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Materials Chemistry
Cite this: J. Mater. Chem., 2012, 22, 24202
www.rsc.org/materials HIGHLIGHT
Metal oxides for interface engineering in
polymer solar cells
Song Chen, Jesse R. Manders, Sai-Wing Tsang and Franky So*
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DOI: 10.1039/c2jm33838f

Significant progress in power conversion efficiencies and stabilities of polymer solar cells has
been achieved using semiconducting metal oxides as charge extraction interlayers. Both
n- and p-type transition metal oxides with good transparency in the visible as well as infrared
region make good Ohmic contacts to both donors and acceptors in polymer bulk
heterojunction solar cells. Their compatibility with roll-to-roll processing makes them very
attractive for low cost manufacturing of polymer solar cells. In this review, we will present the
recent results on synthesis and characterization of these metal oxides along with the device
performance of the solar cells using these metal oxides as interlayers.

1. Introduction
Polymer solar cells (PSCs) have drawn a
lot of research interest in the past decade
because of their potential to be low-cost
light harvesting devices.1 The race for
power conversion efficiency (PCE) of
PSCs has been driven by the development
of photoactive materials2,3 and device
architectures.47 In particular, a large
number of donoracceptor (DA) poly-
mers3,810 have been synthesized by
controlling the highest occupied molec-
ular orbital (HOMO) and lowest unoc-
cupied molecular orbital (LUMO) levels
of the donor and the acceptor units of the
resulting conjugated polymers. This
bandgap engineering enables the realiza-
tion of many low bandgap polymers with
deep-lying HOMO energies, resulting in
enhancements in short circuit currents
(Jsc) as well as open circuit voltages (Voc),
which are two key parameters for photo-
voltaic cells. Using these photo-active
materials, PCEs of 79% (ref. 9 and
1116) have already been demonstrated
with the incorporation of charge extrac-
tion interlayer materials, among which
transition metal oxides are very attractive
because of their ability to efficiently
Department of Materials Science and
Engineering, University of Florida, 32611-6400,
USA. E-mail: fso@mse.ufl.edu
extract charge carriers and their compat-
ibility with high volume roll-to-roll (R2R)
processing.17,18 While solution processed
electron extraction materials such as zinc
oxide have been demonstrated in both
lab-scale devices and scaled-up modules,
further development of high work func-
tion solution processed metal oxides for
hole extraction layers is still needed.
Most PSCs are made with bulk heter-
ojunctions (BHJs)19 wherein an electron
donating polymer and an electron ac-
cepting fullerene derivative form nano-
scaled interpenetrating networks allowing
efficient exciton dissociation and carrier
transport. Unlike inorganic solar cells
where Ohmic contacts can be made by
surface doping, PCSs require alternative
strategies for the interface engineering.
Specifically, poor Ohmic contacts with
transparent conducting oxides (TCO) or
metallic electrodes are due to the
mismatch of work function,20,21 the pres-
ence of interfacial dipoles2224 as well as
high densities of interfacial trap states.25,26
To achieve good Ohmic contacts, various
charge extracting interlayers have been
used between the BHJ layer and the elec-
trodes. Among the electrode interlayer
materials used in high performance PSCs,
transition metal oxides are promising
because of their better environmental
stability, higher optical transparency and
easier synthesis routes than alkali metal
compounds,2730 aqueous conducting
polymers3134 and conjugated
polyelectrolytes.14,35
The PCE of PSCs is a product of Voc,
Jsc and fill factor (FF). The Voc is deter-
mined by recombination as well as the
energy level alignment between the pho-
toactive polymer donor and the fullerene
acceptor, Jsc is determined by the light
harvesting and the charge separation
efficiency under large extraction fields,
and FF is determined by the device series
resistance, the dark current and the
charge recombination/extraction rate
under low internal fields. The n- and
p-type semiconductivities in metal oxides
are, in general, due to the intrinsic point
defects such as atomic vacancies present
in the oxides. Fig. 1 shows the HOMO as
well as LUMO energy levels of some of
the state-of-the-art photovoltaic poly-
mers, electron accepting fullerene deriva-
tives and the electron affinities and
ionization energies of high/low work
function metal oxides. These metal oxides
form Ohmic contacts to photovoltaic
polymers and fullerenes through favor-
able vacuum level shift, energy level
bending and Fermi level pinning at the
polymerelectrode interfaces. In addition,
the use of oxide interlayers circumvents
the direct contact between a photoactive

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Fig. 1 The energy level diagram of state-of-art photovoltaic polymers, electron accepting fullerene
derivatives and transition metal oxides.
polymer and electrodes where high
densities of carrier traps or unfavorable
interface dipoles hinder efficient charge
collection. Equally important is the use of
metal oxides for Ohmic contacts to
maximize the Voc because the reduction of
built-in potential leads to an increase in
dark current as well as carrier
recombination.
In this paper, we will review the
synthesis and characterization of some of
the vacuum-deposited and solution pro-
cessed metal oxides including zinc oxide,
titanium oxide, molybdenum oxide,
tungsten oxide, vanadium oxide and
nickel oxide for interlayers in PSCs. We
will also describe how their properties
affect the performance of some of the
state-of-the-art PSCs.
2. Metal oxides as cathode
interlayers
Depending on the solar cell device
geometry, as shown in Fig. 2, the cathode
interlayer is either coupled with the top
electrode, usually a low work function
metal, or with the bottom TCO electrode.
