:PSS, as an
efficient and stable HIL/HTL for high-efficiency OLED devices and compared it with
the pristine device, PEDOT:PSS. It is revealed that the blend, V2O5-PEDOT:PSS based
device exhibit relatively higher device performance, low-efficiency roll-off and low-turn
on voltage than that of the counter device. The device performance of the OLEDs
demonstrated here are so far the highest ever reported for current blend based device
structure.

EXPERIMENTAL SECTION

Vanadium pentoxide solution synthesis and preparation:

Vanadium pentoxide (V2O5) powder was purchased from Sigma Aldrich

(99.99% purity). First, V2O5 powder was dissolved in ammonia water (NH4OH) to

1780
prepare a 1 wt% concentration solution under an ultrasonic bath condition. Later, mixed
V2O5 solution into PEDOT:PSS in 10:1 (by volume ratio) and stirred for 12 h. Final
solution was obtained by filtering through 0.45 μm hydrophilic filter.

Materials:

Indium-tin oxide (ITO) coated glass substrates were purchased from the
Luminescence Technology Corporation, Taiwan. The sublimated grade materials
poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) and lithium
fluoride (LiF) were purchased from Sigma Aldrich. The host 4,4′-bis(N-carbazolyl)-1,1′-
biphenyl (CBP), orange emitter tris(2-phenylquinoline)iridium(III) (Ir(2-phq)3), and a
electron transport material 2,2′,2"-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole)
(TPBi) were purchased from the Luminescence Technology Corporation, Taiwan.
Aluminum (Al) ingots (99.999%) were purchased from Showa Chemical Co. Ltd., Japan.

Device fabrication and characterization:

The solution-processed OLED devices were prepared with following device

structure: ITO (125 nm)/ PEDOT:PSS or V2O5- PEDOT:PSS (40 nm)/ 3 wt% Ir(2-
phq)3:CBP (22 nm)/ TPBi (45 nm)/ LiF (1 nm)/ Al (100 nm). The commercial patterned
ITO coated glass substrates were cleaned successively with the detergent solution,
acetone, and 2-isopropanol each with a 20 min interval in an ultrasonic bath, followed by
ultraviolet-ozone treatment for 20 min to eliminate the organic impurities. PEDOT:PSS
(Device A) and V2O5-PEDOT:PSS (Device B) solutions was spin-coated at 4000 rpm for
20 sec onto the ITO substrate and baked on a hot plate at 120 °C for 30 min. The emitter
solution was prepared by dissolving the host and guest molecules in tetrahydrofuran
(THF) and kept at 40 °C for 60 min in bath sonicator with continuous stirring.
Subsequently, a 22 nm thin film of the emitter was spin-coated at 2500 rpm for 20 sec
under nitrogen atmosphere glove box. Finally, the substrates were transferred into a
thermal evaporator, were TPBi, LiF and Al grown layer by layer at a base vacuum of
>10-6 Torr. The deposition speed and thickness of the layers were scrutinized with a
thickness/rate meter. The electroluminescent and thin film characterization of the
fabricated devices was done at room temperature without encapsulation.
The luminance, CIE chromatic coordinates and electroluminescence spectrum
of the resulting OLED devices were measured by using Photo Research PR-655 spectra-
scan (Novanta Inc., USA). A Keithley 2400 electrometer (Keithley Instruments, Inc.,
USA) was used to measure the current-voltage (I-V) characteristics. The water contact
angle (WCA) was measured with 5 μL water using a Drop Shape Analyzer DSA100
(Krüss Scientific, Germany) under ambient conditions. The average value of five
measurements at the different positions on the film surface was adopted as the apparent
contact angle. Absorption and transmittance spectra of spin-coated films on glass
substrate were measured by an UV-vis spectrophotometer (PerkinElmer Lambda35,
Germany) in spectral wavelength range of 280-780 nm, under the scanning speed of 240
nm min-1.

