Chemical Physics Letters 534 (2012) 34–37

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Chemical Physics Letters

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Quaternary Cu2CdSnS4 nanoparticles synthesized by a simple solvothermal method

Meng Cao a,b,⇑, Liang Li a, Wen Zhe Fan a, Xiu Yong Liu a, Yan Sun b, Yue Shen a
a
School of Materials Science and Engineering, Shanghai University, Shanghai 200072, China
b
National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Sciences, Shanghai 200083, China

a r t i c l e i n f o a b s t r a c t

Article history: Quaternary Cu2CdSnS4 nanoparticles, which are useful for the photovoltaic applications, were success-
Received 16 January 2012 fully synthesized by using a simple solvothermal route. Slightly polydispersed nanoparticles were
In final form 2 March 2012 obtained at temperature of 180 °C, analyzed by transmission electron microscopy (TEM). The cernyite
Available online 19 March 2012
structured Cu2CdSnS4 nanoparticles were confirmed by X-ray diffraction (XRD). The morphology and
the stoichiometric ratio of the nanoparticles were characterized by scanning electron microscopy
(SEM) and energy dispersive X-ray analysis (EDX). The chemical states of the elements in the nanoparti-
cles were analyzed by high-resolution X-ray photoelectron spectroscopy (XPS). The band gap of the as-
synthesized Cu2CdSnS4 nanoparticles was determined by UV–Vis absorption spectra measurement.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction their structure, morphology, valence and optical properties were

Chalcopyrite semiconductors have attracted intense interests re-
cently due to their appropriate band gaps and high absorption coef-
ficients for solar cell applications [1,2]. For example, high efficiency
close to 20% has been achieved based on CuInGaSe2 (CIGS) solar
cells [3]. The quaternary kesterite compound Cu2ZnSnS4 (CZTS) is
also one promising absorption layer material of thin film solar cells
due to its highly suitable optical properties and containing only
abundant and non-toxic elements [4]. Many kinds of methods have
been studied to prepare Cu2ZnSnS4 thin films, such as co-sputtering
[5], thermal evaporation [6], sol–gel [7], spray pyrolysis [8],
chemical bath deposition [9], hot injection method [10] and so
on. For example, high qualities of CIGS and CZTS nanoparticles
were prepared by hot injection method to form nanoparticle inks
[11,12]. Solar cells based on Cu2ZnSn(S,Se)4 nanoparticles
have achieved the power conversion efficiency as high as 10.1%
[13]. Recently, we synthesized high quality CZTS nanoparticles by
solvothermal method whose synthesis process was even easier
[14].
Cu2CdSnS4 with the band gap of 1.37 eV was also considered as
possible photovoltaic material [15]. Because it has similar struc-
ture with that of CZTS and they belong to an entire class of quater-
nary materials. So, the structural, thermodynamical and optical
properties of the Cu2CdSnS4 thin films also attracted great interests
[16]. In this Letter, Cu2CdSnS4 nanoparticles were also synthesized
through solvothermal method at the temperature of 180 °C. And
⇑ Corresponding author at: School of Materials Science and Engineering, Shanghai
University, 149 Yanchang Rd., Shanghai 200072, China. Fax: +86 21 56332694.
E-mail address: caomeng@shu.edu.cn (M. Cao).
studied, which will contribute to the exploration of new photovol-
taic materials.
2. Experimental
In a typical experimental procedure, the product Cu2CdSnS4
nanoparticles can be prepared from a stoichiometric mixture of
analytical grade CuCl2, (C2H3O2)2Cd, SnCl4 and S. The reagents were
added into a stainless steel autoclave with a Teflon liner, which
was filled with ethylenediamine and benzened up to 85% of the to-
tal volume (40 mL). The autoclave was sealed and maintained at
180 °C for 15 h, then allowed to cool to room temperature natu-
rally. Then, 5 mL of chloroform and 40 mL of isopropanol were
added into the reaction mixture and the nanoparticles were col-
lected using centrifuge at 10 000 rpm for 10 min. After centrifuge,
the supernatant was decanted, and the precipitates were redi-
spersed in 40 mL of chloroform to form a stable ink solution.
The crystalline structure of the sample was analyzed by using a
Rigaku D/max 2200 V X-ray diffractometer with high-intensity Cu
Ka radiation (k = 0.15418 nm). The surface morphology and the
elemental composition were recorded using a FEI Sirion 200 scan-
ning electron microscope (SEM) attached with an energy disper-
sive X-ray analysis (EDXA). The morphology was also
investigated by JEOL 2010F transmission electron microscopy
(TEM). X-ray photoelectron spectroscopy (XPS) spectra were mea-
sured by an ESCA commercial instrument (sigma Probe, Thermo
VG-Scientific). Optical absorption measurements were obtained
by employing a UV–Vis spectrophotometer (Lamda-2) and chloro-
form was used as a reference.