In PSCs, three approaches are used to
make Ohmic contacts to the electron
accepting fullerene derivatives in the BHJ
layer. The first approach is to use alkali
metals or related compounds such as
cesium carbonate (Cs2CO3)7,36 and
lithium fluoride (LiF) to make Ohmic
contacts to fullerenes due to their low
work functions (<3.0 eV). The disadvan-
tage of this approach is, however, that
This journal is The Royal Society of Chemistry 2012
alkali metal compounds are prone to
oxidation and lead to rapid device
degradation. The second approach is to
use alcohol/water-soluble conjugated
polyelectrolytes14,35,37 for cathode inter-
layer materials. Due to the intramolecular
dipole moment and their ability to form
self-assembled monolayers, these conju-
gated polyelectrolytes can induce an
interface dipole pointing from the
cathode to the BHJ layer in the conven-
tional device geometry, thus increasing
the built-in potential of the device. Using
this approach, high PCE values (8.3%)
have been achieved in devices using
polyelectrolytes for the top cathode
Fig. 2 Conventional (top) and inverted
(bottom) polymer solar cells. The usage of low
work function (WF) oxide in a conventional
cell is optional.
J. Mater. Chem., 2012, 22, 2420224212 | 24203
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interlayer.14 The third approach is to use
transition metal oxides such as ZnO and
TiO2 with work functions matching the
LUMO levels of fullerenes. Due to their
chemical resistance to oxygen and mois-
ture, optical transparency and facile
solution processability, these n-type
semiconducting oxides effectively replace
low work function metals for cathode
contacts, resulting in high efficiency
devices demonstrated in both conven-
tional and inverted device geometries.
2.1 Zinc oxide (ZnO)
ZnO is currently the most commonly used
electron transporting layer (ETL) mate-
rial in PSCs. Its work function13,38
provides a good Fermi level match to the
Fermi levels of TCOs as well as the
LUMO energy of [6,6]-phenyl-C61 (or
C71) butyric acid methyl ester (PC61BM
or PC71BM). Because of the large
bandgap energy, the ionization potential
of ZnO is large enough to let it act as a
hole blocker and thus increases the shunt
resistance of a BHJ cell. Optically, ZnO
absorbs in the UV part of the spectrum
and hence it serves as a low-pass filter for
PC71BM and photoactive polymers used
for solar cells. Using zinc salts as precur-
sors, solution processable ZnO can be
formed through solgel,39 solvothermal40
or a hydrothermal process,41 as a result,
various nanostructures of ZnO such as
colloidal nanoparticles and solgel ZnO
films have been used as ETLs in PSCs.
2.1.1 ZnO colloidal nanoparticles
(NPs). The use of ZnO NPs enables the
material to be utilized in its crystalline
phase while its thin film deposition is
compatible with solution processing. ZnO
NPs have been used for R2R processing
of large area solar modules.18 For lab-
scale device fabrication, ZnO NPs are
usually deposited by spin-coating as a
bottom or top interlayer depending on the
device geometry.
ZnO NPs are readily synthesized from
zinc acetate dihydrate in alcoholic
solvents with a strong base such as
sodium hydroxide (NaOH),42 potassium
hydroxide (KOH)41,43,44 or tetramethyl-
ammonium hydroxide (TMAH).13,45 The
resulting wurtzite-type ZnO NPs have
diameters of 36 nm, bandgap energies of
3.33.6 eV, and they form transparent
colloids in polar or non-polar

solvents.13,4145 To fabricate PSCs with an
inverted device geometry, i.e., devices
with a bottom cathode, ZnO NP colloids
are spin-coated onto TCO substrates as
the bottom electrode interlayer. Using
such an approach, inverted poly(3-hex-
ylthiophene) (P3HT) cells with a PCE of
4% have been demonstrated.46,47 More
recently, using low bandgap polymers
such as dithienosilole-thienopyrrole-4,6-
dione (PDTS-TPD) and dithienogermole-
thienopyrrole-4,6-dione (PDTG-TPD),
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PCEs of 6.6% and 7.3% have also been
reported.9,44
Because of the defects present in
colloidal ZnO NPs, devices require UV
light exposure to enhance the conduc-
tivity of ZnO NPs. Such photo-conduc-
tivity enhancement occurs within a few
seconds of the UV exposure and the
phenomena can be explained by photo-
doping and defect filling. However, this
photo-doping effect only lasts for a short
time and such a post UV-soaking alone is
not sufficient for optimum device perfor-
mance. While the defect states give rise to
the n-type semiconductivity of ZnO, these
defects also lead to a recombination
pathway for dissociated carriers in the
adjacent BHJ layer. In addition, due to
the small crystal diameter, ZnO NPs are
known to have up to 30% of the atoms
exposed to the particle surface forming
dangling bonds which contribute to a
high density of gap states. These gap state
defects also give rise to the color center
emission in the visible spectrum when
ZnO NPs are photoexcited. Recently, it
has been found that UV-ozone (UVO)
treatment was an effective approach to
passivate these defect states as evident
from the quenching of the color center
while maintaining the work function of
ZnO.13 With UVO-treated ZnO NPs as an
ETL, PDTG-TPD:PC71BM cells show a
significant enhancement of short circuit
current due to reduced interface recom-
bination, resulting in a PCE as high as
8.1% which is among the highest reported
values of a single junction inverted PSC.
These results are illustrated in Fig. 3.
However, this UVO treatment only works
with devices having a photoactive poly-
mer with a deep HOMO energyusually
benchmarked by an oxidization threshold
energy of 5.27 eV.48 Alternatively, for
polymers with shallow HOMO energies,
such as P3HT, it has been reported that
using a self-assembled C60 layer can block
24204 | J. Mater. Chem., 2012, 22, 2420224212
the direct contact between the ZnO NPs
ETL and the absorber, thus enhancing the
efficiency to 4.9%.49
In addition to its use as an ETL in
single junction cells, ZnO is also used to
form the interconnecting unit in tandem
PSCs. Such an interconnecting unit,
essentially a tunneling pn junction
sandwiched by two BHJ cell stacks, forms
a holeelectron recombination zone
across which the Fermi levels of the hole
transporting layer and the electron
transporting layer are aligned to minimize
the Voc loss in a tandem cell. To achieve
good performance in tandem cells, the p
n junction materials should be heavily
doped in order to reach the energy equi-
librium. To date, the most efficient
tandem cell reported utilizes ZnO NPs as
the bottom cathode interlayer, P3HT:
indene-C60 bisadduct (ICBA)50 as the
front cell, ZnO NPs/poly(3,4-ethyl-
enedioxythiophene):poly(styrenesulfonate)
(PEDOT:PSS) as the interconnecting unit
and a low band gap BHJ stack as the rear
cell. The resulting devices have a PCE of
8.6% in which the Voc value is very close
to the sum of the two single junction cells,
indicating a negligible photovoltage loss
across the interconnecting unit.16 Using a
very similar device architecture, a new
Fig. 3 JV characteristics under AM 1.5 G
illumination (top) and external quantum effi-
ciencies spectra (bottom) of the ITO/ZnO NP/
PDTG-TPD:PC71BM/MoO3/Ag device.
