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Solar Energy 86 (2012) 2584–2591

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The study of preparation and photoelectrical properties

of chemical bath deposited Zn, Sb and Ni-doped CuInS2 films
for hydrogen production
Edita Garskaite a, Guan-Ting Pan b, Thomas C.-K. Yang a,b,⇑, Sheng-Tung Huang a,
Aivaras Kareiva c
a
Institute of Biotechnology, National Taipei University of Technology, Taipei, Taiwan, ROC
b
Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, Taipei, Taiwan, ROC
c
Department of General and Inorganic Chemistry, Vilnius University, Vilnius, Lithuania

Received 30 December 2011; received in revised form 8 May 2012; accepted 28 May 2012
Available online 16 June 2012

Communicated by: Associate Editor S.A. Sherif

Abstract

Pure and Zn, Sb, Ni-doped CuInS2 films were prepared by chemical bath deposition method. Structural, morphological, optical, and
photoelectrochemical properties of the as-grown films were investigated. X-ray diffraction analysis revealed that films consisted of the
tetragonal CuInS2 phase. The energy band gaps and carrier densities of these samples were in the ranges of 1.48–1.54 eV and
2.38  1018–9.38  1019, respectively. The maximum photocurrent density of samples with a potential of 1.0 V vs. a Pt electrode
was found to be 8.58 mA/cm2 with the largest hydrogen production capability of 33.26 lmol/cm2 under illumination using a 300 W
Xe lamp system.
Ó 2012 Elsevier Ltd. All rights reserved.

Keywords: Photocatalysts; Electrochemical performance; Optical properties; CuInS2 crystalline

1. Introduction However, the photocatalytic activity of n-TiO2 under the vis-

The development of new energy systems based on renew-
able and clean energy sources has drawn more and more
attention due to the rise of energy consumption and the
shortage of fossil fuels. In this regards, the construction of
photochemical systems as alternative energy resources
becomes one of the solutions to thus urgent problems
(Bolton, 1996). The production of hydrogen from water-
splitting through solar irradiation on an n-type TiO2 elec-
trode was first initiated by Fujishima and Honda (1972).
⇑ Corresponding author. Address: No. 1, Sec. 3, Chung-Hsiao E. Rd.,
Taipei 106, Taiwan, ROC. Tel.: +886 2 2771 2171x2533; fax: +886 2
27760985.
E-mail address: ckyang@ntut.edu.tw (T.C.-K. Yang).
ible-light illumination has suffered low quantum efficiency
due to its high band-gap energy (3.0–3.2 eV). Since then
numerous attempts have been made to enhance photocata-
lytic efficiency and design new photocatalyst for this reaction
(Osterloh, 2007; Scaife, 1980; Zhu and Zäch, 2009). For
example, enhanced photocatalytic activity of TiO2 was dem-
onstrated by codoping with transition metal ions (Colon
et al., 2006; Ishii et al., 2004; Kato and Kudo, 2002; Koh
et al., 2009; Maruska and Ghosh, 1978).
SrTiO3 and (AgIn)xZn2(1x)S2 semiconductor materials
were also verified as visible-light responsive photocatalysts
due to their small band-gap values (1.77–2.40 eV). Their
hydrogen production rates were found as 34 lmol h1 and
35 lmol h1, respectively (Ishii et al., 2004; Tsuji et al.,
2004). Furthermore, CuInS2 and other metal sulfates were

