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de
Sulfur-Doped Nickel Oxide Thin Film as an Alternative
Communication
to Pt for Dye-Sensitized Solar Cell Counter Electrodes
Guan Hong Guai, Ming Yian Leiw, Chee Mang Ng, and Chang Ming Li*
Dye-sensitized solar cells (DSSCs) have attracted intense
research attention because of their low cost and high efficiency
in converting solar energy into electricity.[1,2] Typically, a DSSC
constitutes a dye-loaded mesoporous TiO2 photoelectrode, an
electrolyte containing iodide/tri-iodide (I−/I3−) redox couples,
and a catalytic counter electrode which reduces I3− ions.[3,4]
Since both the photo and counter electrodes are exposed to the
electrolyte, a high DSSC performance is greatly dependent on a
fast reduction reaction at the counter electrode to suppress the
possible reduction reaction by a charge recombination process at
the photoelectrode.[5,6] To achieve such selectivity, noble platinum
(Pt) is often used as a catalyst on fluorine-doped tin oxide (FTO)
conducting glass to enhance the reduction rate at the counter
electrode.[7] However, Pt is expensive and non-sustainable
for long-term applications. Carbon-based materials such as
polymers, carbon black, and carbon nanotubes have also been
reported to replace Pt catalysts.[8,9] However, these carbon mate-
rials have much weaker catalytic activities than Pt and thus
require large carbon loadings (loading ∼300 to >1000 μg cm−2)
to compensate for the lowered electrocatalytic activity, resulting
in poor device energy density.[9–11] Therefore, a low cost and
robust alternative counter electrode with high electrocatalytic
activity towards I3− reduction is in high demand.
Transition metal based materials have been demonstrated to
possess outstanding catalytic performance in redox reactions
because of their multiple oxidation states.[12,13] However, very
few of such materials have been studied and employed as a
DSSC counter electrode.[14,15] In this study, nickel oxide (NiO)
is selected as a potential electrode material because of its good
charge capacity,[16] high chemical stability,[17,18] and a valence
band energy (∼–4.96 eV) comparable to the redox potential of
I−/I3− for favorable charge transfer between the metal oxide
G. H. Guai, Prof. C. M. Li
Center for Advanced Bionanosystems and School of Chemical
and Biomedical Engineering
Nanyang Technological University
70 Nanyang Drive, Singapore 637457, Singapore
E-mail: Ecmli@ntu.edu.sg
G. H. Guai, M. Y. Leiw, Dr. C. M. Ng
GlobalFoundries Singapore Pte. Ltd.,
60 Woodlands Industrial Park D, Street 2, Singapore 738406, Singapore
M. Y. Leiw
School of Electrical and Electronic Engineering
Nanyang Technological University
50 Nanyang Avenue, Singapore 639798, Singapore
Prof. C. M. Li
Institute for Clean Energy & Advanced Materials
Southwest University
Chongqing 400715, P.R. China
DOI: 10.1002/aenm.201100582
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and redox couples,[19,20] although its low conductivity and poor
charge carrier mobility limit its actual charge transfer process. To
improve the charge transfer impedance of NiO, a sulfur-doped
nickel oxide (S–NiO) thin film is fabricated for a DSSC counter
electrode and its electrocatalytic activity towards the I−/I3−
redox process is investigated. By using an electrophoretic depo-
sition method, a porous S–NiO thin film with a nanorod-like
network is fabricated on a FTO substrate to greatly enhance its
effective reaction surface area. The surface composition and
morphology of the S–NiO thin film are characterized using
scanning electron microscopy (SEM), X-ray photoemission
spectroscopy (XPS), and energy dispersive spectroscopy (EDS).
The results obtained from cyclic voltammetry (CV) and alter-
nating current (A.C.) impedance measurements indicate that
the S–NiO\FTO (SNO) electrode possesses high electrocatalytic
activity towards the I−/I3− redox process as compared to both
plain NiO\FTO (NO) and FTO electrodes. When a low loading
of S–NiO (∼40 to 50 μg cm−2) is applied as a DSSC counter elec-
trode, a performance close to that of Pt and much better than
plain FTO and NiO is achieved.
