Journal of Crystal Growth 354 (2012) 157–163

Contents lists available at SciVerse ScienceDirect

Journal of Crystal Growth

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

Structural and morphological dependences of Sb2S3 nanobars synthesised by

organo-colloidal process on precursor concentrations and reaction times
Ivana Lj. Validžić a,n, Nadica D. Abazović a, S. Phillip Ahrenkiel b, Ivana A. Janković a
a
Vinča Institute of Nuclear Sciences, University of Belgrade, PO Box 522, 11001 Belgrade, Serbia
b
Nanoscience and Nanoengineering Department, South Dakota School of Mines and Technology, 501 E. Saint Joseph St., Rapid City, SD 57701, United States

a r t i c l e i n f o abstract

Article history: In this paper we report the synthesis of antimony sulphide (Sb2S3) nanobars performed using a simple
Received 15 February 2012 organo-colloidal synthetic method. The as-synthesised Sb2S3 nanobars with various precursor con-
Received in revised form centrations and heating times showed differences in the morphology (open and enclosing forms) and
30 May 2012
structural parameters. UV–vis absorption measurements revealed that the optical band gap energies
Accepted 1 June 2012
lay in the red part of the solar spectrum. The observed band gap energies, of nearly the same values
Communicated by K. Deppert
Available online 16 June 2012 (  1.6 eV), proved that precursor concentrations and heating times had no effect on them. The structure
refinement showed that the Sb2S3 powder belonged to the orthorhombic type with a space group
Keywords: Pbnm. It was found that Sb2S3 nanobars predominantly grew along the [010] direction, and that the
A1. Crystal structure
unit cell parameters and the preferred orientation parameter (t) refined against experimental data
A1. Growth from solutions
were quite dependent on both the precursor concentration and the heating time. The optimum heating
A1. X-ray diffraction
B1. Antimonides time to nicely follow the dependence of structural parameters on the precursor concentration was
B2. Semiconducting materials observed.
& 2012 Elsevier B.V. All rights reserved.

1. Introduction enclosing morphological forms. We followed the influence of

Antimony sulphide (Sb2S3) is a semiconducting chalcogenide
of the V–VI groups of elements. It has a wide range of industrial
applications as target material in television cameras, and in
microwave, switching and optoelectronic devices, due to its
attractive photo-conducting properties and high thermoelectric
power [1–4]. Sb2S3 is an important photoconductive semiconduc-
tor that crystallises in the orthorhombic system (pbnm space
group) [5,6] and some of its physical properties like photoelectric
properties [7], conduction and charge carrier transport mechan-
ism [8] have been reported in the literature. Besides, these
characteristics make it a promising candidate for application in
solar energy conversion industry as absorbing material [9].
Colloidal syntheses of Sb2S3 nanomaterials in organic media
are very rare by dealt with in scientific papers. So far, Deng et al.
[10] have described the first synthesis of Sb2Se3-xSx nanotubes
across the entire compositional range (x ¼0–3), using a colloidal
synthetic method. We performed the first synthesis of the pure
Sb2S3 nanomaterial by the colloidal synthetic method [11].
Here, we report a modified colloidal synthetic route in organic
media. It is the first time oleic acid has been used as a complexing
agent/ligand for the synthesis of Sb2S3 nanobars with open and
n
Corresponding author. Tel.:þ 381 118066428; fax: þ 381 113408607.
E-mail address: validzic@vinca.rs (I.Lj. Validžić).
precursor concentration and reaction time on the morphology,
band gap energies and structural parameters of the as-synthe-
sised nanobars. Structural refinement of the obtained materials
reveals that Sb2S3 nanobars predominantly grow along the [010]
direction, while unit cell parameters and preferred orientation
parameter (t) are quite dependent on both the precursor con-
centration and the heating time. It was found that there was an
optimum heating time for which structural parameters exhibited
a pronounced dependence on the precursor concentration. No
similar results concerning the band gap and structural parameter
dependences of the as-synthesised Sb2S3 material have been
found in the literature.
2. Experimental
All chemicals (antimony (III) chloride (SbCl3) (99.0% min. Alfa
Aesar), sulphur powder (S) (99.999% Alfa Aesar), paraffin liquid
(J. T. Baker), oleic acid (OA) (C18H34O2) (65% GC Fluka), oleylamine
techn. (70% Aldrich), hexan (J. T. Baker), isopropyl alcohol
(J. T. Baker), methanol (J. T. Baker) and benzene (J. T. Baker)) were
of the highest purity available and were used without further
purification.
In a typical synthesis of Sb2S3 nanobars, Sb(III)-oleic acid-com-
plex precursor solutions and sulphur precursor solutions were
prepared simultaneously. Sb(III)-oleic acid-complex solutions were