Reprinted with the permission of ref. 13.
Copyright 2012 Wiley-VCH.
This journal is The Royal Society of Chemistry 2012
View Article Online
record efficiency of 10.6% was mentioned
in a recent progress report.51
Compared with low work function
metals and polyelectrolytes, the electronic
properties of ZnO are insensitive to the
moisture and oxygen in the ambient; as a
result, the device lifetime is enhanced
using ZnO as a cathode interlayer.
Without any device encapsulation, in-
verted P3HT:PC71BM cells with ZnO
NPs as the bottom cathode interlayer and
evaporated molybdenum oxide as the top
anode interlayer experienced less than
20% reduction in PCE after being exposed
to ambient for 40 days.46 Similarly,
inverted PDTS-TPD:PC71BM cells
retained 85% of their initial PCE (6.6%)
after storage in air over a period of a
month.44 Similar trends have also been
observed in polymerCdSe hybrid solar
cells39 and quantum dot light emitting
diodes (QLED),45 indicating the use of
ZnO NP ETL is promising to enhance
lifetimes of solution processable elec-
tronic devices.
2.1.2 Solgel ZnO (films). In addition
to nanoparticles, ZnO thin films can also
be formed through solgel reaction
between zinc salts and hydroxyl groups
from solvent and ambient water. The so-
called precursor-based52 or solgel
derived53 ZnO refers to the preparation
of ZnO films by annealing zinc acetate
dihydrate solution (in ethanol) at 200
C.
Although this process requires amine
additives and high temperature annealing
to complete the hydrolysis reaction, it is
an effective way to prepare ZnO films as
the bottom cathode interlayers without
any additional material synthesis steps.
Using spray pyrolysis54 and inkjet
printing, solgel ZnO films can be pro-
cessed over a large scale with good
thickness control. For the lab-scale
device fabrication, the first inverted PSC
with a PCE of over 6% was made with
solgel ZnO and poly[[9-(1-octylnonyl)-
9H-carbazole-2,7-diyl]-2,5-thiophenediyl-
2,1,3-benzothiadiazole-4,7-diyl-2,5-thio-
phenediyl] (PCDTBT):PC71BM;53 the
PCE was close to the value obtained for a
conventional device with a top cathode
layer.55
In addition to pristine solgel ZnO
films, solgel ZnO polymer composites
have also been used for inverted PSCs.
For example, ZnOpolyvinylpyrrolidone
(PVP) composites have been made and

PVP has been found to cap the ZnO
clusters in the composite film to improve
the film uniformity.56 However, due to the
smaller surface energy of PVP, the top
surface of ZnO films tend to be PVP-rich
which forms an extraction barrier when
these composite films are used in inverted
cells as a bottom cathode interlayer.
Upon the removal of extra PVP by UVO
treatment, inverted cells of PDTG-
TPD:PC71BM also show improved elec-
trical coupling at the ETLBHJ interface
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resulting in a PCE exceeding 8% with
significantly improved values in FF and
Jsc.15 The surface PVP removal was
confirmed by the significant work func-
tion change of ZnOPVP,13 the composi-
tional change in the X-ray photoelectron
spectra and the morphological change in
the atomic force microscopy (AFM)
phase images.15
In summary, today, ZnO is widely used
as an electron extraction layer for PSCs in
both research and manufacturing and it is
promising for both small area coating and
large area printing.
2.2 Titanium dioxide (TiO2)
TiO2 is a wide gap semiconductor with its
conduction band minima composed of
the Ti 3d band and its valence maxima
composed primarily of the O 2p states. As
a result of oxygen deficiency and the
occupied defect states, TiOx (x < 2) is an
n-type semiconductor. However, as a
typical electron transporting material in
dye sensitized solar cells (DSSC),57,58 the
traditional preparation methods of
nanocrystalline TiOx are not compatible
with processing of PSCs. For example, a
high temperature (450
C) is required to
obtain crystalline TiOx and this high
temperature processing cannot be used
for plastic substrate processing. More-
over, mesoporous TiOx films formed
through TiCl4 treatment59 have a large
roughness and cannot be used as an
electrode interlayer. Thus, to date, most
TiOx films used for PSCs are in amor-
phous phase made by a solgel process.
The solution precursor is typically
prepared using titanium isopropoxide
along with solvent additives. After spin-
coating, TiOx films are formed upon
hydrolysis at 150
C. Such a method is
practically similar to the synthesis solgel
ZnO presented above. According to
X-ray photoelectron spectroscopy results,
This journal is The Royal Society of Chemistry 2012
solution processed TiOx was found to be
oxygen deficient with x 1.34.60
PSCs fabricated with solgel TiOx have
been reported in both conventional and
inverted cells. In conventional cells, the
incorporation of TiOx as an ETL shows
enhanced Jsc and FF when compared with
devices using aluminum electrodes. Using
PCDTBT:PC71BM as the absorber, the
optimum devices have a PCE of 6.1%.55
The enhancement of PCE was attributed
to the improved electrical coupling with
PC71BM and the enhanced light harvest-
ing due to optical interference with the
TiOx film as an optical spacer.60 With a
BHJ layer as thin as 6080 nm, this is
usually a good strategy for polymers with
low hole mobilities and high absorption
coefficient, the optical field distribution in
the absorber is sensitive to its distance to
the back electrodes, making the JV
characteristics highly dependent on the
spacer thickness.61 When TiOx is used as
the bottom electrode interlayer and PE-
DOT:PSS/gold as the top electrode, the
PCE of the resulting inverted
P3HT:PC71BM cells is about 3%.62,63
Similar to ZnO, TiOx has also been used
as the n-type material for the interconnect-
ing charge recombination layer for solution
processed tandem PSCs. With P3HT:ICBA
and poly(4,4-dioctyldithieno(3,2-b:20 ,30 -d)
silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-
4,7-diyl) (PDTS-BTD):PC71BM as the two
absorbing layers, a PCE of 7% (ref. 64) was
reported.
