Materials Science in Semiconductor Processing 30 (2015) 48–55

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Materials Science in Semiconductor Processing

journal homepage: www.elsevier.com/locate/mssp

Copper selenide nanorods grown at room temperature

by electrodeposition
S.S. Dhasade a,n, J.V. Thombare a, R.S. Gaikwad a, S.V. Gaikwad b,
S.S. Kumbhare b, Swati Patil c
a
Vidnyan Mahavidyalaya, Sangola 413307, India
b
D.B.F. Dayanand College of Arts and Science, Solapur, India
c
Pratap Singh Mohite Patil Mahavidyalaya Karmala, India

a r t i c l e in f o abstract

In this work we employed an electrodeposition technique to prepare copper selenide

Keywords: nanorods with various dimensions by changing bath concentration and keeping deposi-
Electrodeposition tion time fixed. This study reports the effect of bath concentration on the crystal structure,
Semiconductor surface morphology and optical properties of copper selenide thin films. The electro-
Recrystallization deposited films were characterized using X-ray diffraction (XRD), scanning electron
Nanorods microscopy (SEM), Raman spectra properties, the ultraviolet–visible (UV–vis) and com-
Red-shift positional analysis. Upon bath concentration, the band gap energy of copper selenide
decreases from 2.54 eV to 2.35 eV along with an increase in the crystal size form 7–17 nm.
The crystal size was found to increase upon increase in bath concentration and materials
exhibit better crystallization. Similar results were also observed in the XRD studies, where
peak intensity increased upon bath concentration.
& 2014 Elsevier Ltd. All rights reserved.

1. Introduction heat treatment in argon atmosphere in the range of 350–

450 1C [4]. Copper selenide is sensitive to ethanol and acetone
In the past few decades, copper selenide attracts much gas is reported by Wang et al. [5]. Nanosheets having abso-
interest due to its potential applications in photoelectrical rption onsets near infra red optical absorption region is
properties, electronic optoelectronic devices, photothermal synthesized [6]. Copper selenide nanodiscs with current
therapy, Li ion batteries and electrochemical hydrogen storage difference under light, compared to the dark state is reported
and gas sensing properties. Comparable to nanorods and [7]. The morphologies of copper selenide have a great
nanoshells of gold (Au), the copper selenide nanocrystals influence over to electrical transport properties were studied
produce major photothermal heating with a photothermal by Xiao et al. [8]. Increase in the bandgap energy and decr-
transduction of more efficiency [1]. Thermoelectric properties ease in the grain size of copper selenide with increase in
of copper selenide were studied by Yu et al. [2]. Cop- atomic % of copper is reported [9]. Reports are also available
per selenide nanosheets were used as an anode material for on photosensitivity of copper selenide having band gap
lithium ion batteries due to a good cycle and rate performance energy 2.74 eV [10–12]. Different sizes of monodispersed
[3]. Photoactivity studies of copper selenide were done by Cu2
xSe nanocrystals were synthesized by colloidal method
[13]. Copper selenide thin films with different phases Cu2
xSe,
Cu3Se2 were prepared by Lakshmi et al. [14]. Copper selenide
n
Corresponding author. Tel.: þ91 02187221221. thin films deposited by the solution growth technique shows
E-mail address: [email protected] (S.S. Dhasade). polycrystalline nature having average grain size of 144 nm

http://dx.doi.org/10.1016/j.mssp.2014.09.021
1369-8001/& 2014 Elsevier Ltd. All rights reserved.
 S.S. Dhasade et al. / Materials Science in Semiconductor Processing 30 (2015) 48–55 49

