ES Mater. Manuf., 2020, 10, 22-28
2 2 | ES Mater. Manuf., 2020, 10, 22-28 © Engineered Science Publisher LLC 2020
Effect of Copper Content on Structural, Morphological,
Optical and Photoelectrochemical Properties of SILAR
Deposited Cu3SnS4 Thin Films Harshad D. Shelke,1 Abhishek C. Lokhande,2 Jin H. Kim3 and Chandrakant D. Lokhande4,*
Abstract
In this study, Cu3SnS4 (CTS) thin films were deposited by successive ionic layer adsorption and reaction (SILAR) method at
room temperature. X-ray diffraction, Raman spectroscopy, scanning electronic microscopy, Ultra-violent-visible-near infrared
absorbance spectroscopy and photoelectrochemical analyses were used to follow the evolution of the investigated properties.
The results outlined a tetragonal (I-42m) CTS phase and a secondary copper sulfide (Cu2-xS) and Cu4SnS4 phase, and their
ratio strongly depends on the copper concentration. No traces of secondary phases of tin sulfide is found while CTS was
obtained. It was found that the application of additional Cu concentration increases from 0.025 to 0.075M, enhances the grain
growth in size and induces significant improvement of CTS crystallinity and power conversion efficiency. The optical band
gap ranges between 1.90, 1.21 and 1.07eV depending on the copper concentration 0.025, 0.050 and 0.075 M, respectively. This
study shows promising results, as a developing photovoltaic applications, using SILAR CTS as absorber.
Keywords: Band gap; Cu3SnS4; Optical properties; Molarity; Nanocrystals.
Received: 8 August 2020; Accepted date: 8 November 2020.
Article type: Research article.
1. Introduction
Last few decades, the copper based multinary compound
semiconductor materials are used as absorber materials in
photovoltaic technology.[1] Cu2ZnSnS4 (CZTS) has been
regarded as the alternative absorber layer to Cu(In,Ga)Se2 due
to its earth abundance and eco-friendly ingredients, optimal
direct band gap of 1.45 eV and high absorption coefficient in
the visible range.[2] But compositional control and growth of
single phase CZTS films are quite difficult to be processed.
The control of composition and phase structure in Cu3SnS4
compound is more convenient due to its fewer elements
compared with CZTS.
In particular, copper-based CuxSnSy, including Cu2SnS3,
Cu3SnS4, Cu4SnS4, Cu2Sn3S7, Cu5Sn2S7, etc., is an ideal
candidate material for solar cell and photocatalysis
applications owing to its high photocatalytic activities towards
hydrogen evolution, high absorption coefficient (>104 cm-1) in
the visible spectral range and proper band gap order (0.93 to
1.35 eV).[3-6] Currently, Cu3SnS4 (CTS) based ternary
semiconductors have grown more interests as significant
ternary I-IV-VI group semiconductors with diminutive or mid
band gap. Eco-friendly, low cost and non-toxic nature of CTS
similar to that of CZTS material has fascinated immense
attention due to its wide-ranging applications in photovoltaic
devices. The renewable energy resources necessitate to use
new materials in optoelectronic applications. In recent period,
CTS has received rising consideration as a promising
photovoltaic material for scalable production of thin film solar
cells because of its non-toxic and earth abundant elements, and
a tunable direct band gap of 0.9 to 1.5eV.[7] As for the synthesis
methods of CTS compound, a few studies have been reported
on chemical methods such as chemical bath deposition
(CBD),[8] electrodeposition,[9] successive ionic layer
adsorption and reaction (SILAR),[10] ball milling,[11]
solvothermal,[12] etc.
Among these chemical methods, SILAR is a simple, less
expensive and less time consuming method for the deposition
of semiconductor thin films. In SILAR method, sufficient
reaction time favors the complete chemical reaction and hence
produces pure phase compounds without secondary phases. In
the present work, CTS thin films have been synthesized by the
SILAR method. There are only a few reports existing for the
deposition of CTS thin films using the SILAR method. The
ES Materials and Manufacturing DOI: https://dx.doi.org/10.30919/esmm5f922
1 Thin Film Physics Laboratory, Department of Physics, Shivaji
University,
Kolhapur-416 004 (M.S.), India. 2 Department of Physics, Khalifa University of Science and
Technology, P.O. Box-127788, Abu Dhabi, United Arab Emirates
(UAE) 3 Optoelectronic Convergence Research Centre, Department of
Materials Science and Engineering, Chonnam National University,
Gwangju 500-757, South Korea. 4,* Centre for Interdisciplinary Research, D. Y. Patil University,
Kolhapur-416 006 (M.S.), India.
