Arabian Journal of Chemistry (2019) 12, 2439–2447

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Simple one-pot sonochemical synthesis of copper

sulphide nanoparticles for solar cell applications
Alok Singh a, R. Manivannan b, S. Noyel Victoria a,*

a
Department of Chemical Engineering, National Institute of Technology Karnataka, Surathkal, Karnataka 575025, India
b
Department of Chemical Engineering, National Institute of Technology Raipur, Chhattisgarh 492010, India

Received 26 November 2014; accepted 21 March 2015

Available online 27 March 2015

KEYWORDS Abstract Copper sulphide nanoparticles for solar cell applications were synthesized by a single
Sonication; step sonochemical method using copper acetate and thiourea as precursors. The effects of
Copper sulphides; sonication time, ultrasonic bath temperature and annealing temperature on particle properties
Nanoparticles; were studied. Synthesized particles were characterized using scanning electron microscope, trans-
XRD; mission electron microscope, X-ray diffraction spectrophotometer and UV–visible spectropho-
SEM; tometer. The particles were found to be a mixture of chalcocite, covellite and djurleite. The
TEM optical band gap of the particles was found to be in the range of 1.6–2.1 eV. Heat treatment of
the particles was found to give rise to needle shaped particles while a bath temperature of 55 C
yielded few nanoplates.
ª 2015 The Authors. Published by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction characteristic band gap, high extinction coefficient which

makes them an ideal candidate for solar cells applications as
In recent times the synthesis of metal chalcogenide nanoparti- light absorbers (Saraf, 2012). Simplest among the semiconduc-
cles has gained importance because of their unique properties tor metal chalcogenides are copper sulphides which fall in the
at the nanoscale when compared to their bulk counterparts. binary semiconductor category. The CuxS, which is a P-type
Such unique properties of the semiconductor nanoparticles semiconductor with the copper vacancies as acceptor sites with
make them an ideal candidate for photovoltaic applications x taking values between 1 and 2, Cu2S (chalcocite), CuS (cov-
(Kassim et al., 2010). Of the semiconducting materials, their ellite), Cu1.96S (djurlite), Cu1.8S (digenite), Cu1.75S (anilite) are
metal sulphides are studied in abundance because of their more common (Zhao et al., 2009, 2010). The optical properties
of CuxS greatly depend on the copper vacancies (Zhao et al.,
* Corresponding author. Tel.: +91 824 2474 3608; fax: +91 824 2009). The CuxS have varying band gap depending on the
2474 4033. value of x, for instance, Egind is 1.05 eV and Egdir is 1.7 eV
E-mail address: [email protected] (S. Noyel Victoria). when x takes the value 2 which is for Cu2S (Chalcocite)
Peer review under responsibility of King Saud University. whereas djurleite which has x in the range from 1.935 to
1.955, Egdir takes the value 1.3 eV (Nair et al., 1998). The elec-
trical conductivity of the material also varies with composition
from 0.07 to 2400 ohm1 cm1 when x varies from 2 to 1.8
Production and hosting by Elsevier (Nair et al., 1998). The CuxS thin films are effectively used in

http://dx.doi.org/10.1016/j.arabjc.2015.03.013
1878-5352 ª 2015 The Authors. Published by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2440 A. Singh et al.

