JOURNAL OF DISPLAY TECHNOLOGY, VOL. 11, NO.

4, APRIL 2015

341

Inverted Tandem Phosphorescence Organic

Light-Emitting Diodes Based on MoO Al/Cs CO
Charge Generation Unit
Jun Liu, Xindong Shi, Xinkai Wu, Jing Wang, and Gufeng He

AbstractA multilayer charge generation unit (CGU)

MoO Al/Cs CO has been developed for inverted tandem
organic light-emitting diodes (OLEDs). The current efciency of
inverted tandem phosphorescence OLED with MoO (8 nm)/Al
(1 nm)/Cs CO (0.5 nm) CGU is almost twice as high as that of
individual electroluminescent (EL) device. Charges generate at
hole-transporting host material/MoO interface and MoO bulk
layer, and electrons are extracted by Cs CO /electon-transporting
layer (ETL) interface. The signicantly enhanced performance
of the tandem device with MoO Al/Cs CO CGU compared
with a MoO Cs CO -based one may be attributed to preventing
chemical reaction of MoO and Cs CO by the inserted ultrathin
Al layer. Moreover, the current efciency and EL spectrum of
another inverted tandem OLED combining red and green stack
further prove the effective charge generation and separation with
the multilayer MoO Al/Cs CO CGU. It is expected that such a
CGU is a promising candidate for inverted tandem white OLED
for active matrix organic light-emitting diode display driven by
an n-type thin-lm transistor backplane.
Index TermsCharge generation unit (CGU), inverted, organic
light-emitting diode (OLED), phosphorescence, tandem.

I. INTRODUCTION

HE active matrix organic light-emitting diode

(AMOLED) display has attracted considerable attention
because of its advantages such as fast response time, wide
viewing angle, high contrast ratio, and potential exibility [1],
[2]. Due to excellent properties including high transparency,
low temperature process, high mobility and good uniformity,
the amorphous indiumgalliumzinc oxide thin-lm transistor
(IGZO TFT) has been recently developed as backplane for
AMOLED [3][5]. For large-size AMOLED display fabricated
on 8th Generation substrate, white OLED (WOLED) and color
lters (CF) are proposed to be embedded into AMOLED panel
[6]. In order to obtain high performance WOLED with high
Manuscript received July 09, 2014; revised October 28, 2014; accepted January 08, 2015. Date of publication January 15, 2015; date of current version
March 24, 2015. This work was supported in part by National Natural Science Foundation of China under Grant 61377030 and the Science and Technology Commission of Shanghai Municipal under Grant 12JC1404900. (Corresponding author: Gufeng He.)
The authors are with the National Engineering Lab for TFT-LCD Materials
and Technologies and the Department of Electronic Engineering, Shanghai Jiao
Tong University, Shanghai 200240, China (e-mail: gufenghe@sjtu.edu.cn).
Color versions of one or more of the gures are available online at http://
ieeexplore.ieee.org.
Digital Object Identier 10.1109/JDT.2015.2392118

