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Alloyed (ZnS)x(Cu2SnS3)1x and (CuInS2)x(Cu2SnS3)1x nanocrystals
with arbitrary composition and broad tunable band gapsw
Qinghui Liu,ab Zechen Zhao,a Yuhan Lin,a Peng Guo,a Shenjie Li,a Daocheng Pan*a and
Xiangling Ji*b
Published on 15 November 2010. Downloaded by University of California - Irvine on 25/10/2014 16:13:49.
Received 30th August 2010, Accepted 13th October 2010
DOI: 10.1039/c0cc03560b
Cu2SnS3 nanocrystals with metastable zincblende and wurtzite
structures have been successfully synthesized for the rst time.
Alloyed (ZnS)x(Cu2SnS3)1x and (CuInS2)x(Cu2SnS3)1x nano-
crystals with arbitrary composition (0 r x r 1) and ultra-broad
tunable band gaps (3.63 to 0.94 eV) were obtained.
The ternary semiconductor Cu2SnS3 is one of the most important
group I-IV-VI semiconductors and has a high potential in
photovoltaic and photocatalytic applications due to its low cost,
high optical absorption coecient (up to 105 cm1), and
environmentally friendly properties.1 It is well known that
Cu2SnS3 possesses a tetragonal chalcopyrite structure at low
temperatures. According to the Cu2SnS3 phase diagram,2 the
tetragonal chalcopyrite structure is converted to a metastable
zincblende structure at temperatures higher than 780 1C, and
another high temperature metastable wurtzite phase for bulk
Cu2SnS3 has not been observed before Cu2SnS3 melts (mp.
856 1C). The zincblende structure of Cu2SnS3 can be considered
as being derived from the zincblende structure of ZnS (space
group, F-43m), where 2/3 and 1/3 Zn2+ cations are replaced by
Cu+ and Sn4+, respectively. Notice that Cu+ and Sn4+ are
randomly distributed in the Zn2+ positions, i.e. they occupy the
same position, and the sulfur positions are maintained in the unit
cell of zincblende ZnS. Fig. S1w shows the structure relations
between ZnS, CuInS2, and Cu2SnS3. Obviously, Cu2SnS3 should
have the same zincblende and wurtzite structures as ZnS. However,
there are no reports on the synthesis of zincblende and wurtzite
Cu2SnS3 nanocrystals at low temperatures in the literature.
It is well known that, in the synthesis of nanocrystals,
capping agent, reaction temperature, and the reactivity of
precursors strongly aect their crystalline phase.3 The crystal
structure obtained for nanocrystals can be dierent from the
structure usually obtained for the bulk materials. By changing
the reactivity of precursors and/or bonding strength of capping
agents, some of the high temperature and metastable phases
can be achieved for nanocrystalline materials by wet chemical
methods at low temperatures. Recently, we successfully
a addition, the zincblende and wurtzite structures of Cu2SnS3
State Key Laboratory of Rare Earth Resource Utilization,
Changchun Institute of Applied Chemistry, Chinese Academy of
Sciences, Graduate School of the Chinese Academy of Sciences, 5625
Renmin Street, Changchun 130022, China. E-mail: pan@ciac.jl.cn
b
State Key Laboratory of Polymer Physics and Chemistry, Changchun
Institute of Applied Chemistry, Chinese Academy of Sciences,
Graduate School of the Chinese Academy of Sciences, 5625 Renmin
Street, Changchun 130022, China. E-mail: xlji@ciac.jl.cn
w Electronic supplementary information (ESI) available: Detailed
information on the nanocrystal preparation; The Cu2SnS3 unit cell
and crystal data; XPS, EDS spectra and chemical compositions as well
as additional UV-Vis-NIR spectra. See DOI: 10.1039/c0cc03560b
964 Chem. Commun., 2011, 47, 964966
synthesized zincblende and wurtzite CuInS2 nanocrystals by
using oleic acid and dodecanethiol as the capping agents, respec-
tively.3d The crystalline structures of CuInS2 nanocrystals are
equivalent to those of ZnS. Therefore, it is also possible to obtain
the metastable zincblende and wurtzite phases for Cu2SnS3
nanocrystals at low temperatures. Although there are a number
of reports on the synthesis of nanocrystalline Cu2SnS3 in the
literature, almost all of them exhibited a tetragonal chalcopyrite
structure.4 In addition, hexagonal Cu2SnS3 nanocrystals were
reported by Xie et al., but the crystal structure they proposed is
totally dierent from a wurtzite structure (space group, P63mc),
because Cu+ and Sn4+ have a xed position rather than
randomly distributed in the unit cell, which reduces the space
symmetry of the unit cell and leads to the appearance of many
diraction peaks.5 To the best of our knowledge, zincblende and
wurtzite Cu2SnS3 nanocrystals have not been reported to date.
One of our aims in this paper is to synthesize zincblende and
wurtzite Cu2SnS3 nanocrystals by a wet chemical method at low
temperatures, which will enable the synthesis of homogenous
alloyed (ZnS)x(Cu2SnS3)1x and (CuInS2)x(Cu2SnS3)1x nano-
crystals with arbitrary composition and tunable band gaps.
Experimentally, Cu2SnS3 nanocrystals were synthesized by
the reaction of metal chloride and sulfur in the presence of
oleylamine. Oleylamine was used as the capping agent and
solvent. The crystal structure of Cu2SnS3 nanocrystals can be
controlled by changing the capping agents and the reactivity of
sulfur precursors. Detailed experimental procedure and
synthetic conditions were provided in the ESI and Table S1w.
Fig. 1 top shows the X-ray diraction (XRD) patterns of
Cu2SnS3 nanocrystals with zincblende and wurtzite structures.
It was found that our diraction patterns did not match those
reported in the literature4 and the standard JCPDS card
database (JCPDS No.27-0198). We therefore simulated the
diraction patterns for zincblende and wurtzite Cu2SnS3 and
compared them with the experimental patterns. As can be seen
in Fig. 1, the simulated and experimental patterns match very
well, signifying that these nanocrystals possess a zincblende
and a wurtzite structure rather than a chalcopyrite structure. In
nanocrystals were further conrmed by selected area electron
diraction (SAED) (Fig. 1, bottom). It is noteworthy that the
reactivity of the precursors and the bonding strength of the
capping agents strongly aect the crystalline structures of
Cu2SnS3 nanocrystals, and the mixture of zincblende and
wurtzite structures can also be obtained under certain
conditions. Detailed eects will be published elsewhere.
Semiconductors with tunable composition and band gaps
are of great interest for photovoltaic and photocatalytic
This journal is c The Royal Society of Chemistry 2011
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Fig. 2 Top: A series of XRD patterns of (ZnS)x(Cu2SnS3)1x and