[15]. The processes carried at room temperature avoid oxida- 2.2. Reaction mechanism
tion and corrosion of thin films on tin doped indium oxide
(ITO) substrates and any conducting films (substrates). This At the beginning of reaction, copper sulfate in water
can potentially lead to a new generation of photovoltaic gets dissociated as follows,
devices that are light in weight, foldable, and flexible. The
2

wide range of associated structural, surface morphological, CuSO4-Cu2 þ þSO4 (1)
optical properties makes these films potentially attractive for
application as solar cell devices. In the present research work unstirred reactions are
As per author's knowledge, present work describes in carried out at room temperature. Mean while electroche-
detail the formation mechanism of CuSe nano rods with mical reduction of SeO2 becomes
precursor's concentration. As far as solar cell device
fabrication is concern, their basic requirement is materials SeO2 þ6H þ þ4e
-H2Se þ2H2O (2)
structural, morphological and optical properties. So, pre-
sent investigation reports on the tuning of structural, Cu2 þ þH2Se-CuSe þ2H þ (3)
morphological and optical properties with precursors
concentration. Thus, present work is a reference data to
the research group which working on CuSe based solar 2.3. Instruments and characterization
cell. Also, present work is the addition to the knowledge
which is useful for the material synthesis by electrodepo- The phase and identity of the copper selenide were
sition method. The electrodeposition method provides recorded and verified by the X-Ray powder diffraction
various advantages, because of relatively simple as well using a Rigaku Rint-2000 X-ray diffractometer system with
as inexpensive equipment. Films can be fabricated on large a Cu/30 kV/15 mA (λ 1.5417 Å) radiation with a scan step of
area and irregular surfaces. The deposition happens closer 0.001. The surface morphology and the compositional
to equilibrium than in many high temperature methods, analysis of CuSe were confirmed by energy-dispersive X-
and there is no problem with inter element diffusion. The ray analysis, using JEOL model, JSM-6300 (LA). Raman
process can be rather precisely controlled because of its spectra of the films were collected on a combination
electrical nature; the toxic gaseous precursors are not used system including research grade FTIR model VERTEX 70
unlike in chemical gas phase methods. with model- Ram- II FT Raman spectrometer equipped
with Nd-YAG laser at 1064 nm wavelength. The spectra
were recorded at laser power 0–450 mW, the wave num-
2. Experimental ber range from 200 to 4000 cm
1. Optical absorption
study of the as deposited CuSe thin films on ITO coated
2.1. Preparation of solution glass substrate is carried out using UV–vis spectrometer.

Bath (1): bath (1) is prepared by taking the mixture of 3. Results and discussion
0.05 M of CuSO4  5H2O and 0.025 M of SeO2 in
distilled water. 3.1. Cyclic voltammetry
Bath (2): bath (2) is prepared by taking the mixture of
0.10 M of CuSO4  5H2O and 0.050 M of SeO2 in Fig. 1 shows that the cyclic voltammograms recorded
distilled water. onto stainless steel substrate from electrolytic solutions
Bath (3): bath (3) is prepared by taking the mixture of
0.15 M of CuSO4  5H2O and 0.075 M of SeO2 in
distilled water.
Bath (4): bath (4) is prepared by taking the mixture of
0.20 M of CuSO4  5H2O and 0.1 M of SeO2 in
distilled water.

Copper selenide thin films were prepared on stainless

steel/ITO substrate by the electrodeposition technique.
Stainless steel substrate was polished by polish paper,
deeped in 10% HCl for 15 min. and then cleaned with
double distilled water. Electrodeposition study of
copper selenide thin films was made using potentiostat
(Princeton Perkin-Elmer, Applied Research Versa-stat-II;
Model 250/270) in three-electrode configuration. Pure
graphite plate was used as an anode, stainless steel was
used as cathode and saturated calomel electrode (SCE) was
used as reference electrode. Violet, yellow, blue, red
colored, smooth, uniform copper selenide thin films were Fig. 1. Cyclic voltammogram onto stainless steel substrate for copper
obtained. selenide thin film.
50 S.S. Dhasade et al. / Materials Science in Semiconductor Processing 30 (2015) 48–55

Fig.2. Photograph of copper selenide thin films with different bath compositions (a) 0.05 M CuSO4  5H2Oþ0.025 M SeO2; (b) 0.1 M CuSO4  5H2Oþ 0.05 M
SeO2; (c) 0.15 M CuSO4  5H2Oþ 0.075 M SeO2 and (d) 0.2 M CuSO4  5H2Oþ0.1 M SeO2, with deposition time of 20 min.

containing 0.05 M of CuSO4  5H2O and 0.025 M of SeO2

in order to find the suitable reduction potentials of
copper selenide. The potentiodynamic scan was applied
to find to deposition potential in the potential window of