efciency and long lifetime, tandem structure connecting blue

with red/green stack in series by charge generation unit (CGU)
has been introduced [7][10]. Since the IGZO TFT is n-type,
the inverted OLED structure with a bottom cathode is preferred
to be integrated with backplane in AMOLED. Therefore, the
inverted tandem structure is a promising candidate for developing AMOLED plane based on IGZO TFT.
In the conventional tandem OLED, an n-doped electron-transporting layer (n-ETL)/p-doped hole-transporting
layer (p-HTL) junction is widely used as CGU [11]. Despite
that the n/p junction as CGU in the conventional tandem
OLED should be reversed as the p/n junction in the inverted
tandem device, their mechanism of charge generation and
separation should be similar. Krger et al. had an in-depth
investigation on the mechanism of such CGU, where electron tunneling from lled highest occupied molecular orbital
(HOMO) states of the HTL to unoccupied lowest unoccupied
molecular orbital (LUMO) states of the ETL through a narrow
depletion zone at the interface [11]. Since holes and electrons
are generated in the p-HTL, effective p-doping of HTL is
preferred. Most of the p-HTLs focus on doping an triphenylamine-based material with electron-rich property such as
N N -diphenyl-N N -bis -naphthyl -biphenyl-4,4 -diamine (NPB) and N N N N -tetrakis(4-Methoxy-phenyl)benzidine (MeO-TPD) with strong electron acceptor, such
as
2,3,5,6-tetra-uoro-7,7,8,8-tetracyanoquinodimethane
(F4-TCNQ) [12]. However, the triphenylamine-based material with low triplet energy cannot be as a host for high
efciency green or blue phosphorescence OLED (PhOLED).
Carbazole-based materials with high triplet energy, such
as 4,4 -bis 9-carbazolyl biphenyl (CBP) and 1,3-bis(carbazol-9-yl)benzene (mCP) are commonly used as hosts for
green or blue PhOLED. Due to shallower HOMO of HTL than
that of host (e.g., NPB's HOMO: 5.4 eV, CBP's HOMO: 6.1
eV), holes are easily accumulated at the HTL/host interface,
leading to exciton quenching by the HTL cations [13]. If such
hosts can be effectively p-doped and act as charge generation
reservoir and HTL, the tandem PhOLED structure is simplied,
and hole accumulation and exciton quenching can be suppressed as well. However, these emitter hosts are hardly doped
by widely used organic p-dopant F4-TCNQ due to large difference between the deep HOMO of the hosts and the LUMO of
F4-TCNQ. On the other hand, it has been reported that electron
afnity of MoO (6.7 eV) is deeper than the HOMO (6.1 eV)
of carbazole-based host CBP, and the host CBP can be p-doped

1551-319X 2015 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.

342

JOURNAL OF DISPLAY TECHNOLOGY, VOL. 11, NO. 4, APRIL 2015

Fig. 1. Schematic diagram of inverted single and tandem devices and chemical structures of materials.

by MoO in the form of charge transfer from host's HOMO

to MoO 's conduction band (CB) [14]. Nevertheless, MoO
clustering within the matrix causes the low doping efciency
of less than 2% for CBP:MoO system [15], which makes it
unsuitable for charge generation reservoir, since high doping
efciency of p-HTL corresponding to effective free charge
generation is required for CGU. The bulk MoO lm has been
proved to own gap states where electrons jump to MoO 's CB
[16], indicating that it can serve as charge generation reservoir
in CGU. Under an operating electric eld, holes generated in
MoO can inject into the neighboring HTL, and electrons are
extracted by the n-doped ETL of CGU, which mostly employs
an n-type ETL doped by alkali metals or their compounds, such
as Li [10], CsN [16], Mg [17], and Cs CO [18], or an ultrathin interlayer, e.g. Liq/Al [12], [19], LiF/Al [20]. However,
the n-doping requires complicated and time-consuming process
for precise control, and Li liberated from Liq or LiF may act as
luminescence quencher when it diffuses into EML, due to its
small atomic dimensions.
In our inverted tandem PhOLED, the wide band gap blue
host mCP was used as both HTL and host, and a multilayer of
MoO Al/Cs CO was applied as CGU. The MoO lm and
bilayer Al/Cs CO acted as charge generation reservoir and
electron extraction layer, respectively. The current efciency of
tandem device with MoO (8 nm)/Al (1 nm)/Cs CO (0.5 nm)
CGU was almost twice as high as that of single device. The
inuence of Cs CO thickness on charge separation process
of MoO Al/Cs CO was investigated. The enhanced performance of tandem device with reduced Cs CO thickness
referred optimized electron injection at Cs CO /ETL interface.
Moreover, tandem device with MoO Cs CO interconnected
layer (IL) exhibited signicantly decreased performance, compared to MoO Al/Cs CO -based case. Since both Cs CO
and Al/Cs CO possessed identical electron injection ability,
the role of ultrathin Al inserted layer in CGU is considered
to hinder chemical reaction of MoO and Cs CO , which
induced charge depletion zone with high resistance. To further
understand mechanism of MoO Al/Cs CO as CGU, another
inverted tandem device combining red and green stack was
fabricated. The EL spectrum of tandem device was superposed