solid junction solar cells which have many applications as it is 2. Experimental

a direct energy conversion device (Sartale and Lokhande,
2000). The short-circuit current (Isc) of a heterojunction solar 2.1. Material
cell using CuxS as absorber layer solar cell is dependent on
the value of x. It was observed that with increase in the value
Copper sulphide nanoparticles were synthesized using liquid
of x, short-circuit current increases (Sartale and Lokhande,
phase synthesis method in the presence of ultrasonic irradia-
2000). The CuxS thin films have been found to have near ideal
tion. Copper acetate monohydrate (99%), thiourea (99%)
solar control features with the transmittance in the infrared
and NaOH (99%) were used as the precursor materials for
<10% and high reflectivity in the near infrared region (Isac
the synthesis. All the chemicals used were of analytical grade.
et al., 2007).
Deionized water was used for all the experiments. A 200 mM
There are reports on various stoichiometric copper sulphide
copper acetate solution was used as copper precursor.
nanoparticles synthesis by high temperature solution phase
Thiourea solution of 1.8 M was used as sulphur precursor.
methods (Ye and Qi, 2008), low temperature solution route
The pH of the thiourea precursor solution was 13.4.
(Ye and Qi, 2008), colloidal route (Boey et al., 2007),
microemulsion method (Solanki et al., 2010), sonochemical
2.2. Synthesis
route (Kumar et al., 2002; Wang et al., 2002), thermolysis
route (Larsen et al., 2003), microwave assisted heating (Liao
et al., 2003), solvothermal route (Gorai et al., 2005a; Gorai Bath type ultrasonicator (Elmasonic P60H) was used for the
et al., 2005b), chemical precipitation route (Pop et al., 2011), synthesis of the CuxS nanoparticles. To the copper precursor
electrophoresis deposition (Sabet et al., 2014) and successive solution in the ultrasonic bath, the sulphur precursor solution
ionic layer adsorption and reaction (SILAR) method (Sartale was added dropwise. The solution pH tends to drop with pro-
and Lokhande, 2000). However, the solvothermal route gress of reaction; however, it was maintained at pH 5.5 by add-
requires high pressure and temperature conditions, thermal ing NaOH. The temperature of the ultrasonic bath was
routes need high temperature conditions and liquid phase syn- maintained constant by circulating the cold water. Black pre-
thesis at low temperature involves more reaction time. cipitate formed was centrifuged and washed with acetone
Microwave method and sonochemical synthesis share an and distilled water at least ten times to remove the impurities.
advantage of reduced reaction time. The CuInS2 and CuS All the synthesis experiments were conducted at 37 kHz fre-
nanoparticles were reported to be synthesized by microwave quency. The experiment was performed at different bath tem-
method (Sabet et al., 2011; Sabet et al., 2012; Sabet et al., peratures and sonication times. The powder thus obtained was
2013; Yousefi et al., 2012a). Apart from CuInS2, various solar heated at various temperatures to study the effect of treatment
cell materials have also been synthesized and used microwave temperatures.
method (Yousefi et al., 2012b). The use of ultrasonic waves
for the nanoparticle synthesis has been in practice for many 2.3. Characterization
decades. Many metal and metal oxide nanoparticles have been
successfully synthesized using sonochemical method (Xu et al., The crystallinity of the synthesized samples was characterized
2003; Xu et al., 2013). Apart from these, the semiconductor by XRD (PANalytical 3 kW X’pert Powder XRD), surface
nanomaterials have also been synthesized using sonochemical morphology was studied using scanning electron microscope
methods (Gao et al., 2005; Xu et al., 2003; Xu et al., 2013; (JEOL) and composition was analysed using EDX station
Amiri et al., 2013; Amiri et al., 2014). Among the solar cell (JED-2300). The particle size was characterized using trans-
materials, CuInS2 has been synthesized by sonochemical route mission electron microscopy unit (TEM, JEOL 3010). The
(Amiri et al., 2013; Amiri et al., 2014). The ultrasonic irradia- optical characterization studies were done in UV–visible spec-
tion helps in refining the shape of the desired particle, changes trophotometer (Labomed UVD-3500). The thermal character-
the surface morphology and also helps in degassing of the ization was performed in a Perkin Elmer thermal analyzer. For
medium (Chu et al., 2006). The most dominant effects of ultra- electrical characterization, the CuxS sample was dispersed in
sonic waves are cavitation and acoustic streaming. The col- water and filtered to get a thick residue, which was coated
lapse of the bubbles causes hot spots with transient on an Indium coated tin oxide (ITO) substrate (Sigma
temperatures of 5000 K and cooling rates in excess of Aldrich, 25 X) using doctor blade technique. The coating
1010 K s1. These extreme conditions during sonication cause thickness for the samples varied between 4 lm and 5 lm. To
enhanced mixing, which helps in decreasing the particle size the coated slide another ITO coated glass slide was placed
and increasing the reactive surface area (Gao et al., 2005; Xu and IV characterization studies were made. The IV studies
et al., 2003; Xu et al., 2013). There is relatively less report on were conducted in a CHI660E (CH instruments, USA) electro-
the sonochemical synthesis of copper sulphides (Xu et al., chemical workstation. The linear sweep voltammetry was car-
2003; Xu et al., 2013). ried out with a scan rate of 0.1 V s1 in a potential range
The present work reports the single step sonochemical ±1 V.
synthesis of copper sulphide nanoparticles under various
reaction conditions. The morphology of particles was 3. Results and discussion
studied by scanning electron microscopy (SEM) and trans-
mission electron microscopy (TEM). The crystal nature of 3.1. X-ray diffraction
the particles was analysed by X-ray diffraction (XRD).
The optical properties were studied using UV–visible The results of the XRD analysis for the samples synthesized at
spectroscopy (UV–vis). different bath temperatures, different sonication times and
Simple one-pot sonochemical synthesis for solar cell applications 2441