0038-092X/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.solener.2012.05.031
 E. Garskaite et al. / Solar Energy 86 (2012) 2584–2591
suggested as potential catalysts for photochemical water
splitting because of their small band gaps (0.8–2.0 eV) that
allow absorption of visible light. Tsuji et al. demonstrated
that I–III–VI2/ZnS photocatalysts inherit outstanding
capacity in hydrogen generation from aqueous solutions
2
containing sacrificial reagents (SO2 3 and S ) under the vis-
ible-light irradiation (Tsuji et al., 2005). The H2 evolution
rate was reported to be 8.2 L/h m2 from irradiated area of
33 cm2.
The separation of gas products (hydrogen and oxygen)
and the recycling of the powder catalysts in the production
of hydrogen from the catalytic splitting of water by solar
irradiation (Momirlan and Veziroglu, 2002; Stamatis,
1974) are difficult to manage in large-scale operations.
Instead of using powders, films for photocatalytic elec-
trodes provide an easier and more efficient way to generate
and collect hydrogen. Furthermore, p-type semiconductors
normally inherit stronger corrosive resistance since they are
cathodically protected under light illumination when com-
pared with that of n-type semiconductors (Khaselev and
Turner, 1998).
CuInS2, in addition to its potential applications as pho-
tocatalyst, is also one of the most promising polycrystalline
materials for solar cell applications. Due to its near opti-
mum band gap value of 1.42 eV and high absorption coef-
ficient, it is considered as a light absorbing layer for solar
cells (Gurinovich et al., 1998; Jayadevan and Tseng,
2005; Kuo et al., 2009; Li et al., 2012; Syrbu et al., 1998).
It can also be considered as an n-type film when incorpo-
rated with CuInS2/CdS, CuInSe2/CdS heterojunction solar
cells. Therefore, because of the functionality and broad
applicability of this semiconductor material, the efforts in
the preparation of CuInS2 thin films and their associated
photochemical properties are greatly needed.
A variety of different methods and their modifications
have been used to produce CuInS2 films, such as electrode-
position (Whang et al., 2009), sulphurization (Bandy-
opadhyaya et al., 2000), thermal evaporation (Schlenker
et al., 2005), spray deposition (Roncallo et al., 2010) and
solution growth techniques (Pan et al., 2008; Park et al.,
2010; Zhou et al., 2011). Among them, the chemical bath
deposition (CBD) process as a wet chemical approach
shows several advantages, such as good controllability
and reproducibility, low temperature processability and
higher uniformity of the final products (Mitzi, 2009).
In this work Zn, Sb and Ni-doped CuInS2 films were
deposited on indium-doped tin oxide (ITO) coated glass
from acidic aqueous solutions by CBD. Additionally,
structural, optical, and photoelectrochemical properties
of the as-grown films were investigated.
2. Experimental
2.1. Materials
Copper chloride (CuCl22H2O), indium chloride (InCl3),
thioacetamide (CH3CSNH2, TAA), zinc nitrate (Zn(NO3)2),
2585
antimony (III) chloride (SbCl3) and nickel (II) nitrate hexa-
hydrate (Ni(NO3)26H2O) were used as the sources of Cu2+,
In3+, S2-, Zn2+, Sb3+ and Ni2+ ions, respectively. In this
study triethanolamine (C6H15NO3, TEA) was used as a com-
plexing agent and ammonium nitrate (NH4NO3) as a buffer.
All reagents and organic solvents were analytical grade, pur-
chased from Sigma–Aldrich (St. Louis, USA) or Acros
Organics (New Jersey, USA).
2.2. Fabrication of films by CBD
Reaction solutions were formed by first mixing the 0.4 M
CuCl22H2O, 0.4 M InCl3 and 0.4 M TAA aqueous solutions
in appropriate volumes to obtain the molar ratios of 1:1:2 for
Cu:In:S. Next, 7.4 M TAA and 0.4 M NH4NO3 solutions
were added to the mixtures to form copper and indium com-
plexes. In order to avoid a formation of hydroxide-com-
plexes, the 18 M sulfuric acid then was titrated into the
mixtures by adjusting pH value to 1.36. The temperature of
bath solution was kept constant at 80 °C. In a following step,
various volumes of 0.4 M Zn(NO3)2, SbCl3 or Ni(NO3)2
6H2O aqueous solutions were added to the mixtures when
doping was performed. The volume of each reaction solution
used for producing films was 20 ml and the deposition time of
48 h. Deposited films were further analyzed without any
additional annealing. The molar ratios of metal ions in the
reaction solutions are presented in Table 1.
The indium doped tin oxide (ITO) glass plates (Pilkington,
USA) with sheet resistance of 40 X cm were used as sub-
strates. The deposition of films on the conducting glass is
essential for the electrochemical measurements. The sub-
strates were cleaned in acetone, deionized water and 96% eth-
anol under sonication for 90 min before producing the films.
2.3. Characterization of deposited films
X-ray diffraction (XRD) was performed on a PANalyti-
cal X’Pert PRO diffractometer using Cu Ka (k = 1.5405 Å)
radiation. The morphology and elemental composition of
the deposited films were investigated using a Hitachi S-
3000H scanning electron microscope (SEM) equipped with
an energy dispersive X-ray spectrometer (EDX), and high
magnification images were taken with JOEL, JSAM-6500F
field emission scanning electron microscope (FE-SEM).
The samples for the morphological analysis were sputter-
coated with Au. The electron beam accelerating voltage
was 15 kV for SEM and EDX analysis. UV–Vis transmit-
tance spectra were recorded on a Perkin–Elmer Lambda
25 spectrophotometer. The thickness of the deposited films
was estimated using Mahr Perthometer S2.
2.4. Electrical property measurements
Photocurrent measurements of films were carried out in
a Pyrex electrolytic cell. The semiconductor film of CuInS2,
a Pt plate electrode (both with an average area of 1.0 cm2),
and an Ag/AgCl electrode were employed as the working,
2586 E. Garskaite et al. / Solar Energy 86 (2012) 2584–2591