by those of single red and green devices, and the current efciency of tandem device was sum of those of single devices,
demonstrating that MoO Al/Cs CO is a promising CGU in
inverted tandem device.
II. EXPERIMENTAL
Fig. 1 shows schematic diagram of inverted single and
tandem PhOLEDs, and the chemical structure of materials
used in this study. Cs CO and MoO are used as electron-injecting layer (EIL) and hole-injecting layer (HIL), respectively.
mCP and 1,3,5-tris (N-phenylbenzimidazole-2-yl)benzene
(TPBI) act as HTL and ETL, respectively, and both of them
are hosts of the emitter. 4,7-diphenyl-1,10-phenanthroline
(Bphen) acts as ETL with high electron mobility. The phosphorescent emitter is a bis-cyclometalated iridium complex of
Ir tfmppy tpip (tfmppy
triuoromethylphenylpridine,
tpip
tetraphenylimido-diphosphinate) featured with aggregation-induced phosphorescent emission (AIPE) [21], which
is a phenomenon showing weak phosphorescence in solution and enhanced phosphorescence emission in solid state.
The inverted single and tandem PhOLEDs were fabricated
on patterned indium tin oxide (ITO)-coated glass substrates.
Prior to lm deposition, the ITO glass substrates were cleaned
successively using deionized water, acetone and isopropanol
ultrasonic bath, dried and then treated with oxygen plasma. The
EIL, ETL, EML, HTL, HIL and Al anode were successively
thermally deposited within a high vacuum deposition system
at a base pressure of
torr. The deposition rate for organic
materials was monitored by quartz-crystal monitors and kept
constant within the range from 0.01 to 0.1 nm s . Current
density-voltage (J-V) and luminescence-voltage (L-V) characteristics were measured with a computer controlled Keithley
2400 source meter and BM-7A luminance colorimeter under
ambient conditions.
III. RESULTS AND DISCUSSION
For inverted bottom emission OLED, indium tin oxide (ITO)
is usually used as cathode due to its high optical transparency
and electrical conductivity. However, high work function of
ITO limits electron injection into the neighboring ETL. In

LIU et al.: INVERTED TANDEM PHOSPHORESCENCE OLEDs

343

Fig. 2. (a) Current density-voltage, (b) luminance-voltage, (c) current efciency-current density, and (d) power efciency-luminance characteristics of inverted
single and tandem PhOLEDs.

our research, a buffer layer of Cs CO is applied as EIL in

inverted single or tandem device to promote electron injection
from ITO cathode. As shown in Fig. 2, the current efciency
of inverted tandem device with MoO Al/Cs CO (0.5 nm)
as IL is 1.93 times as high as that of single device at a current density of 10 mA/cm , indicating that such IL acts as
an effective CGU. The mechanism of CGU is described as
follows. Charge generation process occurs in the MoO bulk
layer by electron jumping from gap states to CB of MoO , and
also happens at the mCP/MoO interface via electron transfer
from HOMO states of mCP to CB of MoO . Under a proper
electric eld, holes at HOMO states of mCP and gap states of
MoO transport into the neighboring EL unit, and electrons
at CB of MoO transport into the adjacent BPhen layer under
assistance of EIL Al/Cs CO , as shown in Fig. 3. The Cs CO
thickness for optimized electron injection should be less than
1 nm, otherwise inverted tandem device shows increased
operating voltage and reduced current efciency. This infers
that electron injection is favorable at Cs CO /Bphen interface
instead of Cs CO bulk layer. Compared to inverted tandem
device using MoO Al/Cs CO CGU, tandem device with
MoO Cs CO IL requires signicantly increased operating
voltage at the same current density, and exhibits dramatically
reduced current efciency, indicating unqualied CGU for
MoO Cs CO .
The superior property of MoO Al/Cs CO
to
MoO Cs CO seemingly manifests better electron injection
property of Al/Cs CO than Cs CO . To further verify the

Fig. 3. Schematic electric eld-assisted charge generation and separation

process. The dotted lines in the MoO frame represent the gap states of MoO .