0022-0248/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jcrysgro.2012.06.003
158 I.Lj. Validžić et al. / Journal of Crystal Growth 354 (2012) 157–163

prepared by adding 0.2 mmol (C1), 0.6 mmol (C2) or 1.8 mmol (C3)
of SbCl3 to 9.6 ml oleic acid (OA). Mixtures were kept at 90 1C and
stirred for 30 min until Sb (III)-complex was formed. The other flasks
were loaded with 0.3 mmol (C1), 0.9 mmol (C2) or 2.7 mmol (C3) of S
powder, 2 ml oleylamine and 25 mL of paraffin liquid. Mixtures
were kept at 240 1C for about 30 minutes, i.e. until transparent
yellow solutions were formed. Then, the Sb(III)-oleic acid-complex
solutions were swiftly injected into the S-precursor solutions. The
mixtures were kept at 240 1C, with continuous stirring. Immediately
after reaching the temperature of 240 1C, the colour of the mixed
solution turned from orange–yellow to grey black, indicating the
formation of the Sb2S3 species. The as-synthesised Sb2S3 precipitates
(for each separate concentration C1, C2 and C3) at 240 1C were
heated for 0, 5 and 10 minutes from the moment when the grey
black Sb2S3 species appeared. After this time, the reaction was
stopped by the injection of hexane/isopropyl mixture (1/1 v/v). The
resulting solid precipitates were retrieved by centrifugation and
washed/precipitated a few times with methanol/benzene mixture,

Fig. 1. SEM images of the as-synthesised Sb2S3 powders obtained for different precursor concentrations (C1, C2 and C3) and heating times: A (0 min), B (5 min)
and C (10 min) compared at the same magnification.
 I.Lj. Validžić et al. / Journal of Crystal Growth 354 (2012) 157–163 159

until the paraffin liquid was removed. The final products were It can be observed that with the increase of the concentration
dispersible in organic solvents such as isopropyl alcohol. from C1 to C2 the length of the nanobars increases and their
The scanning electron microscopy (SEM) observations and morphology changes from open to enclosing form. It should be
measurements were performed using a JEOL JSM-6460LV instru- emphasised here that no visible morphological differences were
ment (Tokyo, Japan). The Sb2S3 samples were coated with a thin observed between the concentrations C2 and C3, and no signifi-
layer of gold deposited by sputtering process. cant differences in the lengths and diameters of the nanobars.
The Field Emission Scanning Electron Microscopy (FESEM)
measurements were performed using a TESCAN Mira3 XMU at
20 kV.
Selected area diffraction pattern (SAED) was acquired on a
JEM-2100 LaB6 HRP transmission electron microscope (TEM) at
200 KV. Energy Dispersive X-Ray Analysis (EDX) data were
acquired in the TEM using an Oxford Inca system with an
X-Max silicon-drift detector.
Absorption spectra of the Sb2S3 samples in isopropyl alcohol
were recorded using a Perkin Elmer Lambda 9 UV–vis-NIR
Spectrophotometer.
The X-ray Powder Diffraction (XRPD) patterns of investigated
samples were obtained on a Philips PW-1050 automated diffract-
ometer using CuKa radiation (operated at 40 kV and 30 mA). A
fixed 11 divergence and 0.11 receiving slits were used. Diffraction
data for structural analysis were collected in the 2y range
10–1201, counting for 12 s in 0.021 steps. Structural analysis was
done using the KOALARIE computing programme [12] based on the
Rietveld full profile refinement method [13]. Samples for XRPD
measurements were prepared using the standard protocol [14].