Table 1 can be seen that samples made are phase pure, with no
The molar ratios of Cu/In/Zn/Sb/Ni/S ions in the reaction solutions used impurity phases such as Zn, Sb, Ni alloys or other binary
for the growth of CuInS2 films.
or ternary compounds. The characteristic diffraction lines
Samples Molar ratios of Cu/In/ located at 2h = 27.91, 32.25, 46.39, and 54.99° correspond
Zn/Sb/Ni/S in the solution bath
to the (1 1 2), (0 0 4), (2 0 4), and (3 1 2) crystallographic
CuInS2 1:1:0.0:0.0:0.0:14 planes of the tetragonal CuInS2 structure (JCPDS No.
CuInS2:Zn (1%) 1:1:0.2:0.0:0.0:14
CuInS2:Zn (2%) 1:1:0.4:0.0:0.0:14
00-047-1372), respectively. In addition, in several patterns
CuInS2:Zn (2.5%) 1:1:0.6:0.0:0.0:14 the diffraction lines located at 2h = 30.61, 36.33, 50.97,
CuInS2:Zn (3%) 1:1:0.8:0.0:0.0:14 and 61.07° were obtained. These lines match well with
CuInS2:Zn (4%) 1:1:1.0:0.0:0.0:14 the (2 2 2), (4 0 0), (4 4 0), and (6 2 2) crystallographic planes
CuInS2:Zn (4.5%) 1:1:1.1:0.0:0.0:14 of cubic bixbyite In2O3 (JCPDS No. 06-0416) and were
CuInS2:Zn (5%) 1:1:1.2:0.0:0.0:14
CuInS2:Sb (1%) 1:1:0.0:0.2:0.0:14
assigned to the ITO substrate. This was confirmed by
CuInS2:Sb (2%) 1:1:0.0:0.4:0.0:14 recording XRD pattern of uncoated ITO substrate glass
CuInS2:Sb (4%) 1:1:0.0:0.6:0.0:14 (data not presented). Also, some patterns of the deposited
CuInS2:Ni (1%) 1:1:0.0:0.0:0.2:14 films exhibit more intense peaks assigned to ITO. This fea-
CuInS2:Ni (2%) 1:1:0.0:0.0:0.4:14 ture is due to the films thickness variation which was also
CuInS2:Zn (4%) 1:1:0.0:0.0:0.6:14
confirmed by measuring the actual thickness of the depos-
ited films. The thickness of all deposited films was esti-
counter, and reference electrodes, respectively. A Cu wire
mated to be in the range of 1.38–1.89 lm and it decreases
was attached to the conducting layer of working electrode
with an increase of dopant concentration.
with silver paste, and the back contact and edges of the
Further, it is interesting to note that the intensities of
working electrode were sealed with epoxy resin. Aqueous
observed CuInS2 peaks decreased with an increase of the
K2SO3 (0.25 M) and Na2S (0.35 M) solution was used as
Zn, Sb and Ni ion concentrations in the chemical bath
electrolyte and it was degassed by purging with Argon
solution. The possible explanation is that some defects
gas (99.99% purity) before each experiment. The photocur-
formed in the crystal structures with an increase in Zn,
rent measurements under dark and illumination conditions
Sb, Ni doping, which effectively decreased the intensities
were carried out by a computer-controlled Autolab
of the tetragonal CuInS2 phase of the film. Further, a small
PGSTAT 30 potentiostat with working and counter elec-
broadening of peaks in the diffraction patterns with the
trodes. Additionally, the applied potential was scanned at
increasing Zn, Sb, Ni contents in the solution was noticed
the rate of 5 mV/s in the range of 1.0 to 1.0 V. A solar
to compare with the reference pattern. This broadening of
light was simulated by using Perkin–Elmer (PE300UV)
peaks shows that crystallite size decreasing when dopant
300 W Xe short arc lamp with an intensity of 100 mW/cm2.
content is increased and this might be explained by the fact
The Mott-Schottky plot of the grown films was mea-
that the In3+ ion was replaced by Zn2+, or Sb3+, or Ni2+
sured using computer-controlled Autolab PGSTAT 30
ion having a smaller atomic radius (Shannon, 1976) and
potentiostat equipped with an Autolab FRA2 frequency
leading to the contraction of the unit cell. Similar tendency
response analyzer. The electrolyte for the Mott-Schottky
in the particle size reduction of ZnO with the increase of Al
measurement was K2SO4 (0.5 M) solution with pH values
concentrations, due to the replacement of Zn2+ by Al3+
of 6, 8 and 10.