RESULT AND DISCUSSION

Figure 1 displays the studied solution processed orange phosphorescent OLED

device structure and their corresponding energy level diagram consisting of two different
HIL/HTL namely, PEDOT:PSS and V2O5-PEDOT:PSS. The lowest unoccupied

1781
molecular orbital (LUMO) level of V2O5-PEDOT:PSS (1.9 eV) is 1.4 eV higher than that
of pristine PEDOT:PSS (3.3 eV), which divulges that V2O5-PEDOT:PSS have high
electron blocking ability when compare with PEDOT:PSS. Moreover, V2O5 possess high
work function (5.6 eV) that significantly reduces the interfacial energy barrier between
anode and HIL/HTL, hence introducing a step-wise energy state. These effective energy
level configuration may assess the efficient energy transfer to the emissive layer. In
multilayered devices, development of a continuous, unbroken, smooth, and uniform film
is considered an important aspect to resolve the layer thickness and surface morphology.
The film roughness and film forming nature are the most significant for the solution
processable organic materials in OLED devices. Meanwhile, the uniform solution
leveling emphasize on the film roughness, which significantly influence the charge flow
[12].

Figure 1.(a) Schematic and (b) energy levels diagram of solution-processed OLED devices consisting of two different
HIL/HTL in device A and B, respectively.

The contact angle predominantly depends on the surface roughness, surface

tension and its chemical heterogeneity [13]. To investigate surface roughness and film
forming features, water contact angle (WCA) analysis of the spin-coated PEDOT:PSS
and V2O5-PEDOT:PSS was executed. Smaller contact angle demonstrates smooth and
uniform morphology, whilst wider contact angle reveals high rough surface and poor
film-forming ability over the substrate. As shown in Figure 2, the contact angle of
PEDOT:PSS and V2O5-PEDOT:PSS is 35.19° and 13.99°, respectively. This result
elucidate that V2O5-PEDOT:PSS possesses stronger hydrophilic nature than that of
PEDOT:PSS.

Figure 2. Static contact angles of a water drop on PEDOT:PSS and V2O5-PEDOT:PSS spin-coated films on glass
substrate.

1782
 Furthermore, the optical properties of the film, absorption and transmittance,
plays a vital role in light harvesting. Figure 3 displays the UV-vis absorption and
transmittance spectra of films coated on glass substrate. It shows an identical absorption
spectrum for both layers, whilst a minor peak rises from 325 to 410 nm, that consider the
characteristic absorption nature of PEDOT:PSS. However, comparing the transmittance
spectra of these two samples, V2O5-PEDOT:PSS possesses excellent light transmittance
(~86%), although it is slightly superior to that of PEDOT:PSS.

Figure 3. UV-vis absorption and transmittance spectra of PEDOT:PSS and V2O5-PEDOT:PSS thin films on glass
substrate with a specific thickness of 40 nm.

To study the hole injection/transport functionality of V2O5-PEDOT:PSS, we

fabricated solution process OLED devices and characterize their electroluminescent
performances. Table 1 summarizes electroluminescent properties of the devices
including power efficiency (PE), current efficiency (CE), external quantum efficiency
(EQE), and maximum luminance. The control device A, exhibits a maximum PE of 17.2
lm W-1, CE of 16.4 cd A-1 and an EQE of 8.4%. It also shows a PE of 13 lm W-1, CE of
15.6 cd A-1, an EQE of 7.3% at 100 cd m-2 and maximum luminance of 17010 cd m-2. It
is interesting to note that by replacing the HIL/HTL, i.e. from PEDOT:PSS to V2O5-
PEDOT:PSS, a slight drop off in the operating voltage noticed in the device.
The device B exhibits better electroluminescent properties with relatively low-
efficiency roll-off, brightness, and low turn-on. It demonstrates a maximum PE of 19.4
lm W-1, a CE of 18.6 cd A-1 and an EQE of 8.7% with a maximum luminance of 17670
cd m-2. An enhancement of 5% and 8% in PE was observed at 100 and 1000 cd m-2, as
compared to counter device A, respectively. The V2O5-PEDOT:PSS layer has efficient
hole injection/transport property, resulting in high currents in the low voltage region as
shown in Figure 4a and 4b. This efficient hole injection/transport property of V2O5-
PEDOT:PSS is associated with its high work function, high conductivity, step-wise
energy band structure, and high electron affinity of V2O5, which extract electrons from
the HOMO of the PEDOT:PSS to the conduction band of V2O5. Figure 4c and 4d shows
current efficiency-luminance and power efficiency-luminance characteristics of OLED,
respectively. The V2O5-PEDOT:PSS based OLEDs show higher current and power
efficiencies than those of the PEDOT:PSS based device because of the hole injection
improvement by higher conductivity of V2O5-PEDOT:PSS.