3. Results and discussion

The synthetic method used in this work is a modified techni-

que for colloidal synthesis established by Deng et al., which uses
‘‘green’’ and low-cost paraffin liquid as a solvent [15]. As far as we
are aware, this is the first organo-colloidal synthesis of Sb2S3 Fig. 2. SEM (A), FESEM (B1) and TEM (B2) images of the as-synthesised Sb2S3
nanobars where oleic acid is used. Dependences of the morphol- powders obtained for precursor concentrations (C1 (image A) and C2 and C3 (image
B1 and B2) where open (A), enclosing (B1 and B2) morphological forms of nanobars
ogy, band gap energies and structural parameters of the synthe-
were observed.
sised nanobars on the concentration and heating time were
followed. This technique avoids the use of TOP (trioctylpho-
sphine), because it is an unstable, hazardous, expensive and
environmentally harmful solvent. On the other hand, paraffin
liquid is a nontoxic, environmentally friendly solvent, stable at
very high temperatures. Also, the synthesis can be carried out
under nitrogen or in the open air.
The morphology of Sb2S3 nanobars was checked by SEM.
Fig. 1A shows the as-synthesised Sb2S3 powders obtained for
different precursor concentrations C1, C2 and C3, heated for the
same time (0 min from the moment of the appearance of grey
black Sb2S3 species) and compared at the same magnification. As
can be seen, there is a mixed morphological system for the lowest
concentration (C1), composed of a small number of spherical
nanoparticles and the majority of nanobars, with open morpho-
logical form. The lengths of the open nanobars range from 5 to
10 mm, with diameters around 100 nm, while the nanoparticles
diameters range from 50 to150 nm. With increasing concentra-
tion (C2 and C3), only longer nanobars with enclosing morpholo-
gical form were observed (nanobars that blend with each
other and form an enclosing form, see explanation further in
the text). The length of the nanobars exceeds 5 mm. No visible
morphological differences between concentrations C2 and C3
were observed.
Further, Fig. 1B shows the as-synthesised Sb2S3 powders
obtained for different concentrations C1, C2 and C3, heated for
5 min (from the moment of the appearance of grey black Sb2S3
Fig. 3. TEM images and SAED pattern for the synthesised Sb2S3 nanobars,
species). Compared with the previous sample, no spherical revealing the single-crystalline orthorhombic structure. The growth direction
nanoparticles were observed for the sample with the lowest (010) of the nanobars is perpendicular to the (102) planes indexed on the SAED
concentration, C1, only morphologically open form nanobars. pattern.
160 I.Lj. Validžić et al. / Journal of Crystal Growth 354 (2012) 157–163

Finally, Fig. 1C shows Sb2S3 powders obtained for different
concentrations C1, C2 and C3, heated for 10 min (from the moment
of the appearance of grey black Sb2S3 species). With the smallest
concentration (C1), prolonged heating time leads to the formation of
slightly deformed nanobars with open form morphology. The length
of the nanobars increases with the increase of the concentration from
C1 to C2, although a slight deformation of nanobars is still present, and
their morphology form changes from open to enclosing. With the
highest concentration C3 there is no deformation. The thickness and
lengths of the nanobars are mostly the same as described above.
From Fig. 1A, B, and C it is obvious that the morphologies of
the Sb2S3 nanobars are dependent on both the precursor concen-
tration and the heating time. With the increase of concentration
for each separate heating time, the Sb2S3 nanobars on the record

Fig. 4. EDX analysis of the Sb2S3 dispersion placed on the grid. Fe and Cu are artifacts from the grid.

Fig. 5. UV–vis absorption spectra of the Sb2S3 products dispersed in isopropyl alcohol, first derivative absorption spectra of the Sb2S3 products and corresponding plots for
determination of band gap energies Eg, for each separate precursor concentration (C1 (solid line), C2 (dashed line) and C3 (dotted line)), obtained for different heating times:
A (0 min), B (5 min) and C (10 min).
 I.Lj. Validžić et al. / Journal of Crystal Growth 354 (2012) 157–163 161

grow in length. For a heating time of 5 min we found that the
sample was morphologically quite homogeneous, no nanoparti-
cles or deformed nanobars were observed. Taking into account
the concentration dependence, for the highest concentration (C3)
we found quite homogeneous Sb2S3 nanobars. On the heating
time scale (by comparing the same concentration from the three
separate images, A, B and C), the morphology changes in such a
way that for C1 we observed clearly visible nanobars with open
form and spherical nanoparticles, then quite regular open form
nanobars, which ended up with deformed open form nanobars.
Further, for C2 we observed regular nanobars that form enclosing
forms and on the heating time scale end up with deformed
nanobars. Finally, the same enclosing forms composed of nano-
bars were observed for the highest concentration.