0009-2614/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cplett.2012.03.016
 M. Cao et al. / Chemical Physics Letters 534 (2012) 34–37 35

(a)

Element Wt% At%

(b)
S SK 24.80 47.65
SnL 20.92 12.77
CuK 29.85 25.70
CdK 24.43 13.88

Cd
Cu Sn
Cu
Figure 1. XRD pattern of as-synthesized (a) and annealed (b) Cu2CdSnS4
nanoparticles.
0 200 400 600 800 1000
Energy(Kev)

Figure 3. SEM (a) and EDX (b) characterization of as-synthesized Cu2CdSnS4

nanoparticle thin films.

Figure 2. TEM characterization of annealed Cu2CdSnS4 nanoparticles.

36 M. Cao et al. / Chemical Physics Letters 534 (2012) 34–37

3. Results and discussion

As a strongly polar solvent, ethylenediamine plays an important

(ahv)2 (a.u.)
role in the formation of quaternary Cu2CdSnS4 nanoparticles in the

Absorbance (a.u.)
synthetic process. A nucleophilic attack by ethylenediamine can
activate elemental sulfur to form S2. In this electron transfer reac-
tion, Cu2+ was also reduced to Cu+ ion by ethylenediamine. Then,
Cu+ complexes with ethylenediamine to form [Cu(en)2]+, which
can effectively prevent the formation of binary copper chalcoge- 1 2 3
nides. So, the reactions shown in Eqs. (1)–(5) may occur in the Bandgap(eV)
solvothermal process.

CdðCH3 COOÞ2 þ S2 ! CdS þ 2CH3 COO ð1Þ

 400
SnCl4 þ 2S2 ! SnS2 þ 4Cl
2
CdS þ SnS2 þ 2S2 $ CdSnS4
þ þ
Cu þ 2en $ ½CuðenÞ2 
2
CdSnS4 þ ½CuðenÞ2 þ ! Cu2 CdSnS4 þ 2en
Figure 1a shows the XRD pattern of the as-synthesized
Cu2CdSnS4 nanoparticle thin films dip coated onto the quartz sub-
strate. The diffraction peaks at 2h = 28.0°, 32.3°, 36.5°, 46.7°, 55.8°,
67.2°, 75.2°, 87.2° can be attributed to the diffraction of (1 1 2),
(2 0 0), (2 0 2), (2 2 0), (3 1 2), (4 0 0), (3 3 2) and (4 2 4) orientation
of cernyite structure of Cu2CdSnS4 (JCPDS 29-0537). Beside these,
CdS and CuS nanoparticles were also found to be existed because
the peaks at 2h = 24.8, 43.8 were diffracted from (1 0 0), (1 1 0) ori-
entation of orthorhombic structured CdS (JCPDS 47-1179) and the
peak at 2h = 21.8° correspond to (0 0 4) orientation of hexagonal
structured CuS (JCPDS 65-3928). After annealed at 500 °C for one
hour in Ar/H2S (5%) mixed atmosphere, the crystallinity and the
purity of Cu2CdSnS4 nanoparticles were enhanced greatly, as indi-
cated from the XRD pattern in Figure 1b. None diffraction peaks
indicated the existing of CdS and CuS in the nanoparticles. The full
width at half maximum (FWHM) of the strongest diffraction peak
of the (1 1 2) plane of Cu2CdSnS4 nanoparticles were 0.82 and
0.24 eV, respectively. According to Debye–Scherrer formula [17]:
D = 0.89k/(B cos(h)) (k is the incident X-ray wavelength, B is the
800 1200 1600 2000
ð2Þ
Wavelength(nm)
ð3Þ
Figure 5. Absorbance measurement of annealed Cu2CdSnS4 nanoparticles, the inset
ð4Þ shows an obtained band gap of 1.35 eV.
ð5Þ
FWHM of diffraction peak, h is the diffraction angle), the diameter
D of as-synthesized and annealed Cu2CdSnS4 nanoparticle were
evaluated to be about 10.9 and 36.3 nm, respectively. After anneal-
ing process, the sizes of the nanoparticles become bigger which is
beneficial to fabricate much higher efficiency solar cells, because
the saturation current density is relatively low for bigger grain size
due to its long minority-carrier diffusion length, which will pro-
mote the increase of the open-circuit voltage of the solar cells
[18,19].
Figure 2a shows the TEM image of the annealed Cu2CdSnS4
nanoparticles. The nanoparticles are slightly dispersed and the size
of the separated nanoparticle is about 30–35 nm, which agrees
well with the calculated value from the XRD pattern. High-resolu-
tion TEM of the individual nanocrystal in Figure 2b demonstrates
the crystalline nature of the Cu2CdSnS4 nanoparticles. The clear lat-
tice fringe with interplanar spacing of 3.15 Å corresponds to the
(1 1 2) plane of Cu2CdSnS4 nanoparticles. Meanwhile, the selected
area electron diffraction (SAED) pattern in Figure 2c matches the
structure of Cu2CdSnS4, as indicated by the diffraction spots corre-