different calcination temperatures are shown in Fig. 1. The It is also shown that increase in the sonication bath tempera-
XRD results in all the cases show high intensity peaks at 2h ture along with increased sonication time resulted in decreased
values of 31.7 and 32.7 which corresponds to Cu1.92S and crystallinity (Yuliana et al., 2012). The deceased crystallinity
tetragonal Cu1.81S, in accordance with the JCPDS 30-0505 with increase in the sonication time could be due the formation
and 41-0959 respectively (Andronic et al., 2011; Ye et al., of hot spots during the collapse of cavitation and physical
2014). The medium intensity peaks at 37.2, 42.5, 44.8, stress due to the acoustic cavitation (Sumari et al., 2013).
48.3 and 51.5 show the presence of hexagonal Cu2S The loss of crystallinity during heating could be due to libera-
(JCPDS-26-1116) with lattice constant a = 3.9610 A, tion of gases during transformation of CuS to other forms
b = 3.9610 A and c = 6.7220 A (Head, 2009). The peaks at (Yousefi et al., 2012b).
33.8 and 35.2 show the presence of Cu1.97S, orthorhombic The crystallite size of the particles under various reaction
djurleite (JCPDS-20-0365). In fact, these peaks also match conditions was calculated using Debye–Scherrer equation
with chalcocite phase (JCPDS-31-0482). Peaks at 42, 50 (Eq. (1)) (Vasuhi et al., 2014):
and 56 correspond to rhombohedral digenite, Cu1.8S Kk
(JCPDS 26-0476 and 47-1748) with a = 3.951 and c = 48.13 t¼ ð1Þ
bcosh
A (Ramirez et al., 2014; Kumar et al., 2012). The particles syn-
thesized at 55 C show decreased intensity and broadening of where t is crystallite size, K is a crystallite shape factor which
the peaks with increase in sonication time. A decrease in the takes the value of 0.9, k is the wavelength of X-ray which is
intensity of the peaks with broadening of the peaks indicates 0.154 nm for Cu Ka, b is full width at half maximum
decreased crystallinity and decrease in size of the particles (FWHM) in radians and h is the Bragg’s diffraction angle.
(Vasuhi et al., 2014). The amorphous nature increases with The crystallite sizes thus calculated are presented in Table 1.
the sonication time (Vasuhi et al., 2014). The particles synthe- The crystallite size decreases with increase in sonication time
sized with 60 min sonication time at different bath tempera- for the samples synthesized while maintaining the bath tem-
tures also showed decreased crystallinity with increase in perature at 35 C. The crystallite size of the particles was found
bath temperature. The heat treatment of the sample synthe- to increase for the particles synthesized at different bath tem-
sized at 45 C bath temperatures with 60 min sonication time peratures with 60 min sonication time. However, the crys-
also showed similar trend of decreased crystallinity with tallinity is lost completely at an ultrasonic bath temperature
increase in treatment temperature. Decreased crystallinity with of 55 C. The particles synthesized at 45 C bath temperatures
sonication treatment time was also observed in the case of cel- with 60 min sonication time showed an increase in crystallite
lulose and chitosan (Sumari et al., 2013; Yuliana et al., 2012). size at 100 C and 200 C but decreased for heat treatment at
400 C.

3.2. UV–vis spectroscopy

C 100 ͦC 200 ͦC 400 ͦC
The absorbance characteristics of the samples synthesized
under different sonication times at 35 C bath temperature
are shown in Fig. 2. All the particles show a broad absorption
peak over the entire visible region. The broad absorption peak
over the entire visible region is a desirable feature for solar cell
window material. The absorbance pattern also shows absor-
bance in the near infrared region towards visible range, which
makes it ideal for solar cell application (Vasuhi et al., 2014). A
b 55 ͦC 45 ͦC 35 ͦC sharp increase in the absorbance in the wavelength range
Intensity (a.u)

