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CuIn(S,Se)2 thin films prepared from a novel

Cite this: Phys. Chem. Chem. Phys.,
2014, 16, 7548
thioacetic acid-based solution and their
photovoltaic application†
Yian Xie,a Yufeng Liu,*a Yaoming Wang,a Xiaolong Zhu,a Aimin Li,a Lei Zhang,a
Mingsheng Qin,a Xujie Lüa and Fuqiang Huang*ab

Received 6th January 2014,
Accepted 25th February 2014
DOI: 10.1039/c4cp00045e
www.rsc.org/pccp
Low-cost and high-yield preparation of CuInSe2 films is the bottleneck for promising CuInSe2-based
thin film solar cells. Here, we developed a simple, safe and cost-effective method using thioacetic acid
to fabricate the absorber films of CuIn(S,Se)2 (CISSe). Dissolution of Cu2O and In(OH)3 in thioacetic acid
was attributed to the strong coordination ability of S. The adhesive precursor solution can be prepared
without any heating, centrifugation and inert gas protection, superior to the previously reported
methods. The precursor CISSe layer was easily deposited in air by spin coating to ensure low cost.
Uniform and compact CISSe thin films with well-crystallized and pure-phased CISSe grains were
obtained after one step annealing. The as-prepared CISSe thin films were successfully applied to
solar cells and a energy conversion efficiency of 6.75% was achieved. This facile preparation provides a
low-cost and easy method to fabricate Cu-based thin film solar cells.

1. Introduction such as bad atomic stoichiometry control because of the wide

Cu-based chalcopyrite is one of the most important light
absorber materials for thin film solar cells due to high absorp-
tion coefficients, good photo durability and a desired band gap
range. These materials include CuInS2 (CIS), CuInSe2 (CISe),
CuIn(S,Se)2 (CISSe) and Cu(In,Ga)Se2 (CIGS) with record photo-
voltaic efficiencies of 12.5% (CIS) and 20.4% (CIGS) in lab.1,2
However, the deposition of Cu-based absorbers by the vacuum-
based methods (e.g. sputtering3,4 and co-evaporation5–7) involves
highcost and produces a lowyield, which hinders mass-production
of large-area solar cells.
Non-vacuum solution-based deposition methods possess the
advantages of simplicity, high throughput and inherent low invest-
ment requirements. So far, promising conversion efficiencies
(410%) have been achieved.8,9 Solution-based deposition
techniques include nanoparticle ink-based techniques,10–12
electrochemical depositions,13–15 pure precursor solution
methods,16–18 etc. While nanoparticle ink-based techniques
usually involve complicated synthesis and purification processes,
electrochemical depositions also have significant drawbacks
a
CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of
Ceramics, Chinese Academy of Sciences, Shanghai 200050, P.R. China.
E-mail: liuyf@mail.sic.ac.cn, huangfq@mail.sic.ac.cn; Fax: +86-21-52416360
b
State Key Laboratory of Rare Earth Materials Chemistry and Applications, College
of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c4cp00045e
differences in the standard potentials of Cu, In, Ga and Se.19
In contrast, pure precursor solution methods generally provide
a high yield, are simple in the scale-up process, and have
precise stoichiometry control at the molecular scale.20,21 The
hydrazine-based solution method has been successfully used to
fabricate high-efficiency thin film solar cells because of the
excellent ability of the solution to dissolve metal chalcogenides
such as Cu2S and In2S3,9,22–24 Nevertheless, the highly toxic and
explosive hydrazine is a barrier for the mass production of those
films. It is essential to develop a facile, green and low-cost method
to prepare an air-stable precursor containing Cu, In and S
(and/or Se), which is an important direction for the current
non-vacuum CISSe-based solar cells.
In this paper, we proposed a thioacetic acid-based solution
method to fabricate CISSe thin films. The raw materials copper(I)
oxide and indium(III) hydroxide were found for the first time
to be dissolved in a thioacetic acid-based solution with the
assistance of ammonia. Compared with other metal sources
(metal chloride, nitrate, etc.), using Cu2O and In(OH)3 could
lead to pure CISSe films without introduction of impurity
anions like Cl, N, etc. In addition, thioacetic acid was stable
enough to operate without inert gas protection, and it can be
easily removed completely by heating (boiling point, 93 1C), leading
to no carbon residue. A sulfide raw film was formed before
annealing with thioacetic acid as the sulfur source, avoiding the
long annealing time25 or usage of explosive H226 which was required
in the annealing process for oxide raw films. More importantly,