The surface morphology of the S–NiO thin film electro-
deposited on FTO glass in Figure 1a depicts a porous network
consisting of intertwined nanorods with diameter ca. 60 nm
and length ∼200 nm. Based on the cross-sectional FESEM
image of the film, the thickness of the film is approximately
60–140 nm depending on the deposition duration. Because
of its thin porous nature, the SNO electrode possesses a low
optical absorbance similar to bare FTO as shown in Figure 1b.
Compared to the opaque or non-transparent electrode formed
by Pt nanoparticles or carbon based materials, the high optical
transmittance of the SNO electrode (∼80%) appreciably allows
possible application to other DSSC layouts, such as a tandem
structure or metal-foil-supported DSSCs.
The corresponding XPS survey spectrum against binding
energy (BE) in Figure 1c shows that five elements, Ni, O, S,
Sn, and C, are detected and the various XPS peaks are labeled
accordingly. The presence of a C 1s peak (BE 284.2 eV) is likely
attributed to the adventitious carbon from the equipment. Since
the S–NiO film is porous, a Sn 3d peak (BE 485.8 eV) from the
underlying FTO substrate is also slightly detected. As the XPS
peak position is highly sensitive to the chemical environment
of the elements, high resolution XPS spectra are obtained to
further characterize the oxide film. As shown in Figure 1d, the
measured Ni 2p peak position of the NiO film is located at BE
854.4 eV with increased energy as compared to that of pure Ni
metal (BE 853.1 eV). The oxide-associated O 1s peak position
is determined at 530.4 eV (see inset (i) of Figure 1d). Similarly,
the measured S 2p peak is also shifted from BE 164 to 168.2 eV,
and is contributed by a sulphate (SO4) group (see inset (ii) of
Figure 1d). Thus, the S–NiO thin film could be confirmed to
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Figure 1.  a) Surface morphology of a S–NiO\FTO (SNO) electrode. The inset shows its cross-sectional FESEM image. b) UV–vis optical absorbance
and transmittance (inset) spectra of a S–NiO thin film and bare FTO substrate. c) XPS survey spectrum of S–NiO\FTO (SNO) electrode. d) XPS high
resolution Ni 2p, O 1s, and S 2p spectra of a S–NiO thin film.
be a composite consisting of NiO and NiSO4 with the former
as the main component. The higher BE peak positions of both
measured Ni 2p and S 2p peaks are a result of the attraction
of valence electrons in the Ni-O and Si-O bonds towards the
more electronegative O atoms. Consequently, both Ni and S
possess slightly positive net charges which increase the binding
energies with the core electrons. The EDS spectrum obtained
further confirmed the presence of Ni, S, and O in the SNO elec-
trode (see Figure S1, Supporting Information).
To understand the catalytic mechanism of the S–NiO thin
film, the electrochemical behaviors of a SNO electrode toward
the I−/I3− redox reaction were studied by CV and impedance
measurements. Figure 2a displays the CV curves of a SNO
electrode with 48.1 μg cm−2 S–NiO loading in an iodide-based
electrolyte at different scan rates (ν). When the potential is
decreased from +1.0 V to –0.6 V, two reaction peaks occur.
Since the cyclic voltammograms of the S–NiO film is alike that
of reported works for Pt catalysts, the I3− reduction pathway
on the oxide film can be assumed to be similar.[11,21] Peak A
(at ∼ +0.6 V) denotes the adsorption process while peak R repre-
sents the I−/I3− reduction reaction (at ∼–0.3 V). As shown below
in Equation 1 and 2, I3− is first adsorbed onto the unoccupied
S–NiO catalytic surface (Θ) and reduced to form intermediates,
followed by reduction of the adsorbed molecules (I2*) to I− and
desorption.[5] It is noted that the peak at +0.3 V is not a redox
peak as the peak current remains zero and does not vary with
increasing ν. Instead, it may be a result of the overpotential
compensation of the SNO electrode.