1.5 V/SCE to 0.5 V/SCE at the scan rate 20 mV/s. Fig. 1
shows the two successive cycles obtained at same scan
rate. From Fig. 1 the reduction and oxidation peaks are
seen. The deposition potential of copper selenide was
found to be
0.65 V/SCE. The electrodeposition of
copper selenide thin films was carried out at the deposi-
tion potential
0.65 V/SCE and current density of 1.5–
2.0 mA/cm2, for various bath concentrations by keeping
deposition time. Films are deposited at room temperature.
Violet, yellow, blue, red colored uniform and nearly
stoichiometric copper selenide thin films were deposited
by potentiostatic mode onto stainless steel and ITO coated
glass substrates for optimized preparative parameters,
which is shown in Fig. 2 (a, b, c, and d). After the Fig. 3. The XRD patterns of copper selenide thin film for, (a) bath
deposition, the films were washed with double distilled composition of 0.05 M CuSO4  5H2Oþ 0.025 M SeO2; (b) bath composi-
water. The pH of the plating bath ranges between 3 and 4. tion of 0.1 M CuSO4  5H2Oþ0.05 M SeO2; (c) bath composition of 0.15 M
CuSO4  5H2Oþ0.075 M SeO2 and (d) bath composition of 0.2 M
CuSO4  5H2Oþ0.1 M SeO2, with deposition time of 20 min.
3.2. XRD studies

Fig. 3 (a, b, c, and d) shows XRD patterns of copper selenide

nanostructure. The phases of copper selenides can be easily detected, further confirming that the precursors have been
distinguished by the powder X-ray diffraction patterns. All of completely transformed into copper selenide nanostructures.
the diffraction peaks (107), (108), (110), (213) can be well Table 1 shows the comparison of measured and standard ‘d’
indexed to those of hexagonal JCPDS card no. (86-1240). values for as-deposited copper selenide thin films for (a) bath
Diffraction peaks of other phases or impurities were not composition of 0.05 M CuSO4  5H2Oþ0.025 M SeO2; (b) bath
 S.S. Dhasade et al. / Materials Science in Semiconductor Processing 30 (2015) 48–55 51

Table 1
Comparison of standard and measured d values for, as deposited CuSe thin films.

(hkl) planes Std. ‘d’ values(Å) Measured ‘d’ values (Å)

0.05 M CuSO4 þ0.025 M SeO2 0.1 M CuSO4 þ 0.05 M SeO2 0.15 M CuSO4 þ 0.075 M SeO2 0.2 M CuSO4 þ 0.1 M SeO2

(107) 2.00 2.02 2.01 2.00 2.00

(108) 1.82 1.81 1.83 1.82 1.79
(110) 1.74 1.73 1.75 1.73 1.73
(213) 1.27 1.27 1.25 1.26 1.25

Table 2 3.3. Scanning electron microscopy

Chemical composition, optical band gap, crystallite size, film thickness
of copper selenide for different bath concentrations with 20 min.
deposition time. SEM images of as-deposited copper selenide thin film for
bath composition of 0.05 M CuSO4  5H2Oþ0.025 M SeO2;
Bath conc. Cu Se Band gap Crystal size 0.1 M CuSO4  5H2Oþ0.05 M SeO2; 0.15 M CuSO4  5H2Oþ
(at%) (at%) (eV) (nm)
0.075 M SeO2 and 0.2 M CuSO4  5H2Oþ0.1 M SeO2; with
0.05 M 45.95 54.05 2.54 7 deposition times of 20 min. are shown in Fig. 4 (a, b, c, and
CuSO4  5 H2Oþ0.025 M d). From the SEM images, it is seen that nanorods are clearly
SeO2 observed. The nanorods size increases by increasing bath
0.1 M 47.80 52.20 2.46 11 concentration. These nanorods are uniformly distributed
CuSO4  5 H2Oþ0.05 M
over smooth homogenous background. The well developed
SeO2
0.15 M 50.39 49.61 2.42 13 and matured copper selenide nanorods growth is observed
CuSO4  5 H2Oþ0.075 M in Fig. 4 (a, b, c, and d). For films with higher bath
SeO2 concentration the growth occurs with multiple nucleation
0.2 M 54.43 45.57 2.35 17
centres resulting in a higher grain size, while for lower bath
CuSO4  5 H2Oþ0.1 M
SeO2
concentration comparatively lower nucleation centres give
lower grain size.