2.5. Hydrogen evolution

The hydrogen-production experiment was carried out

on the photo-electrode with small exposure area (1 cm2)
using a Newport M-66907 solar simulator (300 W Xe short
arc lamp). The photo-intensity was measured to be
100 mW/cm2 on the photo-electrode, and no bias voltage
was applied on the photo-electrode. The volume of evolv-
ing hydrogen was measured volumetrically and the compo-
sition of gas was confirmed by gas chromatography
(Shimadzu, GS-8A, TCD).

3. Results and discussion

3.1. Structural and surface morphology

Fig. 1. XRD patterns of CuInS2, CuInS2:Zn (1%), CuInS2:Sb (1%),
The XRD patterns of the CuInS2 and representative Zn, CuInS2:Ni (1%), CuInS2:Zn (5%), CuInS2:Sb (4%) and CuInS2:Ni (4%)
Sb and Ni-doped CuInS2 films are presented in Fig. 1. It films.
 E. Garskaite et al. / Solar Energy 86 (2012) 2584–2591
ions in ZnO crystal lattice was reported by Suwanboon
et al. (2008).
The morphological features of the CuInS2 and represen-
tative Zn, Sb and Ni doped CuInS2 films are depicted in
Fig. 2. The deposited films appear homogeneous, smooth
and dense. Other samples exhibited similar microstruc-
tures. SEM images show that when elements of Zn and
Ni were used as dopants the grain size of the order of
100–250 nm was obtained in comparison with Sb doped
CuInS2 films. Morphological differences obtained in films
can be explained by complexity of CBD process where fac-
tors such as dopant concentration and nature of dopant
play an important role for the formation of the solid prod-
uct on the substrate (Lokhande, 1991; Niesen and De
Guire, 2002).
An EDX analysis on each sample was performed to
determine the composition of the films. The atomic ratios
of [Cu]:[In]:[S]:[Zn]:[Sb]:[Ni] of all samples are in the range
of 1:0.68–0.85:1.16–1.29:0–0.05:0–0.03:0–0.04. The ratios
of In/Cu and In/S in the films decrease with increasing
Zn, Sb or Ni content. These results support the data
obtained from XRD analysis indicating that the Zn, Sb
and Ni atoms occupy some of the vacancy sites in the
CuInS2 lattice. The molar percentages of dopant in CuInS2
films estimated from the EDX analysis are presented in
Table 1.
3.2. Optical properties
The samples show 35% transmittance in visible light and
the near-infrared region (data not presented). The onset
wavelength of absorption spectra occurred at around
850 nm, corresponding to the band gap of 1.50 eV (Akaki
et al., 2003; Komaki et al., 2003). With the increase of
Zn, Sb, Ni concentration, the onset band tends to shift
slightly toward shorter wavelength, indicating that the
energy required to generate the electron–hole pairs became
higher. A similar tendency was found in the case of Ga-
doped ZnO by Kim et al. (2009) where an increase in the
band gap on ZnO was noted, with an increase of carrier
concentrations.
3.3. Electrical properties
The semiconductor and electrical property of the CBD
films was measured using the capacitance vs. applied
potential on the semiconductor-electrolyte barrier with
the Mott-Schottky equation. The Mott-Schottky equation
is given as follows:
   electrode are presented in Fig. 4. An enhancement of, the
1 2 kT
¼ B  E  E FB  ; ð1Þ
C2 ee0 eN D A2 e
where e is the dielectric constant of the semiconductor, e0 is
the permittivity of the vacuum, e is the electronic charge,
ND is the carrier density of the semiconductor, and A is