Adv. Energy Mater. 2012, 2, 334–338 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Communication
I− − ∗
3 + 2 ↔ I + I2 (1)
I∗2 + 2e−↔ 2I− + 2 (2)
In addition, the linear relationship of the reduction peak cur-
rent (Ipc) versus ν illustrated in inset (i) of Figure 2a indicates
that the reaction process of the I−/I3− redox couple is a surface
adsorption-limited electrocatalytic process. Thus, the Ipc should
be proportional to the adsorption quantity of the reacting ion
(Γ) by the relation:[21]
 
Ipc = (n · F )2 · ν ·  / ( R · T ) (3)
where n is the number of electrons appearing in the half-
reaction for the redox couple (i.e., n = 2), F is the Faraday constant,
R is the universal gas constant, and T is the absolute tempera-
ture. Based on Equation 3, the adsorption quantity of I3− for the
S–NiO electrode is determined to be 6.89 × 10−10 mol s−1.
Figure 2b shows the linear voltammograms of different SNO
electrodes with increasing oxide loading. Compared to bare
FTO, the presence of a S–NiO film significantly increases the
Ipc from 0.16 to 1.06 mA (SNO4), indicating that S–NiO has
a much stronger electrocatalytic activity towards reduction of
I3− than FTO. This is because a higher loading of S–NiO tends
to increase the effective catalytic surface area, thus a larger Ipc
occurs and the onset of the redox peak R is also shifted more
positively from –0.41 to –0.27 V, signifying a better intrinsic
catalytic activity of the SNO electrode than FTO. In addition, the
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the SNO electrode. It is known that in a voltammogram, the

Communication

peak current is proportional to the electrode surface area while

a more positive onset potential indicates a faster charge transfer
rate in a reduction process. Thus, S dopants in the S–NiO film
improve both charge transfer and reaction surface area for
better electrocatalytic performance.
Figure 2c illustrates the A.C. impedance Nyquist plots of
various SNO electrodes, in which the diameter of the semi-
circle represents the Faraday resistance of the electrochemical
reaction. In an electrochemical reaction, a lower Faraday resist-
ance indicates a faster electron transfer rate.[22] Since NiO is
semiconductive and has a lower charge carrier mobility as com-
pared to Pt, the poor conductivity of a thicker oxide film tends
to limit electron transport to the FTO current collector, which
in turn results in a slower electron transfer from the S–NiO\
FTO interface to the S–NiO\electrolyte catalytic surfaces. Thus,
the Faraday resistance is increased from ∼450 to ∼3000 Ω when
the S–NiO loading increases from 27.2 (SNO2) to 63.6 μg cm−2
(SNO6). The charge transfer comparisons by the A.C. imped-
ance measurements agree well with the CV results.
In a DSSC, the electrochemical reduction of the I−/I3− redox
couple can occur on both photo and counter electrodes, and a
slow reaction rate at the counter electrode can cause a serious
charge recombination in the photoelectrode to reduce the power
conversion efficiency (PCE). Thus, optimization of the S–NiO
loading for a high charge transfer rate is required to achieve
good catalytic performance. In this work, a S–NiO loading
of 48.1 μg cm−2 is found to have a relatively low resistance
(∼1000 Ω) while achieving a high Ipc (1.06 mA).
The current–voltage (I–V) characteristics of DSSCs made
from SNO counter electrodes with different S–NiO loadings is
depicted in Figure 3 (and Table S1, Supporting Information).
A conventional platinized electrode, with a Pt loading of 5.7 μg
cm−2, achieved a PCE of 6.08% and is used for comparison. It
is shown clearly that when an S–NiO thin film is introduced
onto a plain FTO substrate, the device performance is greatly
improved from 0.08% (of FTO electrode) to 3.23% (of SNO1
electrode), representing a significant forty times increment.

Figure 2.  a) Cyclic voltammograms of a S–NiO\FTO (SNO) electrode

at increasing scan rate from 0.05–0.20 V s−1. A Pt foil and Ag/AgCl elec-
trode were used as the counter and reference electrodes, respectively.