There have also been reports that PSCs
with a TiOx ETL show a strong depen-
dence on UV illumination6567 acquired
from the A.M. 1.5G light exposure.
Showing poor initial device characteris-
tics before UV illumination, these devices
not only require prolonged UV exposure
to obtain optimum JV characteristics
but continuous UV illumination is also
necessary to keep the TiOx layer acti-
vated as some study has revealed that
both Jsc and FF drop rapidly when the
UV portion of the AM 1.5 G spectrum is
filtered.63,68 Such a phenomenon, along
with the work function change67 upon UV
illumination, is in contrast with what has
been observed in ZnO devices, and cannot
be simply interpreted as a result of UV
induced photo-doping. Schmidt et al.
tracked the change in FFs of P3HT cells
after UV exposure under different
ambient conditions. The results indicated
that oxygen is chemisorbed at the TiOx
J. Mater. Chem., 2012, 22, 2420224212 | 24205
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surface, leading to band bending in the
TiOx and suppressing electron extrac-
tion.67 Unless improvement is made on
the UV sensitivity of these TiOx based
devices, their use for PSCs will be limited.
3. Metal oxides as anode
interlayers
For anode interlayers in PSCs, their work
functions need to large enough so that the
Fermi levels of the interlayers match the
HOMO levels of photovoltaic polymers.
UVO treated TCO have a work function
below 5 eV (ref. 69 and 70) and this low
work function does not match the
HOMO energy of many photovoltaic
polymers; therefore, good Ohmic
contacts cannot be made without an
anode interlayer in conventional cells.
For inverted devices, while a high work
function metal may be used for the top
anode, good Ohmic contacts cannot be
made to conjugated polymers with a high
HOMO energy because of the electron
transfer from the metal to the organic
absorber, thus creating an interface dipole
and reducing the device built-in potential.
This reduction of built-in potential of the
BHJ diode not only increases the series
resistance under forward bias but also
decreases the extraction field at short
circuit condition. Therefore, in order to
achieve high Jscs, Vocs and FFs in PSCs,
anode interlayer materials with high work
functions are needed. To date, despite the
problem of device lifetime, PEDOT:PSS
is still the anode interlayer material used
in most PSCs. Recently, several vacuum-
deposited transition metal oxides with
high work functions, good stability and
high optical transparency have gained
significant research interest and PSCs
incorporated with these metal oxides have
demonstrated good device performance.
Depending on the different mechanisms
of hole extraction, both n-type and p-type
semiconducting oxides are used for anode
interlayers. Most transition metal oxides
such as molybdenum oxide, tungsten
oxide, and vanadium oxide are n-type and
they are commonly used for anode Ohmic
contacts for both OPV and OLED
devices. These oxides have work functions
exceeding 6 eV and form strong acceptors
with organic materials. When they are
used as anode interlayers, Fermi level
pinning occurs and increases the built-in
potential. Under an extraction field,

electrons are injected through the
conduction band of the oxide and re-
combine with the photo-generated holes
at the oxideorganic interface. The
process is equivalent to hole extraction.
Nickel oxide is a transition metal oxide
known to be p-type. The large work
function in NiO allows a good match
between the valence band and the HOMO
level of most photoactive polymers. In
early works, these high work function
n-type and p-type semiconducting oxides
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are vacuum deposited. Recent works also
showed these oxides are solution
processable. In the following section, we
will review examples of both n-type and
p-type oxides which have been used as
anode interlayer materials.
3.1 Molybdenum oxide (MoO3)
3.1.1 Thermally evaporated MoO3
(e-MoO3). The use of MoO3 started with
the exploration of efficient hole injection
materials used in OLEDs where the hole
transporting layer has a deep HOMO
level.71 Because of its low melting
temperature (795
C), molybdenum oxide
can be deposited by thermal evaporation
which allows accurate thickness control at
a nanometer scale. MoO3 is an excellent
hole injection material and was once
misidentified as a p-type semiconductor
until the n-type characteristics were
directly determined by ultraviolet photo-
electron spectroscopy (UPS).72 Similar to
TiOx, the 4d band of molybdenum is
unoccupied and contributes to the
conduction band of the oxide. Evident by
results of XPS and UPS measurements,
oxygen deficiency in e-MoO3 gives rise to
the defect band which lifts the Fermi level
closer to the conduction band.73,74 Like
other n-type oxides, e-MoO3 forms
Ohmic contacts with many organic hole
transporting materials. Based on the
results of in situ UPS results, upon depo-
sition of MoO3 onto ITO substrates, the
interface experiences a significant vacuum
level shift of 2 eV which aligns the Fermi
levels of MoO3 and ITO. The work
function of MoO3 is 6.7  0.2 eV and the
Fermi level lies at an energy of 0.5 
0.2 eV below the conduction band edge
and 2.7  0.2 eV above the valence band
edge.72,7477 Further study reveals that the
work function of MoO3 exhibits a strong
dependence on the stoichiometry and is
highly sensitive to surface contamination.