the surface area of the interface. EFB is the flat band poten-
tial of the semiconductor, which is close to the potential of
2587
Fermi level. For an n-type semiconductor, B is equal to 1,
while for a p-type semiconductor B is equal to 1. From
this relationship, EFB can be obtained from E0, the point
of intersection on the E-axis of a C2 vs. E plot:
kT
E0 ¼ EFB þ ; ð2Þ
e
Furthermore, ND can be determined if e and A are given.
This revealed the Esc or Esv , the positions of conduction and
valance band of semiconductors. The dielectric constant of
CuInS2 was 10.0 (Verschraegen et al., 2004) and the area of
interface was 1cm2 in this work.
In Table 2 the values of flat band potentials of samples
according to various deposition parameters are shown.
The flat band potentials of these samples lie in the range of
0.74 V to 0.42 V vs. normal hydrogen electrode (NHE)
(0.76 V to 0.22 V vs. an Ag/AgCl electrode) for n-type
compound, and 0.43 V to 0.49 V vs. NHE (0.23 V to
0.70 V vs. an Ag/AgCl electrode) for p-type compound.
Also, flat band potentials of samples investigated become
more positive when concentration of Zn, Sb and Ni increases
in solution bath. The values of carrier density of samples cal-
culated from the Mott-Schottky plots are also presented in
Table 2. When Zn, Sb and Ni molar ratios in the solution
bath were higher than 0.6, 0.4, 0.4, respectively, the slopes
of the straight lines in Mott-Schottky plots turned from
the positive values to the negative ones, indicating that the
semiconductor property of the films was changed from n-
type to p-type. The values of carrier densities of the samples
are found in the range of 2.92  1018–4.37  1019 cm3.
Also, the carrier densities tend to increase with an increasing
molar ratio of Zn, Sn or Ni. The carrier effective mass of
CuInS2 is 1.0 m0, where m0 is the mass of electron (Gon-
zález-Hernández et al., 2002).
Fig. 3 shows the photocurrent density curves of the n-type
CuInS2 films with applied potential between 1.0 and 1.0 V
vs. the Pt electrode. It is noticeable that the photocurrent
densities of the undoped CuInS2 and CuInS2:Sb (2%)
reached to 4.18 and 6.22 mA/cm2 at the external potential
+1.0 vs. a Pt electrode, respectively. In addition, the occur-
rence of the photocurrent on the positive potential repre-
sents a remarkable characteristic of an n-type
semiconductor. As well, photocurrent density of n-type
CuInS2 decreases with increasing Zn, Sb or Ni concentration
in solution. As a result, the use of CuInS2:Sb (2%) will give
more driving force in comparison with that of the undoped
CuInS2 under the same external bias.
The photocurrent density curves of the p-type CuInS2
films under a potential between 1.0 and +1.0 with a Pt
photocurrent densities from 7.29 to 8.58 mA/cm2 under
the external potential of 1.0 V with a Pt electrode was
observed for the p-type CuInS2 films. The photocurrent
occurs on the negative potentials as verified by the Mott-
Schottky plots. Additionally, the photocurrent density val-
ues of p-type CuInS2 films increased when higher molar
ratios of transition metals were present in the solution
2588 E. Garskaite et al. / Solar Energy 86 (2012) 2584–2591

Fig. 2. The SEM images of: (a) and (b) CuInS2 (low and high magnification, respectively); (c) CuInS2:Zn (1%); (d) CuInS2:Zn (5%); (e) CuInS2:Sb (4%);
and (f) CuInS2:Ni (4%). Insets in (d), (e) and (f) images show grain size of deposited films.