2p3/2
Cu2p 3d5/2 Cd3d
3d3/2
Intensity(a.u.)
Intensity(a.u.)

2p1/2

920 930 940 950 960 405 410 415

Binding Energy (eV) Binding Energy (eV)

3d5/2 S2p
Sn3d 2p3/2
2p1/2
Intensity(a.u.)

Intensity(a.u.)

3d3/2

480 485 490 495 500 158 160 162 164 166
Binding Energy (eV) Binding Energy (eV)

Figure 4. XPS characterization of annealed Cu2CdSnS4 nanoparticles.

 M. Cao et al. / Chemical Physics Letters 534 (2012) 34–37
sponding to the (1 1 2), (2 2 0) and (3 1 2) planes. The surface image
of the spin coated Cu2CdSnS4 nanoparticle thin films on the silicon
substrate was shown in Figure 3a. The continuous and compact
films indicated the suitable application in solar cells because nano-
crystal thin films of better quality is very critical to the perfor-
mance of the solar cells. In fact, to be applied as the absorber
layer materials, various kinds of methods have been tried to pre-
pare the high quality nanoparticle thin films such as surgical knife
method and so on [20]. EDX measurements of Cu2CdSnS4 nanopar-
ticle thin films indicated that the chemical composition ratios of
Cu:Cd:Sn:S were close to 2:1:1:4, as shown in Figure 3b. To control
the composition ratios exactly, high reactivity of sulfur element
but low reactivity of the copper element should be selected in
the precursors to avoid copper rich or sulfur deficiency of the nano-
particles [21].
Figure 4 shows the high-resolution XPS analysis of the four con-
stituent elements of annealed Cu2CdSnS4 nanoparticles. The copper
2p peaks located at 935 and 954.8 eV indicative of Cu(I) with a
peak separation of 19.8 eV [22]. The cadmium 3d spectrum shows
peaks at 404.9 and 411.7 eV, and a peak splitting of 6.8 eV indicates
Cd(II) [23]. The tin 3d peaks located at 486.4 and 494.9 eV confirm
the Sn(IV) [24]. The sulfur 2p peaks located at 161.1 and 162.1 eV
in the spectra consist with the 160–164 eV range of S in sulfide
phases [25].
Figure 5 shows the UV–Vis absorption spectroscopy of the
Cu2CdSnS4 nanoparticles. As known, Cu2CdSnS4 is a direct band
gap semiconductor, so the band gap value can be estimated from
the absorption spectra according to the following equation [26]:
a2 ¼ Aðhv  Eg Þ (A is a constant.). By extrapolating the straight por-
tion of the curve to zero absorption coefficient, the determined
bang gap value of Cu2CdSnS4 nanoparticles is about 1.35 eV, as
shown in the inset of the Figure 5. Its value is close to the optimum
for solar cell applications.
4. Conclusion
In conclusion, Cu2CdSnS4 nanoparticles were successfully syn-
thesized by a simple solvothermal process. Cernyite structured
Cu2CdSnS4 nanoparticles with nearly stoichiometric were ob-
tained. The narrow FWHM of the XRD pattern and the clear crystal
lattices of the annealed nanoparticles shown by HR-TEM indicate
their high quality. The band gap of annealed Cu2CdSnS4 nanoparti-
cles was about 1.35 eV indicating the suitable optical properties for
efficient solar energy conversion.
37
Acknowledgements
The work was supported by National Basic Research Program of
China (2012CB934300), National Nature Science Foundation of Chi-
na (61006089), Shanghai City Committee of Science and Technol-
ogy (11ZR1412700), Innovation Program of Shanghai University.
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