Email: [email protected] (C. Lokhande)
ES Materials & Manufacturing Research article
© Engineered Science Publisher LLC 2020 ES Mater. Manuf., 2020, 10, 22-28 | 23
aim of this present work is showing the effects of the material
composition (such as copper content) on the structural,
morphological, optical and electrical properties of CTS thin
films.
2. Experimental
2.1 Synthesis of CTS material
CTS thin films were deposited on ultrasonically cleaned soda
lime glass (SLG) and fluorine doped tin oxide (FTO)
substrates by the SILAR method. The chemical approach was
applied to synthesize CTS thin films. The mixed solution of
copper chloride (CuCl2.2H2O), tin chloride (SnCl2.2H2O) and
triethanolamine (TEA) was used as the cationic precursor and
sodium sulfide (Na2S.xH2O) solution was used as an anionic
precursor. In the deposition process of CTS, triethanolamine
solution was used as a complexing agent to bind metal cations
in the solution. The CTS precursor solution contained copper
chloride (0.025-0.075 M), tin chloride (0.025 M) and sodium
sulfide (0.1 M).
In the SILAR method, the substrate was immersed into
separate cationic and anionic precursor solutions for the
adsorption and reaction, and then rinsed with double-distilled
water (DDW) after each immersion to remove the loosely
bound particles and to avoid the precipitation. By repeating the
cycle described above, the CTS thin film with the desired
thickness was obtained by adjusting the preparative
parameters. These films were annealed for 3 hours at 300 °C
in a vacuum to improve the crystallinity. The CTS films were
well adherent, uniform and blackish in color.
To study the effect of copper salt concentration on the
formation of CTS films, copper chloride in the solution varied
from 0.025 - 0.075 M in the steps of 0.025 M. These samples
were further used for structural, morphological, optical and
photoelectrochemical cell (PEC) properties. The samples were
denoted as ‘S1’ for copper 0.025 M, ‘S2’ for copper 0.050 M
and ‘S3’ for copper 0.075 M, respectively.
2.2 Materials characterization
After film layers had been developed, the structural,
morphological, optical and electrical properties were
characterized. The structural characterization of CTS
nanoparticles was carried out using X-ray diffraction (XRD)
by BRUKER AXS D8 Advanced model X-ray diffractometer
equipped with Cu radiation (Kα of λ= 1.54 Ǻ) operated at 40
kV. Raman spectra were recorded in the range of 150–500 cm-
1 by using a micro-Raman spectrometer (Via Reflex UV
Raman microscope, Renishaw, U.K. at KBSI Gwangju center)
using a He–Ne laser source. The morphological features of
CTS nanoparticles were analyzed by scanning electron
microscopy (SEM) JEOL JSM-6390. SEM technique was
used to observe the grain size, rough morphology, and
distribution of the particles on the surface of the system. The
UV–visible optical absorption and transmittance spectra of
CTS thin films had been carried out to explore their optical
properties. The optical analysis was carried out by a HITACHI UV4100 spectrometer in the wavelength ranging from 310 to
900 nm at room temperature. The current density-voltage (J-
V) characteristics of the PEC cell were observed using a
Princeton Applied Research Potentiostat (273A) with a CTS
electrode as the working electrode.
Fig. 1 XRD patterns of a) CTS thin films prepared at different
copper concentration: S1 = 0.025 M, S2 = 0.050M and S3 =
0.075M; b) XRD spectra of diffraction angles, 2θ, around 28º at
copper concentration: S1 = 0.025M, S2 = 0.050M and S3 =
0.075M and c) diffraction angles, 2θ, around 47º at copper con-
centration: S1 = 0.025M, S2 = 0.050M and S3 = 0.075M.