Fig. 1 Top: XRD patterns of Cu2SnS3 nanocrystals with zincblende (CuInS2)x(Cu2SnS3)1x nanocrystals with a zincblende structure.
(black line) and wurtzite (red line) structures. Vertical lines are XRD Bottom: The calculated lattice parameters c of alloyed (ZnS)x
patterns simulated according to the Cu2SnS3 unit cells in Fig. S1w. Bottom: (Cu2SnS3)1x and (CuInS2)x(Cu2SnS3)1x nanocrystals as a function
SAED of zincblende (left) and wurtzite (right) Cu2SnS3 nanocrystals. of the Cu2SnS3 mole fraction.

toward lower angles with increasing and decreasing the

applications. The optimum band gap is around 1.3 eV for a
Cu2SnS3 content for alloyed (ZnS)x(Cu2SnS3)1x and (CuInS2)x
single junction solar cell, and dierent band gaps are also
(Cu2SnS3)1x nanocrystals. The zincblende latticepparameter
c
required for multi-junction devices.6 Cu2SnS3 has a band gap
was calculated via the following function: c 3d111 . The
of 0.93 eV,2 which does not make it a good choice for solar cells.
linear relationships between calculated lattice parameter c and
Therefore, alloying Cu2SnS3 with larger band gap ZnS has been
the Cu2SnS3 mole fraction were observed for both alloyed
extensively studied,7 aiming to expand the band gap of Cu2SnS3.
(ZnS)x(Cu2SnS3)1x and (CuInS2)x(Cu2SnS3)1x nanocrystals,
However, it is quite dicult to synthesize homogeneous (ZnS)x
which conrmed the formation of homogeneous alloys
(Cu2SnS3)1x alloys with arbitrary composition (0 r x r 1) due
according to Vegards law11 (Fig. 2, bottom).
to their dierent crystal structures (zincblende vs. chalcopyrite).8
Fig. 3 displays the UV-Vis-NIR absorption spectra of the
For example, Cu2ZnSnS4 (molar ratio, ZnS : Cu2SnS3 = 1 : 1)
(ZnS)x(Cu2SnS3)1x nanocrystals. Signicant red shifts of the
crystallizes in a tetragonal chalcopyrite structure,7,8 and phase
optical absorption band edges with increasing Cu2SnS3
separations will occur in ZnS-rich regions and Cu2SnS3-rich
content are clearly revealed. The calculated optical band
regions according to the phase diagram of the ZnSCu2SnS3
gaps of ZnS and Cu2SnS3 nanocrystals are 3.63 and 0.94 eV,
system.8 More recently, alloyed (ZnS)x(Cu2SnS3)1x (0 r x r
respectively, which are in good agreement with those of the
0.5, i.e. ZnS to Cu2ZnSnS4) nanocrystals with a sphalerite
corresponding bulk materials (3.68 and 0.93 eV),2 since their
structure were reported by Zhan et al., however, composition
can only be adjusted in a narrow range around 50% ZnS rather
than over the entire composition range.9 Our ndings point to a
way out of this dilemma, because we found that ZnS, CuInS2,
and Cu2SnS3 possess the same zincblende and wurtzite structures
at low temperatures. More importantly, our calculated lattice
mismatches between ZnS and Cu2SnS3 as well as CuInS2 and
Cu2SnS3 are only 0.4% and 1.9%, and such small lattice
mismatches make the growth of multiple component alloys quite
easy. In addition, the dierence in the reactivity of each precursor
must be insignicant for the synthesis of multi-component alloys,
otherwise phase-separation will occur.10 Thus, a highly reactive
oleylamine-sulfur complex was used as a sulfur precursor.
Fig. 2 top shows a series of XRD patterns for (ZnS)x
(Cu2SnS3)1x and (CuInS2)x(Cu2SnS3)1x nanocrystals with a Fig. 3 UV-Vis-NIR absorption spectra of (ZnS)x(Cu2SnS3)1x nano-
zincblende structure. The diraction peaks systematically shift crystals in tetrachloromethane with dierent ZnS to Cu2SnS3 ratios.