Labels A and R signify the adsorption current peak and the I−/I3− redox
current peak, respectively. The inset illustrates the relation between the
reduction peak current (Ipc) versus scan rate (ν) for the SNO electrode.
b) Reduction linear voltammograms for bare FTO, plain NiO\FTO (NO),
and various SNO electrodes with increasing S–NiO loading at a scan rate
of 0.10 V s−1. c) A.C. impedance spectra of FTO, NO, and different SNO
electrodes with increasing S–NiO loading. Figure 3.  Photocurrent–voltage characteristics of DSSCs with various
counter electrodes, namely S–NiO\FTO (SNO), platinized FTO (Pt),
plain NiO\FTO (NO), and bare FTO substrates. The inset illustrates the
NO electrode is also found to have a lower Ipc (0.57 mA) and a relationship between the power conversion efficiency (PCE) versus S–NiO
more negative onset of redox peak R (–0.47 V) as compared to loading for DSSCs with SNO counter electrodes.

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Although the FTO surface could be exposed to electrolyte
through the porous structure of the S–NiO layer, a bare FTO
electrode has a much poorer electrocatalytic activity than a
S–NiO\FTO electrode. Thus the performance of a SNO based
device should be mainly dependent on S–NiO loading as proven
by the optimization shown in Figure 3. A SNO based DSSC is
also found to have a much higher PCE than a device based on a
NO electrode (0.31%). The significantly enhanced performance
of a S–NiO film over plain NiO and FTO films is apparently
contributed by the presence of S dopants, which significantly
improve both charge transfer and reaction surface area for high
electrocatalytic activity at the counter electrode\electrolyte inter-
face as supported by the electrochemical results (see Figure 2).
With greater S–NiO loading, the short circuit current density
(Jsc) and open-circuit voltage (Voc) for SNO based devices are
gradually increased to ∼13.5 mA cm−2 and ∼770 mV, respec-
tively, to finally achieve a PCE of 5.04% (see Figure 3 inset). It is
also found that SNO based DSSCs often have a lower fill factor
(FF) than Pt based DSSCs, which is likely caused by the higher
electron transfer resistance than in the latter device. Further-
more, compared to other non-Pt based counter electrodes such
as carbon black and carbon nanotubes, only a low loading of
S–NiO (48.1 μg cm−2) is required to achieve a DSSC perform-
ance close to that of a Pt electrode. Hence the SNO electrode
has a prominent advantage of using much less materials for
higher energy and power density to replace a Pt counter elec-
trode. Investigations to further improve the electrocatalytic
activity of the SNO electrode are currently underway in our lab.
In summary, a transparent S-doped NiO\FTO (SNO) electrode
with low oxide loading is successfully prepared as a counter elec-
trode for DSSCs. The electrode material has been characterized
by FESEM, XPS, and EDS. Electrochemical behaviors of the SNO
electrode in a I−/I3− redox system are systematically studied, indi-
cating that the I3− reduction pathway by the oxide film electrode
follows a two-step process and is surface adsorption limited. The
enhanced electrocatalytic activity of the SNO electrode is very likely
contributed by the S dopants in the NiO film which significantly
improve both charge transfer and electrochemical reaction surface
area. However, a very high loading of S–NiO tends to cause high
interfacial impedance despite providing a large effective surface.
Hence, optimization of the SNO electrode is required to achieve
a high electrocatalytic effect between the reaction surface and
charge transfer rate towards the I−/I3− redox process. This work
offers a promising Pt-free counter electrode material with high
energy density to achieve good DSSC performance close to the
conventional platinized electrode. The high optical transmittance
of the SNO electrode also provides potential applications in metal-
foil-supported DSSCs or power-producing windows.