20 30 40 50 60 70 80
S3
S2
22
0
Inte
ns
ity
(A
. U
.)
2 (Degree)
S1: 0.025 M
S2: 0.050 M
S3: 0.075 M
JCPDS: 00-033-0501 - Cu4SnS
4
− Cu2-x
S
S1
(a)
13
2
11
2
20 25 30 35 40
S1: 0.025 M
S2: 0.050 M
S3: 0.075 M
S3
S2
(x) Cu2SnS3
(y) Cu3SnS4In
ten
sity
(A
. U
.)
2 (Degree)
(y)(x)
S1
(b)
45.0 45.5 46.0 46.5 47.0 47.5 48.0 48.5 49.0 49.5 50.0
S1: 0.025 M
S2: 0.050 M
S3: 0.075 M
(y)
S3
S2
Inte
nsi
ty (
A. U
.)
2 (Degree)
S1
(x)
(x) Cu2SnS3
(y) Cu3SnS4
(c)
Research article ES Materials & Manufacturing
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3. Results and discussion
3.1 Structural studies
Fig. 1a confirms the XRD patterns of CTS films deposited
with different molar concentrations such as 0.025, 0.050 and
0.075 M as denoted by S1, S2 and S3, respectively. The XRD
pattern gives an idea that the deposited films possess
tetragonal (I-42m) structure with a polycrystalline nature
(JCPDS No. 00-033-0501) of Cu3SnS4 material. For the
sample S1 prepared with 0.025 M concentration, a small peak
located at the angle 28.69° emerges in the XRD patterns. At
0.050 M concentration, the strong peaks at 47.110 are assigned
to (-2010) plane regarding the triclinic phase (JCPDS 00-027-
0198) of Cu2SnS3 material in S2 sample. Further increase the
molar concentration to 0.075 M, the formation of a higher Cu
content compound (Cu3SnS4) was observed with a tetragonal
(I-42m) structure. This result is expectable due to the reaction
mechanism between Cu and S.
The strongly oriented peaks at 2θ = 28.90, 47.620 and
57.010 corresponded to the diffraction planes along the (112),
(220) and (132) direction respectively. As the intensity of these
planes is observed higher in sample S3 compared to others.
Furthermore, the diffraction pattern could also match other
CTS secondary phase such as Cu4SnS4 (JCPDS Card: 00-027-
0196). This is because of an excess of CuCl2 in the solution.
The main information that could be deduced from the XRD
patterns is the presence of copper sulfide (Cu2-xS) in a covelite
structure (JCPDS Card: 00-079-2321) and, especially the
absence of secondary materials such as other binary
compounds (CuS, SnS2 and SnS). Further, it is seen that as the
Cu concentration increases from 0.025 to 0.075 M, the
intensity of prominent peak increases. The intensity of the
peaks was moderately augmented as the Cu concentration was
enhanced along with secondary phases. Similar effects were
also observed by Kermadi et al. during the CZTS formation.[13]
Hence, it is concluded that the secondary phase assists the
formation of CTS film through liquid assisted grain escalation,
resulting in large grains and compact nature of CTS films.
Fig. 1 shows the detailed spectra of the three samples at
diffraction angles, 2θ, around 28º and 47º denoted as (b) and
(c), respectively. The phase assignment and crystallites
orientation were performed using the JCPDS database.
Despite the fact that triclinic Cu2SnS3 and tetragonal phases of
Cu3SnS4 present the peaks close to each other, the detailed
analysis shown allow a clear assignment. In the detailed XRD
patterns of Cu3SnS4 compound at the 2θ close of 28.9º, a
deviation from the JCPDS database value is observed. This
fact may be related to the presence of strain in the sample.[14]
3.2. Raman Analysis
To confirm the crystal structure and phase formation of the
films, Raman spectra of CTS samples were studied. Raman
spectroscopy gives the characteristic vibrational modes of
bulk CTS, other secondary and co-existing phases, which can
be differentiated from each other. The Raman spectra of CTS films deposited with different molar concentrations are shown
in Fig 2. In the Raman spectra, the observed peaks at 252, 291,
318, 322 and 471 cm-1 are related to various optical phonons
modes of CTS phase. As seen in Fig. 2, for the samples S1 and
S2 prepared with 0.025 and 0.050 M concentration, the
observed low-intensity modes at 291 and 320 cm-1 are close to
the reported Raman modes of triclinic CTS.[15] The modes at
291 and 318 cm-1 are endorsed to tetragonal CTS phase, which
is in concurrence with the result reported for Raman analysis
at S3 sample.[9] According to the XRD analysis, these peaks
are attributed to Tetragonal (I-42m) Cu3SnS4.