24206 | J. Mater. Chem., 2012, 22, 2420224212
Upon oxygen or air exposure, the work
function decreases to 5.35.7 eV (ref.
7678) which is still sufficient to yield
good Ohmic contacts with organic hole
transporting materials.76 Further reduc-
tion of the suboxide gives rise to growth of
gap states that will finally reach the Fermi
energy, resulting in the metallic behavior
of MoO2.79
In order to understand how a p-type
contact is made with an electron accepting
material, UPS experiments were con-
ducted to study the energy level evolution
of organic materials deposited onto the
MoO3 surface. Here, we use a small
molecule hole transporting material
aluminum phthalocyanine chloride
(AlPcCl) as an example. As shown in
Fig. 4, the HOMO level of AlPcCl shifts
by 1.6 eV when a few nanometers of the
material are deposited on top of the ITO
surface, resulting in a strong band
bending of AlPcCl within the first few
nanometers at the interface.72 Similar
band bending is also directly confirmed by
studying the N,N0 -diphenyl-N,N0 -bis(1-
naphthyl)-1,10 -biphenyl-4,40 -diamine (a-
NPD)MoO3 interface.74,80 Such band
bending indicates there is a strong elec-
tron transfer from the HOMO levels of
organic materials to the 4d band of
molybdenum, leading to Fermi level
pinning at the oxide interface. Such a
phenomenon can be explained by the
thermodynamics that, for either n-type or
p-type oxides, given the metal oxide work
functions are larger than the HOMO
levels of organic materials, the HOMO
offset, which is defined as the difference
between the HOMO levels and Fermi
energy after equilibrium, will approach a
fixed minimum, resulting in Fermi level
pinning as shown in Fig. 5.81 In addition,
due to such a high work function and a
strong electron accepting capability,
Fig. 4 Energy level alignment at the MoO3
organics interface. Reprinted with the permis-
sion of ref. 72. Copyright 2009 American
Institute of Physics.
This journal is The Royal Society of Chemistry 2012
View Article Online
Fig. 5 Plot of HOMO offset (DEH) versus the
difference between the substrate work function
and organic ionization energy (f-IEorg) for
a-NPD on NiO and MoO3, where the electron
chemical potential of oxides was tuned by
inducing oxygen vacancy defects. Reprinted
with the permission of ref. 81. Copyright 2012
Mcmillan Publishers Limited.
MoO3 is an efficient p-type dopant in
organic hole transporting materials.75
For PSCs with a high PCE, the
optimum HOMO level of the photovol-
taic polymers generally resides between
5.2 eV and 5.6 eV considering the
trade-off relationship between Voc and
optical absorption band.82 With these
HOMO energies, good Ohmic contacts to
organic materials can readily be made
with e-MoO3 as an interlayer and the
device data of the resulting PSCs are
summarized in Table 1. Furthermore, our
recent work also showed that compared
with the conventional bottom MoO3
p-contact, enhanced Ohmic contacts can
be made when MoO3 and silver are
sequentially evaporated onto organic
materials as a top p-contact.83 Using such
a top p-contact, inverted solar cells are
now one of the prototypical structures for
the lab-scale device demonstration.
Inverted P3HT:PC71BM cells with PCEs
of 4.55% (ref. 47 and 49) have been
reported and these values are consistently
higher than those for conventional
devices using PEDOT:PSS as the bottom
electrode interlayer. Similarly, PDTS-
TPD:PC71BM cells with a PCE reaching
7.8% (ref. 13) have been demonstrated
and these results are slightly higher than
the 7.3% PCE reported using PE-
DOT:PSS as a bottom p-contact.12 In
addition, PDTG-TPD:PC71BM cells were
reported showing a PCE exceeding 8%
with the inverted device structures.13,15
Using MoO3 to replace PEDOT:PSS for
the bottom anode contact, the resulting
devices show comparable initial
 View Article Online

Table 1 A summary of high efficiency polymer solar cells using transition metal oxide interlayers prepared precursors by dissolving MoO3
powder into H2O2. However, to form
Polymer Anode interlayer Cathode interlayer Jsc (mA cm2) Voc (V) FF PCE (%) s-MoOx films to be used for PSCs, the
P3HT49 e-MoO3 ZnO NP 12.6 0.63 0.62 4.9 process requires a high annealing
P3HT112 NiOx (PLD) LiF 11.3 0.64 0.69 5.2 temperature (300
C). Zilberberg et al.89
PCDTBT55 PEDOT:PSS s-TiOx 10.6 0.88 0.66 6.1 presented a precursor based on bis(2,4-
PCDTBT53 e-MoO3 solgel ZnO 10.4 0.88 0.69 6.3
pentanedionato) molybdenum(VI)
PCDTBT111 s-NiOx Ca 11.5 0.88 0.65 6.7
PDTS-TPD44 e-MoO3 ZnO NP 11.3 0.89 0.67 6.7 dioxide and isopropanol. After annealing
PCDTBT84 e-MoO3 s-TiOx 11.9 0.91 0.66 7.2 in nitrogen at 150
C, a smooth (rough-
PDTS-TPD13 e-MoO3 ZnO NP 13.1 0.90 0.66 7.8 ness r.m.s. <3 nm) s-MoOx film forms
PDTG-TPD15 e-MoO3 solgel ZnOPVP 14.0 0.86 0.67 8.1
PDTG-TPD13 e-MoO3 ZnO NP 14.1 0.86 0.67 8.1 with a work function of 5.3 eV without
additional treatments.
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s-MoOx is a good candidate to replace

performance with much enhanced
stability84 (Fig. 6), indicating high work
function n-type metal oxides can replace
PEDOT:PSS in both conventional and
inverted devices. In recent years, MoO3
has been widely used as a hole injection
layer in organic electronic devices to
replace PEDOT:PSS.