Table 2
The physical properties of the Zn, Sb, Ni-doped CuInS2 films.
Samples Carrier density (cm–3)a Eg (eV) ENHE
FB (V)a ENHE
CB (V) ENHE
VB (V) EVacuum
CB (V) EVacuum
VB (V) Conduction type
18
CuInS2 2.92  10 1.53 0.536 0.736 0.794 3.764 5.294 n
CuInS2:Zn (1%) 4.89  1018 1.52 0.462 0.662 0.858 3.838 5.358 n
CuInS2:Zn (2%) 7.95  1018 1.52 0.412 0.612 0.908 3.888 5.408 n
CuInS2:Zn (2.5%) 1.36  1019 1.51 0.215 0.415 1.095 4.085 5.595 n
CuInS2:Zn (3%) 4.76  1019 1.50 0.608 0.792 0.708 3.708 5.208 p
CuInS2:Zn (4%) 6.34  1019 1.49 0.733 0.657 0.833 3.843 5.333 p
CuInS2:Zn (4.5%) 8.26  1019 1.48 0.795 0.585 0.895 3.915 5.395 p
CuInS2:Zn (5%) 9.35  1019 1.48 0.815 0.565 0.915 3.935 5.415 p
CuInS2:Sb (1%) 5.23  1018 1.52 0.437 0.637 0.883 3.863 5.383 n
CuInS2:Sb (2%) 9.95  1018 1.51 0.350 0.550 0.960 3.950 5.460 n
CuInS2:Sb (4%) 4.66  1019 1.50 0.226 0.426 1.074 4.074 5.574 p
CuInS2:Ni (1%) 4.83  1018 1.51 0.366 0.566 0.944 3.934 5.444 n
CuInS2:Ni (2%) 8.62  1018 1.51 0.228 0.428 1.082 4.072 5.582 n
CuInS2:Ni (4%) 4.37  1019 1.50 0.701 0.689 0.801 3.811 5.301 p
a
Calculated from the Mott-Schottky plots.

bath. Since the flat band potential of the CuInS2:Zn (5%) is
more positive than the other p-type samples, the energy
potential of holes (at the valance band) for sample
CuInS2:Zn (5%) is the lowest among the prepared samples
under same external bias. As a result, the magnitude of
applied bias to sample CuInS2:Zn (5%) is the largest among
all p-type samples. Consequently, the largest photocurrent
density was observed on sample CuInS2:Zn (5%) under the
same external negative potential.
Fig. 5 shows the time-dependent hydrogen evolution per-
formance of the CuInS2, CuInS2:Sb (4%), CuInS2:Ni (4%)
and CuInS2:Zn (5%), samples in K2SO3 (0.25 M) + Na2S
 E. Garskaite et al. / Solar Energy 86 (2012) 2584–2591 2589

36
6
CuInS2
32
5 CuInS2:Zn (1%)

Evolved H2 (µ mol/cm2 )
CuInS2
Photocurrent (mA/cm )

28
2

CuInS2:Zn (2%) n-type films

4 CuInS2:Zn (5%)
CuInS2:Zn (2.5%) 24 CuInS2:Sb (4%)
3 CuInS2:Sb (1%) CuInS2:Ni (4%)
20
CuInS2:Zn (2%)
2 16
CuInS2:Ni (1%)
1 CuInS2:Ni (2%)
12
0 8