In addition, the presence of shoulder peak at 291 and 322
cm-1 confirms the formation of tetragonal Cu4SnS4, which is
because of an excess of CuCl2 in the cationic solution.[16] These
results also show the presence of Cu2-xS with the characteristic
Raman peak at 251 and 470 cm-1.[17] With Cu-rich conditions,
the neighboring compound of Cu2SnS3 is Cu3SnS4 in the
Gibbs phase triangle.[18] Cu3SnS4 is relatively stable and can
be grown at room temperature.[19] In fact, the calculated
chemical potential phase space of Cu-Sn-S system showed
that Cu3SnS4 has a wide thermodynamic window of
stability.[20] Thus, the formation of that ternary could also
occur in spite of Cu-rich content compound. The formation of
mixed phase of Cu3SnS4 along with secondary phases of
Cu4SnS4 and Cu2-XS is due to the Cu-rich composition
prepared using the single step SILAR method. Thus, it is clear
that due to different molar concentrations of copper in the
single cationic bath, it is very difficult to deposit CTS thin
films with phase purity and stoichiometric composition.
Fig. 2 Raman spectra of CTS thin films prepared at copper con-
centration: S1 = 0.025 M, S2 = 0.050 M and S3 = 0.075 M.
3.3 SEM Analysis
Fig. 3 shows SEM micrographs of CTS films deposited from
solutions having different copper salt concentrations. The
results show that all the surfaces are homogeneous and mainly
composed of spherical grains with some large sparse clusters
and spherical shape. The micrograph of films deposited from
a solution with 0.025 M copper salt concentration, Fig. 3 (S1),
shows a smeary appearance with large island-like regions. As
the copper salt concentration in the solution is increased up to
0.050 M, distinct grains are seen in the film formed (see Fig.
3 (S2)). When the copper concentration in the solution is
further increased to 0.075 M, agglomeration of the grains is
100 150 200 250 300 350 400 450 500
- Cu3SnS4
- Cu2SnS3
- Cu4SnS4
- Cu2-xS
Inte
nsi
ty (
A. U
.)
S1: 0.025 M
S2: 0.050 M
S3: 0.075 M
Raman shift (cm-1)
S1
S3
S2
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found to occur, Fig. 3 (S3). In sprayed CZTS, Kumar et al.[21]
observed similar types of grains increasing in size with
increasing the Cu content. An increase in the surface clusters
with increasing the Cu salt concentration indicates a possible
further reaction of the films on the most active sites,
confirming the aforementioned reports. This effect reaches its
maximum for the 0.075 M sample and proves that the reaction
completion can be different according to the copper content.
The increase of Cu content implies an increase in the mean
grain size from 100 up to 300 nm. It is also useful to mention
that the Cu-poor sample leads to cluster-like aggregates, while
by increasing the copper amount, the aggregates are rounded
and more size-random. This increase in the grain size might be
due to the agglomeration of grains. Increase in grain size
improves the performance of a polycrystalline CTS thin film
with a decrease in grain boundaries that increases the effective
diffusion length of minority carriers.
3.4 Optical analysis
To evaluate the optical band gap for different samples, the
relation between the direct energy gap (Eg) and absorption
coefficient (α) from the Tauc's approximation was shown in
Equation 1:
( )( )
h
EhAn
g−= (1)
where A is a proportionality constant, h is the Planck's constant
and n defines the nature of the radiative transition. In the
present investigation, the values of α are found to obey the
above Equation for n= 1/2, indicating that the optical
transitions are direct-allowed in nature. The effect of Cu
concentration on the optical characteristics such as coefficient
of absorption and band gap of CTS thin film was investigated.