500 nm matches with the earlier reports and it is close to the

effective band gap of Cu2S (Vasuhi et al., 2014). The band

Table 1 Crystal size and band gap of copper sulphide

a 20 min 30 min 60 min synthesized at different conditions.
Sonication Ultrasonic Heat treatment Crystal Band
time (min) bath temperature size (Å) gap
temperature (C) (eV)
(C)
20 35 Air dried 28.11 1.75
30 35 Air dried 27.42 1.8
30 40 50 60 70 60 35 Air dried 25.58 1.8
2θ (degrees) 60 45 Air dried 29.13 2
60 55 Air dried 39.61 2.1
Figure 1 XRD patterns of copper sulphide particles synthesized 60 45 100 35.16 1.3
at different conditions. a. sonication time, b. sonication tempera- 60 45 200 40.76 1.5
ture and c. annealing temperature ( – Cu1.98S, – Cu2S, 60 45 400 34.50 1.6
– Cu1.92S, – Cu1.81S, – Cu1.8S).
2442 A. Singh et al.

gap of the synthesized particles was calculated using the Tauc 7

relation (Eq. (2)) (Mehta et al., 2009): 6 45
45ºCC c
eht ¼ Aðht  Eg Þ n
ð2Þ 5 55 C
55ºC

4
where e is the molar extinction coefficient, A is a constant, Eg is
optical band gap of the sample and ht is photon energy. In Eq. 3
(2), n depends on type of transition which is ½ and 2 for direct 2
and indirect allowed transitions respectively. The (eht)2 values 1
are plotted with ht values, and the intersection of the slope to 0
curve at x axis gives the optical band gap of the synthesized 0 1 2 3 4 5
CuxS nanoparticles. The Tauc plots for all the samples are
shown in Fig. 3. The band gap values calculated from the 16

(αhυ)2 (x 1015 cm-2 eV2)

Tauc plots are shown in Table 1. It is clear from Table 1 that 100º C b
14 100 C

the optical band gap of the particles slightly increases from 200º C
200 C

1.75 eV to 1.8 eV with increase in sonication time at a constant 12

400º C
400 C

bath temperature of 35 C. The crystallite size increases with 10

increase in the bath temperature at a constant sonication time
8
of 60 min. Generally the band gap should decrease for larger
sized particles. However, from Table 1, it is seen that with 6
increase in the size of the particles the band gap increases. 4
The XRD studies reveal that the amorphous nature of the par- 0 1 2 3 4 5
ticles increases with increase in sonication bath temperature.
The band gap of the amorphous particles is reported to be 2
20 min
higher when compared to their crystalline counterparts. The a
30 min
increased degree of disorder in amorphous particles results in
60 min
decreased absorbance leading to higher band gap energy
(Rotaru et al., 1999). The optical band gap of the particles
1
heated at 100 C is 1.3 eV whereas for the particles heated at
400 C the band gap increased significantly to 1.6 eV which
can also be explained by the loss of crystallinity and
accompanying phase transformation. The transmittance spec-
tra for the particles synthesized at various conditions are 0
shown in Fig. 4. The transmittance spectra for the particles 1 2 3
synthesized under different sonication times show decreased hυ (eV)
transmittance values with time. However, they show an
increasing trend in the transmittance values in the lower wave- Figure 3 Tauc plot for copper sulphide particles synthesized at
length region and decreasing trend in the higher wavelength different conditions. (a) Sonication time, (b) annealing tempera-
range. This phenomenon is reported earlier when Cu2S was ture and (c) sonication temperature.
deposited using chemical bath deposition (Vasuhi et al.,
2014). The increase in transmittance in the shorter wavelength
region is attributed to the inter-band transitions from valence trend. The samples annealed at 400 C showed higher trans-
band towards the conduction band. The decrease in transmit- mittance value in all the wavelengths. The heat treatment
tance in the higher wavelength zone is due to the increase in was found to increase the optical transmittance values in all
carrier concentration (Vasuhi et al., 2014). Particles synthe- three calcination temperatures. All the particles synthesized
sized under different bath temperatures also showed similar under various conditions show maximum absorbance in the
wavelength range from 630 nm to 680 nm. The transmittance
values in all the cases are above 50% which makes them an
1.2 ideal candidate for solar control coatings (Vasuhi et al., 2014).
20 min
1
30 min 3.3. Scanning electron microscopy (SEM) and transmission
Absorbance (a.u)

0.8 60 min electron microscopy (TEM)