Fig. 6. Final Rietveld plots of Sb2S3 powders obtained for different concentrations (C1, C2 and C3), and heating times: A (0 min), B (5 min), C (10 min) and D (the standard
pattern of Sb2S3 with corresponding planes (JCPDS 03–065-2432)).
162 I.Lj. Validžić et al. / Journal of Crystal Growth 354 (2012) 157–163
To confirm the existence of an open (C1) and enclosing (C2 and
C3) morphological forms composed of nanobars, we performed
high magnification SEM (A), FESEM (B1) and TEM (B2) measure-
ments and presented them in Fig. 2A (open forms) and B1 and B2
(enclosing forms). It can clearly be seen that the nanobars
presented in Fig. 2A are indeed open (this is the reason that we
named them nanobars with open form), while the nanobars
presented in Fig. 2B1 and B2 stick to each other, creating enclosing
morphology forms.
Fig. 3 shows TEM images and SAED pattern for the synthesised
Sb2S3 nanobars. The SAED pattern is essentially identical along
the nanobars, verifying that the nanobars are single- crystalline.
SAED patterns and lattice images reveal that the lattice vector of
the (102) planes is perpendicular to the (010) direction, along
which the nanobars grow. These results are in agreement with
those obtained from the Rietveld refinements of XRPD patterns
(see further in the text).
EDX spectrum of the synthesised Sb2S3 material confirmed the
purity of our samples, detecting only Sb and S (see Fig. 4). Fe and
Cu are the peaks from the TEM grid and pole piece.
Optical properties of the synthesised materials were charac-
terised by UV/Vis absorption measurements, and presented in
Fig. 5 for different heating times (A (0 min), B (5 min) and C
(10 min)) and different precursor concentrations (C1 (solid line),
C2 (dashed line) and C3 (dotted line)). A common way to extract
band gap from absorption spectra is to get the first derivative of
absorbance with respect to photon energy and find the maxima in
the derivative spectra at the lower energy sides [16,17]. The Eg is
associated with the maximum in the spectrum, i.e. where the
absorbance has the maximum increase with respect to photon
energy. In Fig. 5, next to the UV/Vis spectra, such derivative
spectra of the samples are presented for different heating times
(A (0 min), B (5 min) and C (10 min)) and different precursor
concentrations (C1 (solid line), C2 (dashed line) and C3 (dotted line)).
The observed band gap energies for all the samples obtained for
different heating times and precursor concentrations are almost
identical (with very small oscillation) and are about 1.68 eV. It
is important to emphasise here that by performing the first
derivative of absorbance we limited energy area for determina-
tion of Eg that was used in another estimation of the band
gap values by using the following well-known relation: a ¼
k(hn)  1(hn Eg)n/2, where k is the constant, hn is the photon
energy and n is equal to 1 for direct band gap. The obtained
(ahn)2 ¼f(hn) plots for slightly turbid Sb2S3 dispersions for differ-
ent heating times (A (0 min), B (5 min) and C (10 min)) and
different precursor concentrations (C1 (solid line), C2 (dashed line)
Table 1
Structure R factors values for different precursor concentrations (C1, C2 and C3)
and heating times: A (0 min), B (5 min) and C (10 min).
A (0 min) B (5 min)
R (%) R (%)
C1 12.52 12.82
C2 11.73 12.92
C3 10.99 11.41
Table 2
Structural lattice parameters (a, b and c) values for different precursor concentrations (C1, C2 and C3) and heating times: A (0 min), B (5 min) and C (10 min).
A (0 min)
a (nm) b (nm) c (nm)
C1 1.13176 0.38398 1.12379
C2 1.13187 0.38417 1.12384
C3 1.13212 0.38432 1.12406
and C3 (dotted line)) are given next to the derivative spectra of the
samples. As can be seen, all nine plots (A, B and C) are quite linear.
The values obtained by extrapolating the straight portion to
energy axis at zero absorption coefficients gave the direct band
gap energies of about  1.55 eV for all nine samples. The slight
differences (in the second decimal place) in the values of the band
gap energies are too small for drawing conclusions. To avoid the
difficulties of obtaining Eg from absorption spectroscopy in dis-
persed samples, diffuse reflectance measurements (DRS) of dry
powders were performed (spectra not shown). The values
obtained by using the Kubelka–Munk function for all nine