3.4. Mechanism of copper selenide nanorods

composition of 0.1 M CuSO4  5H2Oþ0.05 M SeO2; (c) bath
composition of 0.15 M CuSO4  5H2Oþ0.075 M SeO2 and (d) The well developed and matured as electrodeposited
bath composition of 0.2 M CuSO4  5H2Oþ 0.1 M SeO2, with copper selenide nanorods growth is shown in Fig. 4 (a, b, c,
deposition time of 20 min. They are in good agreement with and d) with optimized deposition time and different bath
standard ‘d’ values. The growth of an electrodeposit from an concentrations. First, homogeneous mixture of the CuSO4
electrolyte involves a phase transformation from ionic species was synthesized in distilled water, which acted as the
in the solution to a solid phase on the electrode. This phase sacrificial template [16]. In the electrodeposition process,
transformation is the cumulative effect of ionic transport, they partly reacted with SeO2 to form a Cu@Se core–shell
discharge, nucleation, and growth due increased concentration structure. This process can be described as follows: there
of CuSO4 and SeO2 Table 2. were several Cu2 þ ions ionized from CuSO4 that were
Fig. 3 (a, b, c, and d) shows that with increase in bath located around the surface of the Cu nanorods. At the initial
concentration peak intensity goes on increases indicates stage of the reaction, they reacted with Se2
in the solution
that crystal size is better. This is due to changes in local to form copper selenide belts. Then, the Cu nanorods were
structure order of film with increase in bath concentration. covered with a very thin layer of copper selenide. With the
The XRD measurements show that the copper selenide reaction proceeding, the outside shell of copper selenide
thin films contain nanocrystals. The crystal size is deter- was gradually formed and the next layer starts reacting
mined using Scherrer's formula. For bath composition of once the copper selenide in the surface of the crystals got
0.05 M CuSO4  5H2Oþ0.025 M SeO2; crystallite size is peeled off to the solution. The substantial change in surface
7 nm, for bath composition of 0.1 M CuSO4  5H2O þ0.05 M morphology of copper selenide is because of higher bath
SeO2; it is 11 nm, for bath composition of 0.15 M concentration.
CuSO4  5H2Oþ0.075 M SeO2; crystal size is 13, for bath
composition of 0.2 M CuSO4  5H2Oþ0.1 M SeO2; crystallite 3.5. Raman spectroscopy
size is 17 nm, this proposes that with increase in bath
concentration of CuSO4 and SeO2 for deposition time of The typical Raman spectrum of as-deposited
20 min. crystallite size increases. Larger the concentration copper selenide films for bath composition of 0.2 M
of CuSO4 and SeO2 bigger is the crystal size. For films with CuSO4  5H2Oþ0.1 M SeO2 with deposition time of
higher concentration of Cu and Se ions, the growth occurs 20 min. is shown in Fig. 5. A Raman shift of sample is
with multiple nucleation centres resulting in a bigger detected at almost the wave numbers 1014, 1035, 1074, and
crystal size, while for lower concentration of Cu and Se 1151 cm
1, respectively. In the Raman spectrum Fig. 5 the
ions; comparatively lower nucleation centres give lower high intensity peaks recorded at above wave number can
crystal size. be attributed to the formation of copper selenide, by
52 S.S. Dhasade et al. / Materials Science in Semiconductor Processing 30 (2015) 48–55

Fig. 4. SEM images of copper selenide thin film for, (a) bath composition of 0.05 M CuSO4  5H2Oþ0.025 M SeO2; (b) bath composition of 0.1 M
CuSO4  5H2Oþ0.05 M SeO2; (c) bath composition of 0.15 M CuSO4  5H2Oþ 0.075 M SeO2 and (d) bath composition of 0.2 M CuSO4  5H2Oþ 0.1 M SeO2, with
deposition time of 20 min.

correlation with Berzelianite RRUFF ID: R060260 Cu2
xSe

(   0.12). The shift at higher wave number values may be
linked with the vacancies in the copper selenide lattice,
induced during the film growth. Raman spectrum of
copper selenide thin films deposited at 20 min. In Fig. 5
shows that the high intensity peak recorded to 1074, 1109,
1130, 1141 and 1151 cm
1, respectively. This is attributed
to band splitting or ionization of atoms, this leads to
change in the local structure order of film.