3.1.2 Solution processed MoO3
(s-MoOx). For R2R processing, it is
desirable to deposit MoO3 by a solution
process instead of vacuum deposition. To
use s-MoOx for PSCs, the material should
have a high work function as well as low
surface roughness. In the following
section, we will review several represen-
tative routes to prepare s-MoOx and their
use in P3HT:PCBM cells.
Liu et al.85 presented a facile way to
make s-MoOx thin films, which represents
the first attempt for PSC applications.
The aqueous molybdenum containing a
precursor, ammonium molybdate
[(NH4)6Mo7O24], was dissolved in a
Fig. 6 Normalized PCEs as a function of
storage time for PCDTBT:PC71BM cells
fabricated with PEDOT:PSS and MoO3 in air
under ambient conditions (no encapsulation).
The devices with MoO3 had an initial PCE of
6.4%. Reprinted with the permission of ref. 84.
Copyright 2011 Wiley-VCH.
mixture of hydrochloric acid and de-
ionized water before spin-casting. After
annealing the films at 160
C in nitrogen,
the resulting solgel based s-MoOx films
show a very similar X-ray diffraction
(XRD) pattern compared with e-MoO3
films. The reported P3HT:PCBM cells
showed a PCE of 3.1% which is close to
the PEDOT:PSS device fabricated under
the same condition. Despite the low
temperature process and acceptable PCE
values, aggregation of s-MoOx resulted in
poor uniformity and thus limits its use for
large scale processing. Shortly afterwards,
Meyer et al.78 reported the UPS
measurements and hole injection study of
s-MoOx films made by MoO3 nano-
crystals. In order to realize homogeneous
films, a block copolymer was used to
facilitate the nanocrystal dispersion in
xylene. After spin-coating, oxygen plasma
was carried out to remove the dispersing
agent and also to tune the work function
of s-MoOx. With thermal annealing in
nitrogen ambient at 100
C, s-MoOx
showed a work function of 6.0 eV which
was close to the air exposed e-MoO3 film
(5.7 eV). Using these MoO3 nanocrystals,
Stubhan et al.86 fabricated P3HT:PCBM
cells with s-MoOx interlayers with PCEs
of 2.5%, which is lower than the results
obtained for typical P3HT cells. The PCE
was probably limited by the rough surface
of s-MoOx due to the large nanocrystal
size of 15 nm. Hammond et al.87 also
reported that oxygen plasma treatment
on s-MoOx films, made from the molyb-
denum tricarbonyl trispropionitrile
[Mo(CO)3(EtCN)3] precursor, increased
the work function of s-MoOx to 5.4 eV,
resulting in P3HT cells with PCEs of
3.5%. Others also recently reported
similar device performance without using
oxygen plasma treatment. Girotto et al.88
PEDOT:PSS for PSCs with greatly
improved device stability.88,89 However,
the work function values of s-MoOx films
tend to be lower than that of e-MoO3,
thus affecting the quality of the resulting
Ohmic contacts. In the above mentioned
work, P3HT:PCBM cells with s-MoOx
generally show a Voc value of 0.55 V
which is 50 mV lower than that for the
same devices made with e-MoO3. An
exploration of better aqueous precursors
as well as processing conditions is needed.
In spite of progress made, the uniformity
issue of ultra-thin s-MoOx films has to be
resolved to enable their use for large scale
manufacturing.
3.2 Tungsten oxide (WO3)
Another n-type metal oxide with a high
work function is WO3; similar to MoO3,
its electronic structure highly depends on
the stoichiometry, the crystalline struc-
ture and thus the deposition conditions.
Back in the 1980s, the valence band
structure and the Fermi energy of ther-
mally evaporated WO3 (e-WO3) were
well studied by UPS.90 Evaporated films
of amorphous WO3 are generally defi-
cient in oxygen which gives rise to the
gap states and n-type semiconductivity.
Further depletion of oxygen is observed
when WO3 films are annealed at high
temperatures in vacuum and eventually
converted to metallic WO2. During the
annealing process, the occupancy of gap
states at the valence band edge grows
significantly and leads to a reduction of
work function from 6.05 eV to 5.5 eV.
The work function is also sensitive to
oxygen exposure which reduces the work
function further to 4.7 eV. The optical
band gap of these evaporated films has
been determined to be 3.253.41 eV and
was found to decrease by 0.5 eV upon
annealing in air.

This journal is The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 2420224212 | 24207

Inverted P3HT:PCBM cells using
e-WO3 as a top anode interlayer and
s-TiOx as a bottom cathode interlayer
have been reported by Tao et al.91 With an
optimum e-WO3 film thickness, the
devices display a Voc of 0.6 V and a FF
over 0.60, revealing the high work func-
tion that was reported earlier.80,90 Similar
device performance was also demon-
strated using conventional devices
wherein e-WO3 films were used as the
bottom anode interlayer with low surface
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roughness (r.m.s. 0.88 nm).92 The
tungsten suboxide deposited by thermal
evaporation and subsequent hydrogen
reduction shows metallic conductivity
with a large work function and makes
good Ohmic contact to materials with
deep HOMO energies such as poly[(9,9-
dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-
(2,10 ,3)-thiadiazole)] (F8BT) (5.9 eV).
Recently, solar cells with good perfor-
mance using solution processed WO3
have also been reported. Using tungsten
ethoxide [W(OC2H5)6] solution (in
ethanol) as the precursor, spin-coated
films show a larger work function than
PEDOT:PSS, which leads to a 3.4% PCE
(Jsc 8.63 mA cm2; Voc 0.62 V; FF
0.63) for a P3HT:PCBM cell made in a
conventional structure. The devices show
a much enhanced lifetime by maintaining
90% of the initial value after being
exposed to air for nearly 200 hours
without any encapsulation.93 These
promising results make s-WO3 a better
choice than other solution processed
high-work-function oxides for large-scale
coating in the R2R process.
3.3 Vanadium oxide (V2O5)
The third n-type semiconducting oxide
used as the anode interlayer is V2O5. Its
band gap determined by UPS and IPES is
2.8 eV,94 revealing that its absorption
band partially covers the absorption band
of PC71BM. Similar to MoO3 and WO3,
the band structure of e-V2O5 is highly
sensitive to the ambient environment.