1783
Table 1. Comparative analysis of electroluminescence characteristics of solution processed OLEDs.

PEmax/ CEmax/ EQEmaxa PE100/ CE100/ EQE100b PE1000/ CE1000/ EQE1000c

Lum.
Device HIL/HTL
(cd m-2)
(lm W-1/ cd A-1/ %) (lm W-1/ cd A-1/ %) (lm W-1/ cd A-1/ %)

A PEDOT:PSS 17.2/ 16.4/ 8.4 13/ 15.6/ 7.3 8.3/ 12.8/ 6.1 17010

B V2O5-PEDOT:PSS 19.4/ 18.6/ 8.7 13.7/ 16.4/ 7.3 9/ 13.8/ 6.3 17670

a
PMaximum PE, CE and EQE, bPE, CE and EQE measured at 100 cd m-2, cPE, CE and EQE measured at 1000 cd m-2.

The LUMO energy barrier between V2O5-PEDOT:PSS and CBP are much
higher than that of PEDOT:PSS. This illustrates that high LUMO level of V2O5-
PEDOT:PSS possess an excellent ability to block the electrons, hence comparatively
higher efficiency. Moreover, the high efficiency of device B may also be attributed to an
effective charge carrier-confining architecture in the designed device, effective
generation of excitons in the recombination zone and high hole mobility of employed
HIL/HTL. It is clearly discerned that via an increase in positive bias voltage, the forward
bias current across the OLED device increases drastically, hence luminance, which
implies an ambient condition to enhance the device performance. The device B also
displays a low turn-on and operating voltage compared to the counter device as shown in
Table 1. From these results, we conclude that V2O5 leads to increase the conductivity and
to improve the hole injection ability of PEDOT:PSS and effect to charge balance in
active layer of OLED.
(a) 10
5
(b) 10
0

PEDOT:PSS PEDOT:PSS
V2O5-PEDOT:PSS V2O5-PEDOT:PSS
4 -1
10 10
Current density (A cm )
-2
Luminance (cd m )
-2

3 -2
10 10

2 -3
10 10

1 -4
10 10

0 -5
10 10
2 3 4 5 6 7 8 9 10 2 3 4 5 6 7 8 9 10
Voltage (V) Voltage (V)
(c) 2
10 (d) 10
2

PEDOT:PSS PEDOT:PSS
V2O5-PEDOT:PSS V2O5-PEDOT:PSS
Current efficiency (cd A )

Power efficiency (lm W )

-1

-1

1 1
10 10

0 0
10 10
0 1 2 3 4 5 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10 10 10 10
-2 -2
Luminance (cd m ) Luminance (cd m )

Figure 4. Effect of PEDOT:PSS and V2O5-PEDOT:PSS HIL/HTL on the (a) luminance vs voltage, (b) current density vs
voltage, (c) current efficiency vs luminance, and (d) power efficiency vs luminance plots of the fabricated OLEDs.

1784
 1.0 PEDOT:PSS
V2O5-PEDOT:PSS

0.8

Normalized intensity
0.6

0.4

0.2

0.0
380 480 580 680 780
Wavelength (nm)

Figure 5. EL spectra of solution processed OLED device consisting of PEDOT:PSS and V2O5-PEDOT:PSS as HIL/HTL.

The enhanced luminance and low operating voltage of device B may be

attributed to the significant availability of holes and electrons across the EML for exciton
generation and efficient hole transfer at the interface of HIL/EML [14]. Figure 5 displays
the EL spectra of OLED devices A and B. Both the devices show same
electroluminescent behavior and an emission peak at 584 and 586 nm, respectively, with
Commission Internationale de I'Eclairage (CIE) coordinates of (0.58, 0.42) and (0.57,
0.43). Figure 6 indicates the hole transport properties of hole-only-devices consisting of
PEDOT:PSS and V2O5-PEDOT:PSS as the HIL/HTL. In V2O5-PEDOT:PSS based HOD,
the electron transport is blocked due to the large barrier between the work function of
LiF/Al and lowest unoccupied molecular orbital (LUMO) of deposit HIL/HTL. Hence,
the charge transport in this device is possible only by holes. The hole transport
characteristic of V2O5-PEDOT:PSS based devices is significantly higher than the
reference device. This enhancement could be attributed to the high hole mobility of V 2O5.