advantage of Al/Cs CO , we compared the performance of

another inverted single device with Cs CO (1 nm) or Al
(1 nm)/Cs CO (1 nm) EIL. The device structure consists of
ITO/EIL/Bphen
nm Alq (20 nm)/NPB
nm MoO
(6 nm)/Al (100 nm). However, as shown in Fig. 4, both
Al/Cs CO - and Cs CO -based devices exhibit almost
identical performance, indicating no difference of electron
injection capability between Al/Cs CO and Cs CO EILs.
Therefore, the better charge generation for MoO Al/Cs CO
is not originated from better electron injection property of
Al/Cs CO . The high vacuum thermal evaporated Cs CO
is readily decomposed to active metal cesium with low
work function, leading to remarkable electron injection of

344

JOURNAL OF DISPLAY TECHNOLOGY, VOL. 11, NO. 4, APRIL 2015

Fig. 4. (a) Current density-voltage and (b) luminance-voltage characteristics

of inverted single devices with Al/Cs CO and Cs CO EILs.

Fig. 5. Current efciency-current density characteristic and electroluminescence spectrum of single green and red devices and tandem device.

evaporated Cs CO [22]. Deposition of MoO with strong

electron-withdrawing property on top of evaporated Cs CO
may lead to redox reaction of MoO and Cs CO , resulting in
space charge region with high resistance at MoO Cs CO
interface. The space charge region also exists at reported
metal oxide/n-ETL interface, e.g., WO BPhen Cs CO [18],
MoO BPhen Cs CO [23], and electrons tunnel through
the depletion region into the latter BPhen:Cs CO layer.
However, in our case, the chemical reaction of MoO and
Cs CO without ultrathin Al in between damages the n-doped
BPhen surface, leading to large electron injection barrier. Thus,
the role of inserted layer Al is deduced to prevent chemical
reaction of MoO and Cs CO .
The fact that tandem device with two identical monochromatic units shows doubled current efciency of single device
is not a strict proof for the effective CGU MoO Al/Cs CO .
To further understand the mechanism of MoO Al/Cs CO ,
we fabricated another inverted tandem device combining green and red EL units connected by MoO
(8 nm)/Al
nm Cs CO 1 nm . The single green device structure is ITO/Cs CO (1 nm)/BPhen 40 nm Alq
(20 nm)/NPB 60 nm MoO (6 nm)/Al (100 nm), and the
single red device structure is ITO/Cs CO (1 nm)/BPhen
40 nm Alq DCJTB
20 nm NPB
60 nm MoO
(6 nm)/Al (100 nm). Device conguration of tandem device is
ITO/Cs CO (1 nm)/BPhen
nm Alq (20 nm)/NPB (60
nm)/CGU/BPhen
nm Alq DCJTB (3%, 20 nm)/NPB

60 nm MoO (6 nm)/Al (100 nm). As shown in Fig. 5, current efciency of tandem device is almost the sum of those of
single green and red devices. For example, at the current density of 20 mA/cm , tandem device exhibits current efciency
of 7.2 cd/A, and single green and red device show current
efciency of 6.0 cd/A and 1.1 cd/A, respectively. Moreover,
the EL spectrum of tandem device is almost the superposition
of the spectra of single green and red devices at current density
of 10 mA/cm . The characteristic peaks at 530 nm and 630 nm
correspond to emission from Alq and DCJTB, respectively.
IV. CONCLUSION
In summary, we have developed a multilayer structure of
MoO Al/Cs CO as CGU for inverted tandem PhOLEDs.
mCP/MoO interface and MoO bulk layer act as charge reservoir, due to charge transfer from HOMO of mCP to conduction
band of MoO and via thermal diffusion from gap states to
conduction band of MoO . Electrons are extracted by Cs CO
doped Bphen surface instead of Cs CO bulk layer, since
slightly increased Cs CO thickness leads to larger electrical
eld for charge separation. On the other hand, inverted tandem
device with MoO Cs CO IL exhibits signicantly reduced
performance, while Cs CO and Al/Cs CO have identical
electron injection property. Therefore the role of ultrathin Al in
CGU is deduced to prevent chemical reaction between MoO
and Cs CO . Moreover, another tandem OLED combining red
and green stack exhibits both red and green emission, further