3.6. Optical properties

The optical band gap energy of as-deposited copper

selenide thin films were determined from the plot of (αhν)2
versus (hν) as shown in Fig. 6 (a, b, c, and d). Band gap energy
was calculated from the classical relation for direct-band
optical absorption. The optical band gap energy of as-
deposited copper selenide films estimated from the figures
are 2.54 eV with crystal size 7 nm for bath composition of
0.05 M CuSO4  5H2Oþ0.025 M SeO2, it is 2.46 eV with
Fig. 5. Raman spectrum of copper selenide thin film for bath composition crystal size of 11 nm for bath composition of 0.1 M
of 0.2 M CuSO4  5H2Oþ0.1 M SeO2, with deposition time of 20 min. CuSO4  5H2Oþ0.05 M SeO2, 2.42 eV with crystal size of
 S.S. Dhasade et al. / Materials Science in Semiconductor Processing 30 (2015) 48–55 53

, 10 9 (
2
( α ν)

Fig. 6. Optical band gap energy of copper selenide thin films, (a) bath
Fig. 7. Optical absorbance of copper selenide thin films, (a) bath
composition of 0.05 M CuSO4  5H2Oþ 0.025 M SeO2; (b) bath composi-
composition of 0.05 M CuSO4  5H2Oþ0.025 M SeO2; (b) bath composi-
tion of 0.1 M CuSO4  5H2Oþ0.05 M SeO2; (c) bath composition of 0.15 M
tion of 0.1 M CuSO4  5H2Oþ0.05 M SeO2; (c) bath composition of 0.15 M
CuSO4  5H2Oþ 0.075 M SeO2 and (d) bath composition of 0.2 M
CuSO4  5H2Oþ 0.075 M SeO2 and (d) bath composition of 0.2 M
CuSO4  5H2Oþ 0.1 M SeO2, with deposition time of 20 min.
CuSO4  5H2Oþ 0.1 M SeO2; with deposition time of 20 min.