7548 | Phys. Chem. Chem. Phys., 2014, 16, 7548--7554 This journal is © the Owner Societies 2014

Paper
the metal ion and thioacetic acid form stable and soluble metal
complexes owing to the strong coordination ability of thioacetic
acid. Above all, thioacetic acid was an ideal sulfur source and
essential ligand in the precursor. The preparation process of the
precursor was simple and secure without heating, centrifugation20
and inert gas shielding.27 All processes could be operated in air
using the safe and stable precursor. Small molecule organic
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solvents (isopropanol, ethylene glycol, propylene glycol, etc.) could
be easily evaporated, leading to a low carbon content in the final
films. The starting materials were commercially available and
cheap, further lowering the cost. Uniform and compact CISSe thin
films with good crystallization and large grains can be obtained
through this facile solution-based method. The CISSe thin film
solar cells were successfully assembled and a conversion efficiency
of 6.75% was achieved.
2. Experimental
2.1. Precursor solution preparation
All chemicals were used as received without further purifica-
tion. 0.8 mM of copper(I) oxide (Cu2O, analytical grade) and
2 mM of indium(III) hydroxide (In(OH)3, 98%) (Cu/In = 0.8) were
added to a solvent mixture of 6 mL isopropanol (C3H8O,
analytical grade), 1 mL ethylene glycol (C2H6O2, analytical grade)
and 1 mL propylene glycol (C3H8O2, analytical grade). After stirring
for a few minutes, 2 mL of thioacetic acid (CH3COSH, 93%) was
added, and the color of the suspension turned from dark white
to black. Then ammonia was added into the suspension under
continuous stirring at room temperature until an orange-red,
clear precursor solution was obtained. The other two precursor
solutions with a Cu/In of 0.9 and 1.0 were also prepared under
identical conditions for comparison.
2.2. Deposition of CISSe thin films
The CIS thin films were deposited via a spin-coating method
from the as-prepared precursor solution on a fluorine-doped tin
oxide (FTO) transparent conducting glass or molybdenum-coated
soda-lime glass (SLG) substrates. Each layer was spin-coated at
1500 rpm for 20 seconds and subsequently dried on a heating
plate at 300 1C for 3 minutes to evaporate the organic solvents.
Spin-coating and drying processes were performed several times
until the desired thickness was obtained. Finally, the CISSe thin
films were formed through one step sulfuration and selenization
at 500 1C for 30 minutes in a graphite box annealing system
with H2S gas and some elemental Se powders.
2.3. Device fabrication
CISSe-based thin film solar cells were fabricated with the
structure of glass/Mo/CISSe/CdS/i-ZnO/Al-doped zinc oxide
(AZO)/Ag. The Mo layer was deposited onto the SLG substrate
by direct current (DC) planar magnetron sputtering. The
B60 nm thick CdS buffer layer was deposited on the CISSe
layer by chemical bath deposition (CBD). Then i-ZnO (B60 nm)
and AZO (B800 nm) layers were deposited by radio frequency
(RF) magnetron sputtering on top of a CdS layer as the buffer
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Fig. 1 Scheme of the preparation process of CISSe thin films and CISSe
thin film solar cells.
layer and a transparent conduct electrode (TCO). The Ag grid
electrodes were deposited by DC planar magnetron sputtering.
The solar cell area was then calculated to be 0.4 cm2
by mechanical scribing. Fig. 1 illustrates the whole process
including deposition of CISSe thin films and fabrication of
CISSe solar cells.
2.4. Characterization
The crystalline and phase identification of the CISSe thin films
was performed by X-ray diffraction (XRD Bruker D8 Focus)
using a monochromatized source of Cu Ka1 radiation (l =
0.15405 nm) at 1.6 kW (40 kV, 40 mA). Raman spectra were
recorded on a Thermal Dispersive Spectrometer using a laser
with an excitation wavelength of 532 nm at a laser power of
10 mW. UV-vis absorbance spectra were recorded from 500 to
2000 nm on a Hitachi U-3010 spectrophotometer with a scanning
velocity of 300 nm min 1. Top-view field emission scanning
electron microscopy (FESEM) images were acquired using a FEI
Sirion 200 by energy dispersive X-ray (EDS) analysis. Cross-sectional
FESEM images were acquired using a Hitachi S-4800 by EDS
analysis. The energy conversion efficiency of solar cells was
measured using a Keithley Model 2440 source meter under AM
1.5 illumination. The external quantum efficiency (EQE) was
measured using a Newport QE system equipped with a 300 mW
xenon light and a lock-in amplifier.
3. Results and discussion
3.1. Dissolution mechanism
A facile thioacetic acid-based solution method to fabricate
CISSe thin films was proposed. Thioacetic acid was always
used in organic reactions but seldom applied for synthesis of
inorganic sulfide.28–30 In this work, thioacetic acid was a special
constituent which assisted the dissolution of Cu2O and In(OH)3.
The S in thioacetic acid had a strong coordination ability to
coordinate with metal ions and form soluble and stable metal
complexes. However, a sulfide precipitate rather than a clear and
transparent precursor was formed when thioacetic acid was
added alone. So addition of alkali (NaOH, ammonia or amines)
was necessary to obtain the precursor solution. The alkali can
draw off the H of –SH to exhibit the strong coordination ability
of S. In our study, ammonia was chosen because it could be
eliminated easily. The N in ammonia was not considered as the
dominant ligand to coordinate with metal ions because the
Phys. Chem. Chem. Phys., 2014, 16, 7548--7554 | 7549