0
10 PEDOT:PSS
V2O5-PEDOT:PSS
Current density (A cm )
-2

-1
10

-2
10

-3
10
0 1 2 3 4 5 6 7 8
Voltage (V)

Figure 6. Current density-voltage (J-V) characteristics of hole-only device with structures of ITO/PEDOT:PSS or V 2O5-
PEDOT:PSS/LiF/Al.

1785
CONCLUSION

In conclusion, we have demonstrated a metal oxide-organic blend tactic, V2O5-

PEDOT:PSS, as an efficient and stable HIL/HTL for highly efficient solution process
OLED devices. The V2O5-PEDOT:PSS based device exhibits superior
electroluminescece performance i.e. PE of 19.4 lm W-1, CE of 18.6 cd A-1, EQE of 8.7%,
and maximum luminance of 17670 cd m-2. The observed results are significantly higher
than that of device fabricated with PEDOT:PSS. The reason besides this may be
attributed to an efficient hole injection/transfer and electron confining at HIL and EML
interface, step-wise energy level alignments, balanced charge carrier distribution in the
desired emissive and high hole mobility of employed V2O5-PEDOT:PSS HIL/HTL.
These are the highest power efficacies ever reported for this specific blend HIL/HTL
approach and device structure.

ACKNOWLEDGMENTS

This work was financially supported by the Ministry of Science and Technology (MOST,
Grant No. 104-2119-M-007-012) and Ministry of Economic Affairs (MEA, Grant No.
104-EC-17-A-07-S3-012), Taiwan.

References

1. D. K. Dubey, S. Shahoo, C. W. Wang and J. H. Jou, Organic Electronics 69, 232 (2019).
2. J. H. Jou, S. Sahoo, D. K. Dubey, R. A. K. Yadav, S. S. Sujith and S. D. Chavhan, J. Mater.
Chem. C 6, 11492 (2018).
3. S. Kumar, C. C. An, S. Sahoo, R. Griniene, D. Volyniuk, J. V. Grazulevicius, S. Grigalevicius
and J. H. Jou, J. Mater. Chem. C 5, 9854 (2017).
4. J. H. Jou, S. Kumar, A. Agrawal, T. H. Lia and S. Sahoo, J. Mater. Chem. C 3, 2974 (2015).
5. S. Ho, S. Liu, Y. Chen and F. So, J. of Photonics for Energy 5, 057611 (2015).
6. S. D. Chavhan, T. H. Ou, M. R. Jiang, C. W. Wang and J. H. Jou, J. Phys. Chem. C 122, 18836
(2018).
7. D. K. Dubey, R. A. K. Yadav, D.Tavgeniene, S. Grigalevicius and J. H. Jou, Thin Solid Films
660, 956 (2018).
8. K. Zilberberg, J. Meyer and T. Riedl, J. Mater. Chem. C 1, 4796 (2013).
9. F. Huang, Y. J. Cheng, Y. Zhang, M. S. Liu and A. K. Y. Jen, J. Mater. Chem. 18, 4495 (2008).
10. J. Kim, A. Kanwat, H. M. Kim and J. Jang, Phys. Status Solidi A 212, 640 (2015).
11. H. Zhang, S. Wang, X. Sun and S. Chen, J. Mater. Chem. C 5, 817 (2017).
12. K. E. Strawhecker and S. K. Kumar, Macromolecules 34, 4669 (2001).
13. R. Yadav, S. Zachariah and K. Balasubramanian, Adv. Sci. Eng. Med. 8, 181 (2016).
14. J. H. Jou, J. W. Weng, S. D. Chavhan, R. A. K. Yadav and T. W. Liang, J. Phys. D: Appl. Phys.
51, 454002 (2018).

1786