0.6
Fig. 5(a)–(d) shows SEM images of the CuxS particles synthe-
0.4 sized at various reaction conditions. The scanning electron
microscopy (SEM) results show that the size of the particles
0.2 reduces with sonication time. The particles synthesized at
0
45 C bath temperature with 60 min sonication time show rela-
380 480 580 680 780 880 tively low polydispersity. The particles synthesized at 55 C
Wavelength (nm) bath temperature and 60 min sonication time show the pres-
ence of few nanoplates. The particle size increases with the
Figure 2 Absorbance spectra of copper sulphide particles temperature of the sonication bath. The XRD analyses also
synthesized at different sonication time. show that the crystallite size increases with increase in
Simple one-pot sonochemical synthesis for solar cell applications 2443

100 100
20 min a 400⁰⁰C b

Transmittance (%)
Transmittance (%)
80 30min 80 200⁰C
60 min
35⁰⁰C
60 60 100⁰C

40 40
45⁰C
20 20 55⁰C

0 0
380 580 780 380 580 780
Wavelength (nm) Wavelength (nm)

Figure 4 Transmittance spectra of the copper sulphide particles synthesized at different conditions. (a) Sonication time and (b)
sonication temperature and annealing temperature.

sonication bath temperature. Sonication at higher tempera- the particles are crystallized and the diffraction pattern
tures has been linked to the formation of larger sized particles matches with the XRD peaks well, as seen in Fig. 6d.
due to agglomeration or reducing intensity of collapse due to
the cushioning effect of the increasing cavity vapour pressure 3.4. IV Characterization
at higher temperatures (Ambedkar, 2012). The formation of
nanoplates at 55 C could be attributed to the above-men- Fig. 7a–c shows the current voltage characteristics of ITO/
tioned effects. Particles synthesized at 45 C with 60 min son- CuxS/ITO structures in the presence and absence of 200 W
ication time, when calcined at 400 C showed the formation light source which was kept at a height of 55 cm from the sam-
of needle like nanorods. These could be due to the trans- ple. The CuxS synthesized at different sonication bath tem-
formation of CuS to other forms during heat treatment. peratures were used to form coating. Fig. 8a–c shows the IV
Such morphological changes due to transformation are con- curves of the samples heated at different temperatures. In all
firmed from the earlier work which reported the formation the cases, the IV curves show linear behaviour which suggests
of tetragonal Cu1.81S from Cu1.9S resulted in the change in the ohmic nature of the CuxS. The resistance for the samples
morphology from nanospheres to nanorods (Li et al., 2014; synthesized at different sonication bath temperatures is
Yousefi et al., 2012b). The TEM images of the particles synthe- 0.03 X cm2 and for the heat treated samples is 0.05 X cm2.
sized at 45 C with 1 h sonication time are shown in Fig. 6. It is The IV studies show that the coating is conductive with mini-
seen from Fig. 6-a, that most of the particles are spherical with mum resistance.
few nanorods. The size of the particles is in the range of 15–
20 nm. The lattice spacing of the particle shown in Fig. 6b 3.5. Thermal characterization
was found to be 0.19 nm which corresponds to the monoclinic
Cu1.8S (Tiong et al., 2014). The lattice spacing of the particle in
Fig. 9 shows the results of the thermogravimetric analysis
Fig. 6c is 0.33 nm, which corresponds to Cu2S (Ding et al.,
(TGA) of the CuS nanoparticles synthesized at 35 C bath
2012) as in Fig. 6c. The SAED measurements confirmed that

Figure 5 SEM images of copper sulphide particles synthesized at different sonication temperature. (a) 45 C bath temperature 1 h
sonication time, (b) 55 C bath temperature 1 h sonication time, (c) 45 C synthesized particle at 100 C calcination and (d) 45 C
synthesized particle at 400 C calcination.
2444 A. Singh et al.

a b

0.19 nm

50 nm 5 nm

d
c

0.33 nm

10 nm 10 1/nm

Figure 6 TEM images of copper sulphide particles synthesized at sonication time of 60 min at 45 C and air dried (without annealing).
(a) TEM image showing the morphology, (b) TEM image showing the lattice spacing of 0.19 nm – monoclinic Cu1.8S, (c) TEM image
showing the lattice spacing of 0.33 nm – Cu2S and (d) SAED pattern of synthesized particle.