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dissolution could be achieved by adding NaOH instead of
ammonia. The dissolution procedure is shown below:
The dissolution process could be finished in five minutes under
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continuous stirring at room temperature. The precursor could be
directly used for spin-coating without any post-treatment and
was stable for more than 3 months in air at 4 1C, indicating its
long-term stability.
3.2. Structural analysis
XRD analysis was performed to verify the crystallization of the
as-prepared CIS and CISSe thin films on FTO glass. Fig. 2a
shows the XRD patterns of thin films annealed at different
temperatures with a Cu/In ratio of 0.8. The observation of
characteristic peaks of CIS with weak intensity and a broad
shape indicated the formation of the CIS phase even before
annealing.25,26 The crystallization increased slightly after
annealing at 300 1C, and without an obvious increase after
annealing at 400 1C. The diffraction peaks rarely shifted to a
lower theta value, which indicated that Se vapor hardly reacted
Fig. 2 (a) XRD patterns and (c) Raman spectra of the CIS raw film and CISSe films annealed at different temperatures for 30 minutes. (b) XRD patterns and
(d) Raman spectra of CISSe films with different Cu/In ratios after annealing at 500 1C for 30 minutes. JCPDS files: CuInS2 (85-1575), SnO2 (88-0287).
7550 | Phys. Chem. Chem. Phys., 2014, 16, 7548--7554
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with the CIS raw film and a few of the Se atoms replaced S
atoms in the crystalline lattice of CIS below 400 1C. When the
annealing temperature was increased to 500 1C, the intensity
of XRD peaks of the CISSe phase increased significantly,
indicating the formation of the CISSe thin film with good
crystallization. Meanwhile, the diffraction peaks systematically
shifted to lower theta values compared with CIS since Se
substituted for S in adequate amount. The XRD patterns of
CISSe films with diverse Cu/In ratios annealed at 500 1C are
shown in Fig. 2b. All of the diffraction peaks could be assigned
to the CISSe phase without any detection of the impurity peak.
Raman spectroscopy was used to further investigate the
composition of CISSe thin films. The Raman spectra of the
as-obtained CIS and CISSe thin films annealed at different
temperatures with a Cu/In ratio of 0.8 are shown in Fig. 2c.
The peak at 300 cm 1 with a shoulder at around 328 cm 1 of
the as-obtained CIS thin film could be assigned to the typical
molecular vibration of CIS.28 The full width at half maximum
(FWHM) of the peak was comparatively wide, which was
probably caused by the low crystallization of the CIS thin film,
consistent with the XRD result.31 After annealing at 300 1C, a
relatively weak peak appeared at 194 cm 1 in addition to the
vibration of CIS, suggesting the formation of CISSe, as the peak
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Table 1 Cu/In ratio at each processing step, measured by EDS
Precursor solution (calculated) Raw film Annealed at 500 1C
0.80 0.74 0.76
0.90 0.88 0.87
1.00 0.98 0.98
position was located between that of CIS at 300 cm 1 and CISe at
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179 cm 1. After annealing at 400 1C, the peak intensity was
enhanced with position shifting from 194 cm 1 to 199 cm 1,
indicating an increased Se/S ratio in the annealed thin film. When
the annealing temperature increased to 500 1C, the typical Raman
peak of CISe was found at 179 cm 1 with a shoulder at around
214 cm 1. Additionally, one small peak at 295 cm 1, near the peak
at 300 cm 1 of CIS, indicated the formation of CISSe thin films.
The high intensity with narrow FWHM of the peak at 179 cm 1
showed the good crystallization of the annealed thin film,
consistent with the XRD result as well. Considering the stronger
peak intensity of CISe at 179 cm 1 with the weaker peak intensity