This journal is c The Royal Society of Chemistry 2011 Chem. Commun., 2011, 47, 964966 965

sizes are out of their exciton Bohr diameters. As expected, these
alloyed (ZnS)x(Cu2SnS3)1x nanocrystals indeed display
tunable band gaps in an ultra-broad tunable range from 3.63
to 0.94 eV, further conrming the formation of homogeneous
alloys instead of the mixture of their constituents. In addition,
alloyed (CuInS2)x(Cu2SnS3)1x nanocrystals also exhibited
tunable band gaps in the rang of 1.35 to 0.94 eV (Fig. S2w).
Published on 15 November 2010. Downloaded by University of California - Irvine on 25/10/2014 16:13:49.
These ndings enable the synthesis of the alloyed nanocrystals
with targeted band gaps, which can optimize the band gap-
dependent performances of solar cells and photocatalysts.
The chemical compositions of (ZnS)x(Cu2SnS3)1x and
(CuInS2)x(Cu2SnS3)1x nanocrystals were studied by energy
disperse X-ray spectroscopy (EDS) (Fig. S3w). Compositions
of the alloyed nanocrystals are consistent with the amount of
the co-precursors used (Table S2w), indicating that the
compositions of the alloyed nanocrystals can be readily
controlled. In addition, the valence states of the Cu, Sn, and
S in Cu2SnS3 nanocrystals were determined by X-ray
photoelectron spectroscopy (XPS) (Fig. S4w). The Cu 2p core
splits into 2p3/2 (932.2 eV) and 2p1/2 (952.2 eV) peaks, and Sn
3d shows two peaks at 486.3 and 494.7 eV. The observed
binding energy values of Cu 2p and Sn 3d are in good
accordance with those reported in the literature for the
Cu2SnS3 nanocrystals,4b suggesting that the valence states of
Cu and Sn in the Cu2SnS3 nanocrystals are +1 and +4. The
two peaks located at 161.4 and 162.6 eV were assigned to S 2p
with a valence of 2.
Fig. 4 LR- (left) and HR-TEM (right) images of ZnS (top),
(ZnS)1/4(Cu2SnS3)3/4 (middle), and Cu2SnS3 (bottom) nanocrystals.
966 Chem. Commun., 2011, 47, 964966
View Article Online
Fig. 4 shows transmission electron microscopy (TEM)
images for ZnS, (ZnS)1/4(Cu2SnS3)3/4, and Cu2SnS3
nanocrystals. They have almost the same average diameters
of 10.2, 11.5, and 10.4 nm, respectively, which are very close to
the size calculated from XRD by the Scherrer equation. High-
resolution TEM images (Fig. 4, right) clearly indicate that
these nearly spherical nanoparticles are single crystalline. The
reaction temperatures strongly aect the sizes of alloyed
(ZnS)x(Cu2SnS3)1x nanocrystals. To obtain the same
nanoparticle size, dierent reaction temperatures were chosen
to synthesize alloyed (ZnS)x(Cu2SnS3)1x and (CuInS2)x
(Cu2SnS3)1x nanocrystals (see table S1 in the ESIw).
In conclusion, nearly monodisperse Cu2SnS3 nanocrystals
with zincblende and wurtzite structures have been successfully
synthesized for the rst time. It was found that ZnS, CuInS2,
and Cu2SnS3 possess the same zincblende and wurtzite
structures. This nding makes it possible to synthesize multi-
component (ZnS)x(Cu2SnS3)1x and (CuInS2)x(Cu2SnS3)1x
nanocrystals with arbitrary composition. Thus, the band
gaps of alloyed nanocrystals can be tuned in an ultra-broad
range of 3.63 to 0.94 eV, which covers the UV-Vis-NIR region,
providing a series of nontoxic and low-cost semiconductor
nanomaterials for photovoltaic and photocatalytic
applications. Meanwhile, bridges have been built between
group IIVI, IIIIVI, and IIVVI semiconductor
nanocrystals, which could open a new avenue for the
synthesis of nontoxic (ZnS)x(Cu2SnS3)1x/ZnS core/shell
quantum dots emitting in the UV-Vis-NIR region.
This work was supported by a startup fund from Changchun
Institute of Applied Chemistry, the National Natural Science
Foundation of China (50921062, 21071142), the National Science
Foundation for Young Scientists of Jilin Province (20100105),
and Changchun Bureau of Science and Technology (2008228).
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This journal is c The Royal Society of Chemistry 2011