Fig. 4(A) demonstrates the absorption spectra of CTS film
with different Cu concentration. The energy band gap of CTS
thin films was determined from the optical absorption study in
the wavelength having the range of 300–900 nm, which is
important in the design and analysis of various optical devices.
Fig. 4 (B) shows a plot of the square of the product of the
absorption coefficient and photon energy as a function of the
photon energy for the SILAR deposited CTS films with
different Cu concentrations.
The band gap is estimated by extrapolating the straight line
part of the (αhν)2 versus hν curve to the intercept of the
horizontal axis. The values of band-gap for CTS films are
determined to be 1.90, 1.21 and 1.07 eV for 0.025, 0.050 and
0.075 M, respectively. The decrease in the band gap with an
increase in the Cu concentration may be because of: 1)
increase in the crystallinity observed from XRD analysis, 2)
excess of Cu ionsin the cationic bath solution and 3) The
presence of secondary phase Cu4SnS4 carrying a narrow band
gap observed from XRD and Raman analysis. The band gap
tunneling may be understood according to the symmetry of the
valence band maximum (VBM) and conduction band
minimum (CBM) states.[22] It should be noted that the disorder
between Cu and Sn cations is highly possible in the CTS
semiconductors with different compositions, and therefore its
influence on the band gaps is also common.[23]
Fig. 3 SEM images of CTS thin films prepared at copper
concentration: S1 = 0.025 M, S2 = 0.050 M and S3 = 0.075 M.
3.5 Photoelectrochemical cell (PEC) analysis
The PEC performance of the CTS thin films deposited on the
FTO substrates with different Cu concentrations was
investigated using the linear sweep voltammetry (LSV)
measurements. The LSV was performed in a lithium
perchlorate (0.5 M LiClO4) electrolyte under AM 1.5G (100
mWcm-2) illumination using a conventional two electrode
system with a CTS photocathode and graphite as a working
electrode and counter electrode, respectively. The illuminated
J-V curves for CTS based PEC devices fabricated using 0.025,
0.050 and 0.075 M are shown in Fig. 5. The PEC
characterization is selected because it is easier than forming a
solid-state junction. It allows a rapid and nondestructive
S1 S2 S30.025M 0.050M 0.075M
S1 S2 S30.025M 0.050M 0.075M
S1 S2 S30.025M 0.050M 0.075M
Research article ES Materials & Manufacturing
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evaluation of a photoactivity of the CTS thin films. The
photovoltaic output characteristics of CTS thin films are
analyzed by fabricating FTO/CTS/0.5 M LiClO4/C cell. The
anodic photocurrent was enhanced with the negative potential,
which designates the p-type conductivity of deposited CTS
thin films.[24]
Fig. 4 (A) Optical absorption and (B) Variation of (αhν)2 versus
(hν) plot of CTS thin films prepared at a copper concentration: S1
= 0.025 M, S2 = 0.050 M and S3 = 0.075 M.
Fig. 5 J-V characteristics of CZTS thin films prepared at copper
concentration: S1 = 0.025 M, S2 = 0.050 M and S3 = 0.075 M.
Table 1. Solar cell parameters of PEC devices fabricated for
different copper concentration: S1 =0.025 M, S2 = 0.050 M and
S3 = 0.075 M.
Sr.
N
o
Sampl
e
Jsc
(μA)
Voc
(mV)
Jm
(μA)
Vm
(mV)
Fill
Facto
r FF
(%)
Efficienc
y η (%)
1. S1 79.70 48.00 33.78 28.78 0.254 0.001
2. S2 397.3
4 405.0
5 223.7
7 178.3
9 0.248 0.069
3. S3 460.6
7
521.6
8
267.9
1
214.7
5 0.239 0.114
In the dark, the PEC cell device exhibits diode like
characteristics, which shows an insignificant reverse
saturation current. While the J-V characteristics under
illumination appear the images of a linear plot. These linear
manners of J-V plots are mostly ascribed to the digression
from the stoichiometry, extensively elevated series resistance
of absorber layer and the squat shunt resistance of the PEC
device. The detailed PEC parameters are listed in Table 1. The
significant enhancement in the JSC and VOC is observed with
increasing the Cu concentration upon illumination as shown in
Fig. 5. It can be clearly seen from the graph that the solar cell
based on CTS thin films derived from 0.025 M concentration
denoted by S1 shows a relatively poor performance. This may
be due to an insufficient Cu concentration during the CTS
formation process, which may create structural defects in the
CTS film. While the cell derived from 0.075 M concentration
denoted by S3 exhibits a better conversion efficiency of
0.11 %. From the structural analysis, it is observed that the S3
sample shows a very small secondary phase of Cu2-xS and
Cu4SnS4. The 0.025 and 0.050 M concentration films show a
low efficiency as compared to 0.075 M films.