of CIS at 295 cm 1, the Se content was much more than the S
content in the annealed CISSe thin films. Furthermore, a weak
peak near 258 cm 1 should come from copper selenide15 at an
annealing temperature below 400 1C, suggesting the appearance
of copper selenide at low temperature. However, this weak peak
disappeared and no other signal of copper sulfides and selenides
was detected when the annealing temperature reached 500 1C. As
shown in Fig. 2d, copper selenide could still be detected for CISSe
thin films deposited with Cu/In ratios of 0.9 and 1.0 solution after
annealing at 500 1C, and the peak intensity of copper selenide
increased with the increasing Cu/In ratios. As we can see from
Fig. S1 (ESI†), copper selenide was formed after the low tempera-
ture annealing process, the same as that observed in the case of a
Cu/In ratio of 0.8. Therefore, the residual copper selenide phase in
CISSe films probably resulted from the copper selenide that arose
at an early stage of the annealing process and could not be
eliminated to form a single CISSe phase after annealing at 500 1C.
3.3. Composition and optical band gap
EDS was used to measure the content of elements in thin films.
Table 1 summarizes the changes in the Cu/In ratios at each
Fig. 3 (a) Cu/In ratio and Eg variation in CISSe thin films annealed at 500 1C as a function of the composition of Cu, In precursor solution (molar ratio of
Cu2O to In(OH)3). (b) S/(S + Se) ratio and Eg variation in CISSe thin films (Cu/In = 0.8 in precursor solution) as a function of the annealing temperature.
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processing step with different Cu/In ratios in the precursor
solution. However, the Cu/In ratios in CISSe thin films were
a little less than that in the precursor solution. Given that the
Cu/In ratios in CIS raw thin films were almost the same as that
of the annealed CISSe thin films, this loss of Cu might be
caused by the formation of volatile Cu-organic species in the
precursor solution which were volatilized in the spin-coating
process.25 As shown in Fig. 3a, the Cu/In ratios in annealed
CISSe thin films could be effectively adjusted by controlling the
Cu2O and In(OH)3 components in the precursor solution.
As calculated from the UV-vis absorption measurements
(Fig. S2, ESI†), the band gap Eg of CISSe thin films annealed
at 500 1C could be slightly adjusted by the Cu/In ratios (Fig. 3a).
The Eg values of CISSe thin films deposited from the precursor
solution with Cu/In ratios of 0.8, 0.9, and 1.0 were 1.18 eV,
1.14 eV, and 1.09 eV, respectively.
Otherwise, the S/(S + Se) ratios in CISSe thin films (Cu/In =
0.8 in the precursor solution) decreased with increasing
annealing temperature, as shown in Fig. 3b. When the anneal-
ing temperature was below 400 1C, the S content accounted for
more than 50% in CISSe thin films. The relatively high Se
content (440%) could be originated from the copper selenide
and preliminary formation of the CISSe phase, suggested by the
XRD and Raman results. The S content decreased obviously
after annealing at 500 1C, which could be attributed to the
substitution of Se with S in the crystalline lattice and the
formation of the CISSe phase. The band gap Eg of the annealed
thin films changed with the annealing temperature, namely the
S/(S + Se) ratios. As the annealing temperature increased, the Eg
decreased from 1.42 eV to 1.18 eV due to the increasing
Se content in thin films (Eg of CuInS2: 1.52 eV, Eg of CuInSe2:
1.04 eV), as shown in Fig. 3b.
3.4. Absorber morphology
The morphology of as-prepared CISSe thin films was studied by
FESEM. The top-view FESEM images of CISSe films with a Cu/In
ratio of 0.8 annealed at different temperatures are shown in
Fig. S3 (ESI†). No grain was formed and the surface appeared
amorphous in the CIS raw film. When the annealing temperature
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as a flux agent in the annealing process.33 The cross-sectional