samples were found to be  1.6 eV, which is in good agreement
with information extracted from absorption spectra. In general,
Sb2S3 has a band gap that varies between 1.5 and 2.2 eV,
depending on the size, shape and crystallinity in the nanoscale
regime [5,10,18–21]. So, the direct band gap energy of each
sample at around 1.5–1.7 eV corresponds to optical transitions
expected for Sb2S3 in the literature.
Further in the text we concentrate on the dependence of
structural parameters on the concentration and reaction time of
Sb2S3 nanobars. The refinement of the diffraction data showed
that Sb2S3 belongs to the orthorhombic structure, where all
diffraction peaks could be indexed to a pure phase (JCPDS
03–065-2432) (Fig. 6D). The structure refinements were done in
the space group Pnma (no. 62), and the results for all nine samples
are depicted in Fig. 6((A) for 0 min heating time for all three
concentrations, C1, C2 and C3, (B) for 5 min heating time and
(C) for 10 min heating time). The structure of Sb2S3 was refined
down to the R factors whose values obtained for different
precursor concentrations and heating times were summarised in
Table 1. Dependences of the structural lattice cell parameters (a, b
and c) on both the precursor concentrations and heating times are
shown in Table 2.
Results of the Rietveld refinements for all the samples show
that the Sb2S3 nanobars predominantly grow along the (010)
direction, which is in accordance with the fact that in the Pnma
setting the rods and wires are parallel to the (010) direction [22].
As can be seen, the unit cell parameters a, b and c permanently
increase with increasing concentration (from C1 to C3, for the
samples heated for 0 and 5 min), which supports our visual
statement about the enclosing form composed of nanobars (see
Table 2). Very high and the same values of the preferred orienta-
tion parameter (t) refined against experimental data (around
1.50) for the samples heated for 0 and 5 min were observed. In
principle, the non-random particle orientation (when the shapes
are anisotropic, for example platelet-like or needle/wires-like) is
called preferred orientation effect and can be defined by introdu-
cing the preferred orientation factor (Thkl) and the preferred
orientation parameter refined against experimental data (t)
[11,23].
C (10 min) For the samples heated for 10 min, the situation is slightly
R (%) different. Only the unit cell parameter b permanently increases
with the increase of the concentration from C1 to C3. Also, the
13.53 preferred orientation parameter (t) refined against experimental
11.56
11.08
data increases with increasing concentration from C1, where
t ¼1.06 (meaning that no preferred orientation is present) over
B (5 min) C (10 min)
a (nm) b (nm) c (nm) a (nm) b (nm) c (nm)
1.13159 0.38393 1.12340 1.13136 0.38395 1.12363
1.13208 0.38418 1.12405 1.13201 0.38422 1.12407
1.13228 0.38444 1.12423 1.13189 0.38427 1.12390
 I.Lj. Validžić et al. / Journal of Crystal Growth 354 (2012) 157–163
C2, where t ¼1.41 (preferred orientation is present and very high)
to C3, where t ¼1.72 (extremely high preferred orientation is
present). The fact that no orientation is present in the sample C1
could be explained by the most deformed morphology observed,
which could be related to the structure.
At the end of the paper it is important to emphasise that we
performed photoluminescence spectroscopy measurements as an
equally important and nondestructive tool for evaluating the
optical nature of the materials. No peaks were observed either
in PL emission or excitation spectra for a broad spectral range,
typical of this material.
4. Conclusion
To summarise the work described, nanobars with different
morphology (open and enclosing forms, as we name them) of
Sb2S3 were synthesised by organic colloidal synthetic method in
the presence of oleic acid used for the first time for the synthesis
of antimony sulphide. In our work we followed the concentration
and heating time dependences of the as-synthesised Sb2S3 nano-
bars, showing the primary changes in the morphology and
structural parameters. Dependences of the structural factors and
morphology on the factors that we can control (precursor con-
centration and heating time) are inescapable in this analysis, and
certainly can lead to a better understanding of the overall picture.