Based on the results of in situ UPS
measurements, e-V2O5 films deposited
under ultra-high-vacuum conditions
(<1010 Torr) reaches a work function
value as large as 7.0 eV, and thus provides
an excellent Ohmic contact to organic
materials with large HOMO energies.94
P3HT:PCBM cells using e-V2O5 (106
Torr) as an anode interlayer show an
24208 | J. Mater. Chem., 2012, 22, 2420224212
optimum PCE of 3%, which is close to
similar devices with a MoO3 interlayer.7,95
Upon air exposure, the work function of e-
V2O5 drops significantly to 5.3 eV along
with a significant reduction of electron
affinity and growth of gap states.95
Therefore, compared with the V2O5
deposited in high vacuum, such contami-
nated e-V2O5 is just lightly n-doped and
thus less likely to induce efficient charge
transfer, resulting in a larger contact
barrier with organic materials. As is
evident by XPS spectra, the band structure
change is attributed to the adsorbates that
partially reduce V5+ at the top surface.95
Vanadium(V) oxitriisopropoxide is a
common precursor to synthesize solgel
V2O5 at room temperature. Due to air
exposure during the hydrolysis reaction,
the work function, ionization potential
and electron affinity of this solution pro-
cessed V2O5 (s-V2O5) are very close to
those of the contaminated e-V2O5. The
optical gap of solgel V2O5 films is 2.3 eV,
indicating the change of its electronic
structure from the bulk to the top
surface.96 Compared with e-V2O5 without
any air exposure, P3HT devices with
s-V2O5 show a reduction of Voc due to the
poor energy level alignment at the anode
interface. The resulting energy alignment
does not induce a hole extraction barrier;
thus, the reduction of Jsc can only be
explained by the decrease of an extraction
field. Compared with MoO3, less work
has been done on V2O5. For a better
understanding of the charge extraction
mechanism at the s-V2O5polymer inter-
face, further studies of the interface elec-
tronic structures are still needed.
3.4 Nickel oxide (NiO)
Among the metal oxides presented in this
review, nickel oxide (NiO) is the only
p-type semiconducting oxide. In contrast
to all the above n-type oxides where their
semiconductivity originates from the
negative charge compensation at defect
sites of oxygen vacancies and/or cation
interstitials, the p-type characteristics of
NiO stems from positive charge compen-
sation at the thermodynamically favored
Ni2+ vacancies9799 and is related to its
complex band structure100 wherein both
the valence band maximum and conduc-
tion band minimum are believed to
contain contributions from the Ni 3d
states.101103
This journal is The Royal Society of Chemistry 2012
View Article Online
The work function of NiO strongly
depends on its surface chemistry, crystal
orientation and the thin film deposition
conditions. For NiO formed by in situ
oxidization of sputtered nickel films, the
work function is as large as 6.7 eV.104
NiO films can also be formed by UVO
treatment or oxygen plasma treatment of
metallic nickel or solution processed
nickel containing precursors. The work
function of ex situ oxidized NiO films is
5.05.6 eV,104106 close to those of in situ
prepared samples with subsequent air
exposure.104 Such a work function
change is summarized in Table 2 along
with the high work function oxides pre-
sented above. It is well documented that
the NiO surface readily adsorbs surface
contaminants such as nitric oxide,
various carbonaceous species and
hydroxyl species107109 within minutes of
air exposure and results in a work func-
tion reduction. Interestingly, a recent
study by Ratcliff et al. on solution-pro-
cessed NiO concluded that post-deposi-
tion O2 plasma treatment increased the
work function from 4.7 eV to 5.3 eV by
creating a dipolar nickel oxyhydroxide
(NiOOH) on the NiO surface.101
However, in earlier work by Ratcliffs
collaborators,105 it was shown that the
work function quickly decreased after O2
plasma treatment even when the NiO
film was stored in a N2 environment. It is
possible that in these studies, the O2
plasma treatment not only induced a
favorable NiOOH surface dipole but also
removed the surface contaminants, re-
sulting in NiO with a larger work func-
tion and making more surface lattice
sites available for hydroxylation. Upon
exposure to the nitrogen environment
after the O2 plasma treatment, it is
probable that contaminants were ad-
sorbed by NiO, which reduced the work
function again. Despite these changes,
the work function of NiO is sufficient for
the energy alignment with the HOMO
levels of many photovoltaic polymers.
Moreover, due to the small electron
affinity (2.1 eV) and wide band gap,100
NiO acts as an effective electron blocker
by introducing a large electron trans-
porting barrier at the photovoltaic
polymer interface.110,111 As a result of the
electronic structure of NiO thin films,
high efficiency solar cells have been
fabricated and the results will be pre-
sented in the next section.

Table 2 The reported work function values of high-work-function transition metal oxides that are prepared under different conditions. The results were
obtained using UPS or Kelvin Probe
Work function (eV) MoO3
Vacuum deposited 6.56.9 (ref. 72, 7477)
Air exposed 5.35.7 (ref. 7678)
Solution processed 5.36.0 (ref. 78, 87 and 89)
3.4.1 Vacuum deposited NiO. In
earlier studies on PV cells with NiO
interlayers, NiO films were deposited in
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vacuum where the O2 partial pressure and
moisture level during film growth can be
accurately controlled. Irwin et al.112 first
demonstrated NiO hole extracting/elec-
tron blocking layers in conventional
P3HT:PCBM cells by depositing NiO via
pulsed laser deposition (PLD) on top of
ITO. They observed an increase in Jsc, Voc
and FF when compared to devices with
no hole extraction/electron blocking
layers and devices with PEDOT:PSS as
the hole extraction layer. The optimized
solar cells incorporated a 10 nm thick NiO
layer to minimize series resistance and
optical absorption by NiO and achieved a
PCE greater than 5%. Encapsulated
devices with NiO showed good stability
up to 60 days of continuous operation,
while the stability curve trends for much
longer times. Conductive AFM measure-
ments from the same group revealed a
reduction in conductivity hot and cold
spots when NiO is deposited on ITO,
suggesting a homogeneous electrical
surface which reduced leakage and
recombination at the NiOorganics
interface.113 UPS measurements revealed
a large work function and ionization
potential which are sufficient for align-
ment with the HOMO energies of many
state-of-the-art photovoltaic polymers.