Figure 7 IV characteristic curves of ITO/CuxS/ITO with the CuxS synthesized at various sonication bath temperatures. (a) 35 C, (b)
45 C, (c) 55 C. The solid line represents IV curves in the presence of 200 W light source and the dotted lines represent dark.

temperature with 60 min sonication time. The TGA was con- sulphides (Cu1.8S, Cu2S), copper oxides (Cu2O, CuO), copper
ducted in the oxygen environment from 50 C to 700 C with sulphates (Cu2SO4, CuSO4), and copper oxy-sulphates as
a heating rate of 15 C min1. Fig. 10 shows the differential products (Nafees et al., 2013). In general, the increase in mass
scanning calorimetry (DSC) results for the same sample from is attributed to the formation of sulphates and loss of mass is
room temperature to 350 C. The thermogram shows weight believed to be associated with oxidation, release of sulphur
loss of approximately 42% with various decomposition stages. dioxide and evaporation of water (Dunn and Muzenda,
It was shown by the earlier studies that the CuS decomposition 2001). The DSC studies show endothermic peaks at 100 C,
in air follows many steps with various forms of copper 123 C and at 225 C. The endothermic peak at 100 C and
Simple one-pot sonochemical synthesis for solar cell applications 2445

Figure 8 IV characteristic curves of ITO/CuxS/ITO with the CuxS synthesized at various heat treatment temperatures. (a) 400 C, (b)
200 C and (c) 100 C. The solid line represents IV curves in the presence of 200 W light source and the dotted lines represent dark.

100 2CuS þ O2 ! Cu2 S þ SO2 ð4Þ

90 3.6. Mechanism
Weight (%)

80
The reaction was conducted in alkaline medium. The use of
70
copper acetate monohydrate leads to the reduction in pH with
the progress of the reaction, which was adjusted by addition of
60 excess NaOH. The series of reactions involved in the formation
of CuxS are given below:
50 H2 O ÞÞÞÞÞ H þ OH ð5Þ
0 100 200 300 400 500 600 700

H2 NCSNH2 þ 2OH ! 2NH3 þ CO2 þ S2 ð6Þ

Figure 9 Thermogram of CuxS particles synthesized at 35 C
bath temperature with 1 h sonication time (in the oxygen S2 þ S2 ! ðS . . . SÞ3 ! ðS . . . SÞ2 ð7Þ
environment).
xCuðII or IÞ þ S2 ðor S2
2 Þ ! Cux S ð8Þ

123 C and the corresponding weight loss could be due to the In an aqueous sonochemical process, the pyrolysis of water
evaporation of water (Simonescu et al., 2007). The peak at occurs due to the elevated temperature and pressure conditions
225 C may be due to the transformation of CuS to cubic inside the collapsing bubble (Wang et al., 2002). The possible
digenite (Nafees et al., 2013; Simonescu et al., 2007; Dunn products of the water pyrolysis reaction are shown in Eq. (5)
and Muzenda, 2001). This initial reaction in the temperature (Sheng et al., 2008). The thiourea undergoes hydrolysis reac-
range from 220 C to 260 C is given by tion resulting in the production of S2 ions (Eq. (6)) (Sheng
et al., 2008). The reaction is also accompanied by reduction
1:8CuS þ 0:8O2 ! Cu1:8 S þ 0:8SO2 ð3Þ of Cu(II) to Cu(I), which changes the colour of the precursor
A second reaction occurs between 300 C and 370 C result- solution from blue to aqua (Sheng et al., 2008). The formation
ing in the formation of Cu2S (Dunn and Muzenda, 2001) which of CuxS particles is given by the Eq. (8) (Sheng et al., 2008).
corresponds to the weight loss in that temperature interval. No
significant weight loss was observed from 400 C to 700 C. 4. Conclusion

50
An attempt to synthesize CuxS by sonochemical route was
made. The synthesized particles were mixture of Cu1.8S,
Endo Cu2S and Cu1.97S. The band gap of the particles was in the
Heat flow (mW)

40
range of 1.3–2.1 eV. The crystallite size and composition were
found to influence the optical band gap. Spherical shaped par-
30
ticles and nanorods were formed at 45 C bath temperature
with 1 h sonication time. Particles synthesized at 55 C bath
20
temperature with 1 h sonication time showed the presence of
nanoplates and the particles synthesized at 45 C with 1 h son-
10
ication time upon calcination at 400 C showed the presence of
needle like nanocrystals. The TGA shows that the heat treat-
0
25 125 225 325 ment causes the formation of amorphous product due to evap-
oration of water and sulphur dioxide formation and
transformation of CuS to other forms. The IV characterization
Figure 10 DSC of CuxS particles synthesized at 35 C bath shows that the deposit exhibits ohmic nature with a resistance
temperature with 1 h sonication time. in the range 0.03 X cm2 to 0.05 X cm2.
2446 A. Singh et al.

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