LIU et al.: INVERTED TANDEM PHOSPHORESCENCE OLEDs

proving the effectiveness of MoO Al/Cs CO CGU. Our

ndings suggest that MoO Al/Cs CO is a promising candidate for high efciency tandem white OLED for AMOLED
display with IGZO TFT backplane.
REFERENCES
[1] M. G. Helander et al., Chlorinated indium tin oxide electrodes with
high work function for organic device compatibility, Science, vol. 332,
pp. 944947, May 2011.
[2] S. Reineke et al., White organic light-emitting diodes with uorescent
tube efciency, Nature, vol. 459, pp. 234238, May 2009.
[3] J. K. Jeong et al., 12.1-in. WXGA AMOLED display driven by
InGaZnO thin-lm transistor, J. Soc. Inf. Display, vol. 17, pp. 95100,
Feb. 2009.
[4] S. H. Jung, W. J. Nam, and M. K. Han, A new voltage-modulated
AMOLED pixel design compensating for threshold voltage variation
in poly-Si TFTs, IEEE Electron Device Lett., vol. 25, no. 10, pp.
690692, Oct. 2004.
[5] J. H. Lee, W. Nam, B. K. Kim, H. S. Choi, Y. M. Ha, and M. K.
Han, A new poly-Si TFT current-mirror pixel for active matrix organic light emitting diode, IEEE Electron Device Lett., vol. 27, no.
10, pp. 830833, Oct. 2006.
[6] C.-W. Han et al., 55-inch FHD OLED TV employing new tandem
WOLEDs, in SID Symp. Digest Tech. Pap., 2012, pp. 279281.
[7] Y. H. Chen, J. S. Chen, D. G. Ma, D. H. Yan, and L. X. Wang, Tandem
white phosphorescent organic light-emitting diodes based on interfacemodied C /pentacene organic heterojunction as charge generation
layer, Appl. Phys. Lett., vol. 99, Sep. 2011, Art. ID 103304.
[8] J. Liu et al., Double hybrid tandem white OLED employing a novel
charge generation unit, in SID Symp. Digest Tech. Pap., 2013, pp.
14031406.
[9] E. Najafabadi, K. A. Knauer, W. Haske, C. Fuentes-Hernandez, and B.
Kippelen, Stacked inverted top-emission white organic light-emitting
diodes composed of orange and blue light-emitting units, Appl. Phys.
Lett., vol. 103, Nov. 2013, Art. ID 193303.
[10] Y. S. Tyan et al., Tandem hybrid white OLED devices with improved
light extraction, in SID Symp. Dig. Tech. Papers, 2009, pp. 895898.
[11] M. Krger et al., Temperature-independent eld-induced charge separation at doped organic/organic interfaces: Experimental modeling of
electrical properties, Phys. Rev. B, vol. 75, Jun. 2007, Art. ID 235321.
[12] J. Liu, J. Wang, S. Huang, X. Shi, X. Wu, and G. He, A highly efcient, transparent and stable charge generation unit based on a p-doped
monolayer, Org. Electron., vol. 14, pp. 13371343, Mar. 2013.
[13] Z. B. Wang, M. G. Helander, Z. W. Liu, M. T. Greiner, J. Qiu, and
Z. H. Lu, Controlling carrier accumulation and exciton formation in
organic light emitting diodes, Appl. Phys. Lett., vol. 96, Jan. 2010,
Art. ID 043303.
[14] M. Krger, S. Hamwi, J. Meyer, T. Riedl, W. Kowalsky, and A. Kahn,
Role of the deep-lying electronic states of MoO in the enhancement
of hole-injection in organic thin lms, Appl. Phys. Lett., vol. 95, Sep.
2009, Art. ID 123301.
[15] S. Hamwi, J. Meyer, T. Winkler, T. Riedl, and W. Kowalsky, p-type
doping efciency of MoO in organic hole transport materials, Appl.
Phys. Lett., vol. 94, Jun. 2009, Art. I 253307.
[16] J.-P. Yang et al., Electric-eld-assisted charge generation and separation process in transition metal oxide-based interconnectors for
tandem organic light-emitting diodes, Adv. Funct. Mater., vol. 22,
pp. 600608, Feb. 2012.
[17] M.-Y. Chan, S.-L. Lai, K.-M. Lau, M.-K. Fung, C.-S. Lee, and S.-T.
Lee, Inuences of connecting unit architecture on the performance of
tandem organic light-emitting devices, Adv. Funct. Mater., vol. 17,
pp. 25092514, Aug. 2007.
[18] S. Hamwi et al., The role of transition metal oxides in charge-generation layers for stacked organic light-emitting diodes, Adv. Funct.
Mater., vol. 20, pp. 17621766, May 2010.
[19] J. Liu, S. Huang, X. Shi, X. Wu, J. Wang, and G. He, Charge separation
process in an ultrathin electron-injecting bilayer-assisted charge generation unit for tandem organic light-emitting diodes, J. Phys. Chem. C,
vol. 117, pp. 1388713893, Jun. 2013.