FESEM image of the CISSe thin film with a Cu/In ratio of 0.8
annealed at 500 1C is shown in Fig. 4d. The thickness of the
CISSe thin film was about 1 mm and relatively large grains were
obtained. Quite large grains were observed from cross-sectional
images of CISSe films with Cu/In ratios of 0.9 and 1.0, as shown
in Fig. S4 (ESI†). Based on the elemental profile of the CISSe
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thin film shown in Fig. S5 (ESI†), no gradient distribution of all

elements in the depth profile was observed. The carbon content
was very low (Fig. S5, ESI†) in CISSe thin films,16,34 which was a
benefit of the easy evaporation of all the small molecule
solvents. Grain growth was not hampered by such low carbon
content therefore a large grain size layer was formed without
formation of the residual carbon layer.

Fig. 4 Top-view FESEM images of CISSe films annealed at 500 1C for 3.5. Prototype device
30 minutes with different Cu/In ratios (a) 0.8, (b) 0.9, (c) 1.0 and (d) cross-
sectional FESEM image of CISSe film annealed at 500 1C for 30 minutes CISSe thin films with diverse Cu/In ratios annealed at 500 1C
with a Cu/In ratio of 0.8. were chosen to fabricate thin film solar cells. Solar cells were
fabricated with the structure of glass/Mo/CISSe/CdS/i-ZnO/AZO/
Ag. The device properties measured under AM 1.5 with different
Table 2 Summary of devices properties with different Cu/In ratios Cu/In ratios are summarized in Table 2, and Fig. 5a shows the
typical I–V characteristics of the best device with a Cu/In ratio of
Cu/In ratio Voc (V) Jsc (mA cm 2) FF (%) Z (%) Rs (O) Rsh (O)
0.8. The I–V characteristics of devices with Cu/In ratios of 0.9
0.8 0.443 30.39 50.23 6.75 14.7 487.5
and 1.0 are provided in Fig. S6 (ESI†). The conspicuous
0.9 0.301 26.27 33.56 2.65 23.9 92.8
1.0 0.220 26.99 36.42 2.17 13.5 62.0 decrease of shunt resistances (Rsh) with increasing Cu/In ratios
was attributable to the serious shunt paths and short circuit
caused by the conductive copper selenide phase in the absorber
was below 400 1C, small grains were observed with a grain size layer.33 As a result, the open circuit voltage (Voc),35 as well as the
smaller than 100 nm, leading to the low crystallization of the fill factor (FF), decreased significantly leading to the low
thin film. A dense and compact film was formed until the performance of the devices. On the other hand, the Voc of the
annealing temperature reached 500 1C, as shown in Fig. 4a. On best device (443 mV) was much lower than that reported by Liu
the other hand, the grain size increased with increasing Cu/In et al.,23 which may be caused by recombination through the
ratios. However, large rounded grains were formed when the interface, the space charge region or the bulk of the absorber
Cu/In ratio was higher than 0.9 (Fig. 4b), even some pores could layer.36 The relatively small band gap (low S content: 17.8%)
be found in CISSe films with a Cu/In ratio of 1.0 (Fig. 4c). These may have resulted in lower Voc as well. Composition optimiza-