On the contrary, the values of the band gap energies found are
nearly the same (  1.6 eV), proving that the precursor concentra-
tions and heating times have no effect on them.
Acknowledgements
Financial support for this study was granted by the Ministry of
Science and Technological Development of the Republic of Serbia
(Projects 172056 and 45020).
References
[1] T.M. Tritt, Thermoelectric Materials: Holey and Unholey Semiconductors,
Science 283 (1999) 804–805.
[2] R. Venkantasubramanian, E. Siilvola, T. Colpitts, B O’Quinn, Thin-film thermo-
electric devices with high room-temperature Figs of merit, Nature 413 (2001)
597–602.
163
[3] G. Konstantatos, L. Levina, J. Tang, E.H. Sargent, Sensitive solution-processed
Bi2S3 nanocrystalline photodetectors, Nano Letters 8 (2008) 4002–4006.
[4] K.Y. Rajpure, C.H. Bhosale, Effect of composition on the structural, optical and
electrical properties of sprayed Sb2S3 thin films prepared from non-aqueous
medium, Journal of Physics and Chemistry of Solids 61 (2000) 561–568.
[5] Y. Yu, R.H. Wang, Q. Chen, L.M. Peng, High-quality ultralong Sb2Se3 and Sb2S3
nanoribbons on a large scale via a simple chemical route, Journal of Physical
Chemistry B 110 (2006) 13415–13419.
[6] X.W. Zheng, Y. Xie, L.Y. Zhu, X.C. Jiang, Y.,.B. Jia, W.H. Song, Y.P. Sun, Growth of
Sb2E3 (E ¼S, Se) polygonal tubular crystals via a novel solvent-relief-self-
seeding process, Inorganic Chemistry 41 (2002) 455–461.
[7] M.J. Chockalingam, K.N. Rao, N. Rangarajan, C.V. Suryanarayana, Studies on
sintered photoconductive layers of antimony trisulphide, Journal of Physics
D: Applied Physics 3 (1970) 1641–1644.
[8] E. Montrimas, A. Pazra, Charge carrier transport and space charge in thin
films of antimony trisulphide, Thin Solid Films 34 (1976) 65–68.
[9] H. Bao, X. Cui, C.M. Li, Q. Song, Z. Lu, J. Guo, Synthesis and electrical transport
properties of single-crystal antimony sulfide nanowires, Journal of Physical
Chemistry C 111 (2007) 17131–17135.
[10] Z. Deng, M. Mansuripur, A.J. Muscat, Simple colloidal synthesis of single-
crystal Sb Se  S nanotubes with composition dependent band-gap energy
in the near-infrared, Nano Letters 9 (2009) 2015–2020.
[11] I.Lj Validžić, M. Mitrić, Colloidal synthesis of Sb2S3 nanorods/bars with
strong preferred orientation, Materials Letters 65 (2011) 1919–1922.
[12] R.W. Cheary, A.A. Coelho, Fundamental parameters approach to x-ray line-
profile fitting, Journal of Applied Crystallography 25 (1992) 109–121.
[13] H. Rietveld, A profile refinement method for nuclear and magnetic structures,
Journal of Applied Crystallography 2 (1969) 65–71.
[14] V.K. Pecharsky, P.Y. Zavalij, Fundamentals of Powder Diffraction and Struc-
tural Characterization of Materials, Springer, 2005.
[15] Zhengtao Deng, Li Cao, Fangqiong Tang, Bingsuo Zou, A new route to zinc-
blende CdSe nanocrystals: mechanism and synthesis, Journal of Physical
Chemistry B 109 (2005) 16671–16675.
[16] M. Becerril, H. Silva-Lopez, O. Zelaya-Angel, Band gap energy in Zn-rich
Zn1  xCdxTe thin films grown by r.f. sputtering, Revista Mexicana De Fisica 50
(2004) 588–593.
[17] A.E. Morales, E.S. Mora, U. Pal, Use of diffuse reflectance spectroscopy for
optical characterization of un-supported nanostructures, Revista Mexicana
De Fisica 53 (2007) 18–22.
[18] H. Hu, M. Mo, B. Yang, X. Zhang, Q. Li, W. Yu, Y. Qian, Solvothermal synthesis
of Sb2S3 nanowires on a large scale, Journal of Crystal Growth 258 (2003)
106–112.
[19] M.T.S. Nair, Y. Pena, J. Campos, V.M. Garcia, P.K. Nair, Chemically deposited
Sb2S3 and Sb2S3-CuS, Journal of the Electrochemical Society 145 (1998)
2113–2120.
[20] J. Ota, S.K. Srivastava, Tartaric acid assisted growth of Sb2S3 nanorods by a
simple wet chemical method, Crystal Growth and Design 7 (2007) 343–347.
[21] J. Yang, J.H. Zeng, S.H. Yu, L. Yang, Y.H. Zhang, Y.T. Qian, Pressure-controlled
fabrication of stibnite nanorods by the solvothermal decomposition of a
simple single-source precursor, Chemistry of Materials 12 (2000) 2924–2929.
[22] L.F. Lundegaard, R. Miletich, T. Balic-Zunic, E. Makovicky, Equation of state
and crystal structure of Sb2S3 between 0 and 10 GPa, Physics and Chemistry
of Minerals 30 (2003) 463–468.
[23] V.K. Pecharsky, P.Y. Zavalij, Fundamentals of Powder Diffraction and Struc-
tural Characterization of Materials, Springer, 2009.