-1
Electrolyte: aqueous K 2 SO4 (0.25M) + Na2S (0.35M) solution
-2
-1.00 -0.75 -0.50 -0.25 0.00 0.25 0.50 0.75
Applied voltage (V vs. Pt electrode)
Fig. 3. The plot of photocurrent density versus applied voltage in the
range from 1 to +1 V vs. an Pt electrode for n-type CuInS2:Zn,Sb,Ni
films.
(0.35 M) aqueous solution, under the irradiation of a 300 W
Xe lamp. The maximum value of 33.26 ml/cm2 of hydrogen
evolution was obtained on the CuInS2:Zn (5%) film, while
for the undoped CuInS2 the hydrogen evolution obtained
was of 16.42 ml/cm2. Accordingly, the highest activity value
for the Sb and Ni-doped films was 30.47 ml/cm2 and
28.66 ml/cm2, respectively, where doping of 4% was
obtained. The increase of electrical conductance was mainly
attributed to the donor-type defects through the substitution
of Zn atoms in In sites of crystal lattice.
The consistency on the order of electric conductance and
the photocatalytic activity was based on the assumption
that Zn as a good conductor will effectively reduce the
recombination rate of the electrons and holes and thus
extend the lifetime of the exciting state. As a result, the pho-
tocatalytic performance was enhanced. Similar results were
also reported by He et al. (2009) that the better photocata-
lytic reactivity was found in the samples of TiO2 with the
6 et al., 1999). Therefore, based on our observations we are
4
p-type films
Photocurrent (mA/cm )
4
0
0 60 120 180
1.00
Time (min)
Fig. 5. Photocatalytic H2 evolution on CuInS2, CuInS2:Zn (5%),
CuInS2:Sb (4%) and CuInS2:Ni (4%) films.
graphite intercalation. Furthermore, Yang et al. (2012)
recently reported that CdS with small amount of Zn doping
also leads to an enhanced photocatalytic activity and stabil-
ity improvement of synthesized material. Authors indicated
that Zn doping into a CdS crystal lattice can result in the
shift of the valence band of CdS to a positive direction,
which may lead to its higher oxidative ability than pure
CdS.
In addition, it has to be mentioned that obtained electri-
cal conductivity and hydrogen evolution characteristics of
deposited films can also be affected by the obtained actual
doping concentration and different microstructural charac-
teristics. EDX analysis showed that under the same depo-
sition procedure the highest doping concentration was
attained for the Zn doped samples in comparison with that
of Ni and Sb. It has been reported by Ben Rabeh et al.
(2009) that an increase of Zn concentration in CuInS2 host
leads to the higher conductivity. Furthermore, the SEM
analysis showed that higher grain size was obtained for
the Zn and Sb doped samples than for the Ni doped sam-
ples, which leads to the higher electron mobility (Kulkarni
currently designing new experiments where the factors such
as degree of saturation and particle nucleation rate are

taken into consideration. We further aim to obtain narrow

2

2
particle size distribution and investigate how variations of
0 it affect the hydrogen evolution performance of currently
CuInS2:Zn (3%)
proposed films.
-2 CuInS2:Zn (4%)
CuInS2:Zn (4.5%)
-4 CuInS2:Zn (5%) 4. Conclusions
CuInS2:Sb (4%)
-6 CuInS2:Ni (4%) Pure and Zn, Sb, Ni-doped CuInS2 films having tetrago-
-8 Electrolyte: aqueous K 2 SO4 (0.25M) + Na 2S (0.35M) solution
nal crystal structure were deposited on ITO-coated glass
substrates using a CBD method. Grown films possess elec-
-1.00 -0.75 -0.50 -0.25 0.00 0.25 0.50 0.75 1.00 trical properties of n-type and p-type semiconductors and a
Applied voltage (V vs. Pt electrode) conductivity type is changed from n-type to p-type when
Fig. 4. The plot of photocurrent density versus applied voltage in the molar ratios of Zn, Sb or Ni in the solution bath are higher
range from 1 to +1 V vs. an Pt electrode for p-type CuInS2:Zn,Sb,Ni than 0.6, 0.4, 0.4, respectively. Band gap energies were
films. calculated to be between 1.50–1.53 eV and carrier density
2590 E. Garskaite et al. / Solar Energy 86 (2012) 2584–2591
values from 2.92  1018 to 4.37  1019 cm3. The flat band
potentials of grown films lie in the range of 0.74 V to
0.42 V vs. NHE for n-type, while in the range of
0.43 V to +0.49 V for p-type semiconductor films. From
all of the samples investigated the Sb-doped CuInS2 exhibit
the maximum photocurrent density with value of
8.58 mA/cm2 (with an external potential set at 1.0 V)
under photon flux of 100 mW/cm2. The maximum hydro-
gen evolution obtained in this study was 33.26 ml/cm2 of
p-type Zn-doped CuInS2 films. The outstanding electro-
chemical performance of these semiconductor films might
assure their future applications in a water splitting reaction.
Acknowledgements
The financial support from the National Science Council
of ROC (NSC 100-2923-E-027-003-MY3) for Taiwan-Lat-
via-Lithuania Cooperation Project is gratefully appreci-
ated. The authors would like to thank Mr. Yeng-Ting
Wu and Hung-Chang Chen for his assistance in the sample
preparation.
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