The fill factor (FF) is lower in the present PEC devices
because of impurities and defects, including insulating
secondary phases, which cause charge carrier recombination.
This effect would be a similar to that of sprayed CZTS thin
films.[25] The short circuit current (JSC) increases with
increasing the Cu concentration. This is due to the improved
and large grain size, which increases the absorption of incident
photons. Additionally, it helps to increase the current
generation and reduce the minority recombination rates.
Similar results are also mentioned by He et al..[26] The
augmentation of these solar cell parameters could be attributed
to the improved morphology of CTS thin films, which affected
the CTS-electrolyte junction quality and dynamics of charge
carrier recombination. Similar effect was introduced by
Suryawanshi et al. during the formation of CZTS thin films.[27]
The photoelectrochemical measurement confirmed the best
photo-activity of the CTS thin films as illustrated in Table 1.
The presence of the secondary phases could affect the
photovoltaic performance. It has been speculated that the
phase separation of CTS into Cu2-xS and Cu4SnS4 compounds
is one of the factors limiting the efficiency of CTS solar cells.
In thin-film solar cells, Cu-rich compounds tend to show poor
power conversion efficiencies due to their higher electrical
conductivity, leading to the shunting problem.[28]
4. Conclusions
In this paper, the effects of copper concentration on structural,
morphological, optical and PEC properties of CTS thin films
have been investigated. The analysis of XRD patterns
indicates that the CTS film with a copper concentration up to
0.075 M have a sharp and intense peak orientation. Further,
Raman studies confirm the formation of mixed phase of
Cu3SnS4 along with secondary phases of Cu4SnS4 and Cu2-XS
due to Cu-rich composition. SEM results indicate that as the
Cu concentration increases, the average grain size also increases. Decrease in band gap due to increase in copper
concentration was confirmed. Furthermore, the solar cell
fabricated with the copper rich CTS film (S3) showed an
enhancement in the conversion efficiency about 0.11%.
Because of the increased number of elements in CTS, their
1.0 1.5 2.0 2.5 3.0 3.5
h (eV)
(h
)2
(eV
)2
S1: 0.025M
S2: 0.050M
S3: 0.075M
(B) Optical band gap
S2
S3
S1
-100 0 100 200 300 400 500 600
-100
0
100
200
300
400
500 S1: 0.025M
S2: 0.050M
S3: 0.075M
S1
S2
S3
Cu
rre
nt
de
ns
ity
(A
/ c
m-1
)
Voltage (mV)
ES Materials & Manufacturing Research article
© Engineered Science Publisher LLC 2020 ES Mater. Manuf., 2020, 10, 22-28 | 27
synthesis is more difficult than for binary and ternary
semiconductors. The secondary phases in CTS such as Cu2-XS
and Cu4SnS4 could be formed depending on the processing
conditions. Experimentally, it is found that working devices
are obtained for “Cu-poor” compositions.
Acknowledgement
Authors are thankful to the Department of Science and
Technology-Science and Engineering Research Board (DST-
SERB), New Delhi, India for their financial support through
research Project No. SERB/F/001677/2016-17 dated 13th
January 2017.
Support information
Not applicable
Conflict of Interest
There are no conflicts to declare.
References [1] K. Wang, O. Gunawan, T. Todorov, B. Shin, S. Chey, N.
Bojarczuk, D. Mitzi, S. Guha, Appl. Phys. Lett.,2010, 97,
143508, DOI: 10.1063/1.3499284.