345

[20] T. Chiba, Y.-J. Pu, R. Miyazaki, K.-I. Nakayama, H. Sasabe, and J.

Kido, Ultra-high efciency by multiple emission from stacked organic light-emitting devices, Org. Electron., vol. 12, pp. 710715,
Feb. 2011.
[21] Y.-C. Zhu et al., Highly efcient green and blue-green phosphorescent
OLEDs based on iridium complexes with the tetraphenylimidodiphosphinate ligand, Adv. Mater., vol. 23, pp. 40414046, Sep. 2011.
[22] Q. Liu et al., Study on the electron injection mechanism of thermally
decomposable Cs CO , Jpn. J. Appl. Phys., vol. 48, Oct. 2009, Art.
ID 102302.
[23] J.-P. Yang et al., Hybrid intermediate connector for tandem OLEDs
with the combination of MoO -based interlayer and p-type doping,
Org. Electron., vol. 13, pp. 22432249, Jul. 2012.

Jun Liu received the B.S. degree in material engineering and M.S. degree in material science and technology from Nanjing Forestry University, Nanjing, China,
in 2007 and 2010, respectively, and is currently working toward the Ph.D. degree in OLEDs from the National Engineering Lab for TFT-LCD Materials and
Technologies, Shanghai Jiao Tong University, Shanghai, China.
His current research interests include tandem OLED, solution-processed optoelectronic devices, AMOLED display and OLED lighting.

Xindong Shi received the B.S. degree in electric engineering from Hangzhou
Dianzi University, Hangzhou, China, in 2012, and is currently working toward
the M.S. degree from the Department of Electronic Engineering and National
Engineering Lab for TFT-LCD Materials and Technologies in Shanghai Jiao
Tong University, Shanghai, China.
His current research interests are TOLED and Out-coupling design.

Xinkai Wu received the B.S. degree and M.S. degree in polymer science and
engineering from the University of Science and Technology of Jiangsu from
2005 to 2012, and is currently working toward the Ph.D degree in electronics
science and technology from Shanghai Jiao Tong University, Shanghai, China.
His research interests include exible electrode and exible OLED devices
fabrication.

Jing Wang received the B.S. degree in electronic engineering from Xidian University, China, in 2007, and is currently working toward the M.S. degree under
the supervision of Prof. G. He at Shanghai Jiao Tong University, Shanghai,
China.
His research interests include high-efciency OLEDs and charge carrier injection, and transporting in organic semiconductors.

Gufeng He received the B.S. degree in polymer science and engineering from
the University of Science and Technology of China and the M.S. and Ph.D. degrees in organic optoelectronic devices from the Institute of Chemistry, Chinese
Academy of Sciences.
From 2002 to 2005, he performed postdoctoral research on high-performance
organic light-emitting devices at the University of Technology, Dresden, Germany. Thereafter, he worked at Novaled AG as a Senior Scientist for ve years
on high-efciency and long-lifetime white organic light-emitting device development for display and lighting applications. In 2010, he became a Professor
at Shanghai Jiao Tong University, Shanghia, China. His main research interests
are organic optoelectronic functional materials and devices.