rounded grains should be caused due to the low melting point tion and Ga incorporation could further improve Voc. The
(525 1C)32 of the residual copper selenide in films which acted external quantum efficiency (EQE) data of the best device

Fig. 5 (a) Current–voltage (J–V) curve of the best CISSe-based thin film solar cell with a Cu/In ratio of 0.8 under a standard AM 1.5 solar illumination at
an intensity of 100 mW cm 2. (b) EQE spectrum of the best CISSe-based thin film solar cell without any applied bias.

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(Fig. 5b) showed that the efficiency stayed at around 60% at
short to medium wavelengths (510–950 nm) and exceeded 70%
in the range of 520–660 nm. A high efficiency loss was found
below 500 nm due to the absorption of ZnO and the CdS layer.
The steepness of the long-wavelength part of the EQE curve was
by virtue of incomplete absorption in the CISSe layer near the
CISSe band gap. The thickness of the CISSe layer was only
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about 1 mm, which was half of the commonly assumed optimal
thickness of 2 mm.9 Optimizing the film thickness is an effective
way to further improve the device efficiency.
4. Conclusion
A novel and facile thioacetic acid-based solution method was
successfully applied to fabricate CISSe thin films through the
spin-coating process. No heating, vacuum conditions and cen-
trifugation were needed for the preparation of the solution
precursor. It was easy to handle the process with the low cost,
stable solution because all the thin films deposition process
could be operated in air. Thioacetic acid played an important
role in dissolving Cu2O and In(OH)3, thanks to the strong
coordination ability of S in –SH. The Cu/In ratio in the CISSe
thin films could be effectively adjusted by changing the com-
ponent of metal sources in the precursor solution. All the small
molecule organic solvents could be easily evaporated resulting
in a low carbon content in CISSe thin films. Copper selenide
was formed at an early stage of the annealing process and could
not be eliminated when the Cu/In ratio was higher than 0.8.
A conversion efficiency of 6.75% was achieved in CISSe thin
film solar cells with a Cu/In ratio of 0.8, while the presence of
copper selenide in films resulted in the bad device performance
at a Cu/In ratio above 0.9. The device efficiency could be poten-
tially improved by composition optimization, Ga incorporation
etc. The optimization of process conditions and relevant work
are ongoing.
Acknowledgements
This work was financially supported by the National 863
Program of China (Grant 2011AA050505), the National Science
Foundation of China (Grant No. 91122034, 51125006, 51121064,
61376056, 61106088, 61204072, 51102263, 61205177), and
Science and Technology Commission of Shanghai Grant (No.
12XD1406800).
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