[2] H. Katagiri, K. Jimbo, S. Yamada, T. Kamimura, W. Maw, T.
Fukano, T. Ito, T. Motohiro, Appl. Phys. Express, 2008, 1,
41201, DOI: 10.1143/APEX.1.041201.
[3] F. Chen, J. Zai, M. Xu, X. Qian, J. Mater. Chem. A, 2013, 1,
4316, DOI: 10.1039/C3TA01491F.
[4] H. Liu, Z. Chen, Z. Jin, Y. Su, Y. Wang, Dalton Trans., 2014,
43, 7491-7498, DOI: 10.1039/C4DT00070F.
[5] X. Liu, X. Wang, M.T. Swihart, Chem. Mater., 2015, 27,
3378-3388, DOI: 10.1021/acs.chemmater.5b00618.
[6] J. Xu, X. Yang, T.L. Wong, C.S. Lee, Nanoscale, 2012, 4,
6537-6542, DOI: 10.1039/C2NR31724A.
[7] P. Fernandes, P. Salomé, A. Cunha, J. Phys. D: Appl. Phys.,
2010, 43(21), 215403, DOI: 10.1088/0022-
3727/43/21/215403.
[8] M. Alias, I. Naji, B. Taher, IPASJ International Journal of
Electrical Engineering (IIJEE), 2017, 2 (12), 1,
DOI:10.30919/esmm5f922.
[9] S. Chen, J. Tao, H. Shu, H. Tao, Y. Tang, Y. Shen, T. Wang, L.
Pan, J. Power Sources, 2017, 341, 60-67, DOI:
10.1016/j.jpowsour.2016.11.107.
[10] Z. Su, K. Sun, Z. Han, F. Liu, Y. Lai, J. Li, Y. Liu, J. Mater.
Chem., 2012, 22, 16346-16352, DOI:
10.1039/C2JM31669B.
[11] V Maheskumar, P Gnanaprakasam, T Selvaraju, B Vidhya,
Int. J. Hydrog. Energy, 2018, 43 (8), 3967-3975, DOI: 10.1016/j.ijhydene.2017.07.194.
[12] B. Zhao, S. Li, M. Che, L. Zhu, Int. J. Electrochem. Sci.,
2016, 11, 6514-6522, DOI: 10.20964/2016.08.29.
[13] S. Kermadi, S. Sali, F. Ait Ameur, L. Zougar, M. Boumaour,
A. Toumiat, N. Melnik, D. Hewak, A. Duta, Mater. Chem.
Phys., 2016, 169, 96-104, DOI:
10.1016/j.matchemphys.2015.11.035.
[14] S. Chain, J. Tao, H. Shu, H. Tao, Y. Tang, Y. Shen, T. Wang,
L. Pan, J. Power Sources, 2017, 341, 60-67, DOI:
10.1016/j.jpowsour.2016.11.107.
[15] H. Shelke, A. Lokhande, J. Kim, C. Lokhande, J. Colloid
Interface Sci., 2017, 506, 144-153, DOI:
10.1016/j.jcis.2017.07.032.
[16] U. Chalapathi, B. Poornaprakash, S. Park, J. Sol. Energy,
2017, 155, 336-341, DOI: 10.1016/j.solener.2017.06.051.
[17] P. Fernandes, P. Salome, A. Cunha, Thin Solid Films, 2009,
517, 2519-2523, DOI: 10.1016/j.tsf.2008.11.031.
[18] S. Fiechter, M. Martinez, G. Schmidt, W. Henrion, Y. Tomm,
J. Phys. Chem. Sol.,2003, 64, 1859-1862, DOI:
10.1016/S0022-3697(03)00172-0.
[19] U. Chalapathi, Y. Kumar, S. Uthanna, V. Sundara Raja, Thin
Solid Films, 2014, 556, 61-67, DOI:
10.1016/j.tsf.2014.01.005.
[20] P. Zawadzki, L. L. Baranowski, H. Peng, E. S. Toberer, D. S.
Ginley, W. Tumas, A. Zakutayev, S. Lany, Appl. Phys. Lett.,
2013, 103, 253902, DOI: 10.1063/1.4851896.