Experimental Section
Preparation of Counter Electrodes: To fabricate the S–NiO\FTO (SNO)
electrode, a precursor mixture containing NiCl2 (5 × 10−3 m) and CH4N2S
(150 × 10−3 m) in pH 10 KOH solution was first prepared and aged for
3 h at room temperature. Electrophoretic deposition of S–NiO on the
cleansed FTO glass substrate (Nippon Glass Sheet, ∼12 Ω −1) was
then accomplished using a CHI 760B electrochemical workstation (CH
Instrument Inc., Shanghai) at a constant voltage of –0.8 V in a three-
electrode cell setup with a Ag/AgCl reference electrode and a planar Pt
Adv. Energy Mater. 2012, 2, 334–338 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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foil as the counter-electrode. By controlling the deposition time, different
Communication
loadings of S–NiO can be precisely controlled and deposited on different
FTO surfaces for DSSC performance evaluation. After the S–NiO formed
a thin film, the oxide coated electrode was dried at 70  °C for 1 h. A
plain NiO thin film on a FTO substrate was prepared using the above-
described method without CH4N2S, followed by thermal annealing at
350 °C for 30 min. A conventional platinized electrode was also prepared
by sputtering Pt onto a FTO substrate using a JFC-1600 fine coater (JOEL
Ltd., Japan). All chemicals used were purchased from Sigma–Aldrich.
For clearer elaboration, the S–NiO\FTO and plain NiO\FTO electrodes
are referred to as SNO and NO electrodes respectively.
Assembly of DSSC: A DSSC photoelectrode was prepared by screen-
printing a layer of TiO2 paste (DSL 18NR-T, Dyesol Co.) on a clean FTO
substrate, followed by thermal annealing at 450  °C for 30 min. The
thickness of the resultant mesoporic TiO2 film was approximately 10 μm.
A 4 μm scattering over-layer consisting of 400 nm TiO2 nanoparticles
was then deposited and heated at 500  °C for 30 min, followed by an
immersion in N719 dye solution (Solaronix SA, 0.3 × 10−3 m) composed
of a 50:50 mixture of acetonitrile (Sigma–Aldrich) and tert-butanol
(Sigma–Aldrich) for 20 h at room temperature for dye adsorption. A
sandwich-type DSSC device was assembled by placing the dye-loaded
photoelectrode on each prepared counter-electrode. The two electrodes
were clipped firmly together and a drop of liquid electrolyte (HL-HPE,
Dyesol Co.) was injected into the cell. The active area of the cell was
defined by a mask with an aperture of 0.25 cm2.
Characterization: Cyclic voltammetry (CV) measurement was carried
out at scan rates between 0.05 and 0.20 V s−1 in a three-electrode
cell setup using a CHI 760B electrochemical workstation. The cell
setup comprised a S–NiO coated, plain NiO coated, or non-coated
substrate as the working electrode, an Ag/AgCl reference electrode,
and a Pt foil as the counter-electrode. The electrolyte was LiI/I2 (10 ×
10−3 m, molar ratio 9:1) in acetonitrile, with LiClO4 (0.1 m) added as the
supporting electrolyte. Electrochemical A.C. impedance spectroscopy
(EIS) was performed for the fabricated electrodes by using the same
three-electrode cell setup with a CHI 760B workstation. The EIS were
recorded over a frequency range of 0.1 to 105 Hz at an applied voltage
of 5 mV. To study the surface morphology of the fabricated electrodes,
field-emission scanning electron microscopy (FESEM) was performed
using a Jeol JSM-6701F microscope. The element stoichiometry of the
S–NiO thin film was determined by X-ray photoelectron spectroscopy
(XPS) using a Kratos Analytical AXIS Ultra model with a monochromatic
Al Kα source. Energy dispersive spectroscopy (EDS) was performed
using an EDS model 6587 from Oxford Instrument coupled with a SEM
JEOL JSM5600LV and Oxford Instrument Link ISIS system software. A
Shimadzu UV-2450 spectrophotometer was used to record the optical
absorbance and transmittance of the prepared electrode between the
wavelengths of 300 and 800 nm. The current–voltage characteristics of
the DSSCs were measured with a Keithley 2420 multimeter under one
sun condition using a solar light simulator (Abet Technologies S2000
with a 550-W Xe lamp and an AM 1.5 filter, 100 mW cm−2).
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was financially supported by Center for Advanced Nanosystems,
Nanyang Technological University (Singapore), and GlobalFoundries
Singapore Pte. Ltd.
Received: September 28, 2011
Revised: November 24, 2011
Published online: February 6, 2012
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