13 nm for bath composition of 0.15 M CuSO4  5H2Oþ 0.075 M film estimated from the figure were reported [9,18]. For
SeO2 and 2.35 eV with crystal size of 17 nm for bath composi- semiconductor crystal electron excitation consists of
tion of 0.2 M CuSO4  5H2Oþ0.1 M SeO2. The decrease in the loosely bounded electron hole pair (Mott–Wannier excita-
optical band gap energy and appearance of second band gap tion) usually delocalized over length much longer than
with increases in bath concentration implies the creation of lattice constant. As diameter of semiconductor crystallite
additional energy levels due growth in crystal size. approaches this excitation its electronic properties starts
From the XRD results, we propose that the absorption to change this is due to quantum size effect [19,20]
edge red-shift is due to the better crystallinity of therefore we can study optical absorption spectra. Optical
copper selenide thin films grown at room temperature. absorption spectra for as-deposited copper selenide films
The crystallinity of the copper selenide thin films grown have been recorded over the range 300–750 nm. The abso-
with deposition time of 20 min. for bath composition of rbance versus wavelength of as-deposited copper selenide
0.05 M CuSO4  5H2Oþ0.025 M SeO2 and composition of thin films for the set of baths; with deposition time of
0.1 M CuSO4  5H2Oþ0.05 M SeO2 was poor and exhibits 20 min. is shown in Fig. 7 (a, b, c, and d) the plot shows
polycrystalline structure. Qualitatively, the interatomic absorption region in the range of 450–550 nm. For bath
spacing of poor crystalline structure would be relatively composition of 0.15 M CuSO4  5H2O þ0.075 M SeO2 and
long and more disordered than crystalline structure due to composition of 0.2 M CuSO4  5H2Oþ0.1 M SeO2 with dep-
the absence of long-range translational periodicity. As the osition time of 20 min. there is shift of absorption shoulder
fraction of poor crystalline copper selenide phase increases towards higher wavelength side. This shift of absorbance
in the films, the extended localization in the conduction to edge of higher wavelength is attributed to the quantum
and valence bands increases [16,17]. As a result, the size effect due to higher bath concentration of CuSO4 and
absorption of photon is mainly contributed by poor crys- SeO2.
talline copper selenide and hence the absorption edge
blue-shifted [17]. On the other hand, for samples grown at 3.7. Compositional analysis
higher concentration of CuSO4 and SeO2 for bath composi-
tion of 0.15 M CuSO4  5H2O þ0.075 M SeO2 and composi- The sample was characterized by Energy-Dispersive X-ray
tion of 0.2 M CuSO4  5H2Oþ0.1 M SeO2 the crystallinity of Analysis. The compositional analysis of as-deposited copper
copper selenide thin films becomes better. Qualitatively, selenide for bath composition of 0.05 M CuSO4  5H2Oþ
the interatomic spacing of better crystalline structure of 0.025 M SeO2; composition of 0.1 M CuSO4  5H2Oþ0.05 M
copper selenide would be relatively more ordered than SeO2; composition of 0.15 M CuSO4  5H2Oþ 0.075 M SeO2
poor crystalline structure of copper selenide due to the and composition of 0.2 M CuSO4.5 þ0.1 M SeO2 with deposi-
presence of long-range translational periodicity. As the tion time of 20 min. was carried out as shown in Fig. 8 (a, b, c,
fraction of better crystalline copper selenide phase dec- and d).The ratio between the copper and selenide peaks
reases in the films, the extended localization in the should be near about one. From the graph, it is noted that
conduction and valence bands decreases [16,17]. The for bath composition of 0.05 M CuSO4  5H2Oþ0.025 M SeO2;
optical band gap energy reduces to that of the crystall- the atomic percentage of copper is 45.95, while that of selenide
ine copper selenide. It has been reported that the thermal is 54.05, for bath composition of 0.1 M CuSO4  5H2Oþ0.05 M
stability and the band gaps of copper selenides vary SeO2; the atomic percentage of copper is 47.80, while that
depending on their stoichiometries or phases [16,17]. of selenide is 52.20, for bath composition of 0.15 M
Similar values of the band gap energy of copper selenide CuSO4  5H2Oþ0.075 M SeO2; the atomic percentage of copper
54 S.S. Dhasade et al. / Materials Science in Semiconductor Processing 30 (2015) 48–55

Fig. 8. EDAX patterns of copper selenide thin films for (a) bath composition of 0.05 M CuSO4  5H2Oþ0.025 M SeO2; (b) bath composition of 0.1 M
CuSO4  5H2Oþ0.05 M SeO2; (c) bath composition of 0.15 M CuSO4  5H2Oþ 0.075 M SeO2 and (d) bath composition of 0.2 M CuSO4  5H2Oþ 0.1 M SeO2, with
deposition time of 20 min.

is 50.39, while that of selenide is 49.61 and for bath composi- technique. CuSe nanorods are polycrystalline in nature and
tion of 0.2 M CuSO4  5H2Oþ 0.1 M SeO2; the atomic percen- size of nanorods depends on the precursors concentrations.
tage of copper is 54.43, while that of selenide is 45.57. From The band gap of copper selenide depends on their stoichio-
these percentages, it is to be realized that copper selenide thin metries. The optical band gap of as deposited CuSe thin film
films are nearly stoichiometric. changes from 2.35 eV to 2.54 eV. So, precursor concentra-
tion influence on the structural, morphological and optical
4. Conclusions properties of CuSe thin films. These properties play an
important role in the device fabrication. These fundamental
It is concluded that, as deposited copper selenide (CuSe) properties provide basic information for the solar cell
thin films successfully deposited by the electrodeposition fabrication which is prime requirement for the engineers.
 S.S. Dhasade et al. / Materials Science in Semiconductor Processing 30 (2015) 48–55 55

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