Additionally, the Voc enhancement was
attributed to the reduction of electron
leakage current. Since then, several
groups have also showed enhanced device
performance by depositing NiO by sput-
tering,114116 PLD117 and O2 plasma
treatment of evaporated nickel films.118
While NiO films can easily be fabricated
by a wide variety of vacuum based tech-
niques, solution processed NiO is needed
for R2R processing.
3.4.2 Solution-deposited NiO.
Unlike ZnO and TiO2, a direct route from
the metal salt to a colloidal nanocrystal-
line NiO at low temperatures and without
This journal is The Royal Society of Chemistry 2012
WO3 V2O5
6.16.6 (ref. 80 and 90) 6.87.0 (ref. 94 and 123)
4.7 (ref. 90) 5.3 (ref. 95)
4.8 (ref. 93) 5.3 (ref. 96)
aliphatic insulating ligands has not been
demonstrated. This seems to be due to the
fundamental difference in the chemical
behavior of nickel compared to that of
zinc or titanium. For example, during the
synthesis of ZnO nanoparticles under the
excess base condition, the precipitated
zinc hydroxide [Zn(OH)2] does not
terminate the reaction in alcoholic solvent
because it rapidly forms soluble interme-
diate tetrahydroxozincate ions (i.e.
[Zn(OH)4]2) which then undergo water-
catalyzed dehydration to yield colloidal
nanocrystalline ZnO.119 In the case of
synthesizing colloidal TiO2, researchers
take advantage of the oxophilicity of
titanium, i.e. it induces hydrolysis of
ambient water or directly abstracts
oxygen from its surroundings.120 This
process has been shown to readily yield
nanocrystalline TiO2 from a TiCl4
precursor without any bulky insulating
ligands. However, the synthesis of nickel
oxide from wet chemical techniques
cannot follow either of these routes.
Nickel hydroxide is insoluble in alcohol
and cannot accept excess OH to form
soluble complex anions. Also, it has not
been shown that nickel salts possess the
same ability to induce direct hydrolysis or
oxygen abstraction in alcoholic solutions
to form NiO. Despite these limitations,
thus far, there have been several routes to
employing solution-processed NiO in
solar cells, including the solgel route in
the conventional devices,105,110,111 pep-
tized nickel hydroxide in a conventional
device structure,121 and a dispersion of
fine NiO powder into solvents for the top
electrode interlayer in inverted solar
cells.122 The solgel route is more popular
for solution-processed NiO films used in
organic solar cells. The first report of
solution-processed NiO in PSCs came
from Steirer et al.,105 where they reported
that nickel formate formed a complex
with ethylenediamine to compose the
nickel ink. NiO films were formed by spin-
casting followed by heat treatment (250
300
C) in air. O2 plasma treatment
View Article Online
NiO
6.7 (ref. 104)
5.5 (ref. 104)
5.35.4 (ref. 101, 105 and 110)
increased the NiO work function, which
enabled solar cells to be made with iden-
tical PCEs to those of the control devices
with PEDOT:PSS. Further work from
Steirer, Ratcliff, and collaborators has
developed a more comprehensive under-
standing of the surface interaction of NiO
with photoactive layers based on P3HT
and PCDTBT.101,110,111 The O2 plasma
treatment on NiO not only increased its
work function, it also increased its band
gap energy and enhanced its electron
blocking capability. UPS and XPS results
were correlated with device performance
and showed that the dipolar NiOOH
species on the NiO surface was respon-
sible for the increase in work function as
well as the enhanced hole extraction and
electron blocking at the NiOactive layer
interface. As shown in Fig. 7, these effects
produced solar cells with higher values of
Jsc, Voc and FFs than the control devices
using PEDOT:PSS, and the devices ach-
ieved a final PCE of 6.7% using
PCDTBT:PC71BM as the photoactive
layer.110,111
As a very promising solution processed
anode-interlayer material, the high
temperature for annealing during the NiO
film processing may be the bottleneck for
its flexible electronics applications. A
better understanding of the chemical
processes during heat treatment will help
to realize low-temperature solution pro-
cessed NiO films.
4. Summary and outlook
In summary, we reviewed the synthesis
and the electronic properties of transition
metal oxides used for both anode as well
as cathode interlayers in PSCs along with
the performance data of the resulting
devices. Low work function oxides, such
as ZnO and TiO2, with their work func-
tion matching the LUMO levels of elec-
tron-accepting fullerene derivatives are
used as electron extraction interlayers.
High work function oxides such as MoO3,
WO3 V2O5, and NiO form good Ohmic
J. Mater. Chem., 2012, 22, 2420224212 | 24209

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Fig. 7 Solar cell performance of BHJ devices utilizing NiOx or PEDOT:PSS as the anode interlayer.
(a) JV characteristics under AM 1.5 G illumination. Control devices with PEDOT:PSS exhibited
5.7% PCE compared to 6.7% of those with NiOx. Inset: JV curves comparing BHJ solar cells with
as deposited and oxygen-plasma treated NiOx films. (b) Dark JV characteristics and corresponding
fits. Solar cell performance is improved with NiOx via a reduced reverse saturation current and diode
ideality factor. Reprinted with the permission of ref. 111. Copyright 2011 Wiley-VCH.
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Acknowledgements
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15 C. E. Small, S. Chen, J. Subbiah,
We acknowledge the support of Depart-
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