[21] Y. Kumar, P. Bhaskar, G. Babu, V. Raja, Phys. Status Solidi
A, 2010, 207(1), 149-156, DOI: 10.1002/pssa.200925194.
[22] S. Chen, A. Walsh, Y. Luo, J.H. Yang, X. Gong, S. Wei, Phys.
Rev. B., 2010, 82, 195203, DOI:
10.1103/PhysRevB.82.195203.
[23] A. Lokhande, S. Pawar, E. Jo, M. He, A. Shelke, C.
Lokhande, J. Kim, Opt. Mater., 2016, 58, 268-278, DOI:
10.1016/j.optmat.2016.03.032.
[24] D. Brion, Appl. Surf. Sci., 1980, 5, 133-152, DOI:
10.1016/0378-5963(80)90148-8.
[25] M. Patel, I. Mukhopadhyay, A. Ray, J. Phys. D: Appl. Phys.,
2012, 45, 445103, DOI: 10.1088/0022-3727/45/44/445103.
[26] J. He, L. Sun, Y. Chen, J. Jiang, P. Yang, J. Chu, J. Power
Sources, 2015, 273, 600-607, DOI:
10.1016/j.jpowsour.2014.09.088.
[27] M. Suryawanshi, P. Patil, S. Shin, K. Gurav, G. Agawane, M.
Gang, J. Kim, A. Moholkar, RSC Adv., 2014, 4, 18537-18540,
DOI: 10.1039/C4RA01208A.
[28] A. Lokhande, A. Patil, A. Shelke, P. Babar, M. Gang, V.
Lokhande, D. Dhawale, C. Lokhande, J. Kim, Electrochem.
Acta, 2018, 284, 80-88, DOI:
10.1016/j.electacta.2018.07.170.
Author information
Harshad D. Shelke is currently a Ph.D student in Prof. C. D. Lokhande’s group
in Thin Film Physics Laboratory (TFPL)
at Shivaji University Kolhapur. He received his M.Sc. degree from same
University in 2014. He has published 8
papers on Copper based chalcogenide materials with citation over 20 times. His
research focused on the Simple chemical processed Cu2SnS3 thin film solar cell and its optoelectronic
characteristics.
Abhishek C. Lokhande is a
Postdoctoral Fellow of Department of Physics, Khalifa University of Science
and Technology, Abu Dhabi, United
Arab Emirates (UAE). He obtained his Ph.D from Optoelectronic Convergence
Research Centre, Department of
Materials Science and Engineering, Chonnam National University, Gwangju,
South Korea under the supervision of Prof. Jin H. Kim. He has
Research article ES Materials & Manufacturing
2 8 | ES Mater. Manuf., 2020, 10, 22-28 © Engineered Science Publisher LLC 2020
published over 117 papers on Copper based chalcogenide materials with citation over 2000 times. His current research
focuses on thin film photovoltaics using earth-abudant and
nontoxic materials.
Jin H. Kim is Professor of
Optoelectronic Convergence Research Centre, Department of Materials Science
and Engineering, Chonnam National University, Gwangju, South Korea. His
current research focuses on thin film
photovoltaics, Gas-sensor, Photocatalysis, Li-ion batteries and
Supercapacitor using earth-abundant
and nontoxic materials.
Chandrakant D. Lokhande is a
Research Director of Center for
Interdisciplinary Research Centre, D. Y.
Patil University, Kolhapur. He obtained his Master degree and Ph.D degree from
Shivaji University Kolhapur. He then did his postdoctoral research at Dept. of
Materials Science, WeizmannInstitute of
Science, Rehovot, Israel worked on CuIn chalcogenide thin films. He was honored “Alexander Von-Humboldt
Fellowship,Germany” in 1996-2001 and Nomination for
Shanti Swarap Bhatnager Award by Shivaji University, Kolhapur in 1998 & 1999. He has Patents: (46) (Indian 11
accepted, Korean 5 accepted), Applied (Indian) 29, (Korean) 1, World 01. He has published over 600 papers on various
materials with citated over 50,000 times. His current research
focuses on thin film photovoltaics, Gas-sensor and Supercapacitor using earth-abundant and nontoxic materials. .
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