Materials Letters 65 (2011) 1919–1922

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Colloidal synthesis of Sb2S3 nanorods/bars with strong preferred orientation

Ivana Lj. Validžić ⁎, Miodrag Mitrić
Vinča Institute of Nuclear Sciences, P.O. Box 522, 11001 Belgrade, University in Belgrade, Serbia

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

Article history: We report the synthesis of antimony trisulfide (Sb2S3) nanorods/bars via a simple, low-cost and colloidal
Received 25 January 2011 synthetic method. The as-synthesized Sb2S3 nanorods/bars with different heating times from the moment of
Accepted 8 March 2011 appearance of the Sb2S3 precipitate at 240 °C are the longest and thinnest in the beginning (diameters of 50–
Available online xxxx
100 nm and lengths of 3–5 μm). UV/Vis absorption spectroscopy reveals that the optical band gap energy of
the Sb2S3 nanorods/bars slightly decreases with increasing the heating times in the range of 1.54, 1.50 to
Keywords:
Colloidal processing
1.47 eV at the red part of the solar spectrum. The structure of Sb2S3 for all free samples was refined down to
Electron microscopy the R-factor of 9.57, 5.43 and 6.19%. The refinement showed that Sb2S3 powder belongs to the orthorhombic
Semiconductors type with space group Pbnm (no. 62). It was found that Sb2S3 nanorods/bars predominantly grow along the
Solar energy materials [010] direction. The preferred orientation parameter (τ) refined against experimental data is quite high and is
X-ray technique found to be 1.42, 1.21 and 1.19 for all three samples observed. A decrease in unit cell parameter b followed by
increasing the heating times was observed.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction

Antimony trisulfide (Sb2S3) is highly anisotropic V–VI group

semiconductors that crystallize in the orthorhombic system (pbnm
space group) [1]. Its useful properties make it promising candidate for
important applications in diverse area such as solar energy conversion
due to its good photoconductivity, thermoelectric cooling technology,
and photoelectronics in the infrared (IR) region [2].
So far, various synthetic methods have been employed to
synthesize Sb2S3 material [3–5]. As far as we are aware only Deng
et al. [6] report the first synthesis of Sb2Se3-xSx nanotubes across the
entire compositional range (x = 0 to 3) via a colloidal synthetic
method. Here we report the synthesis of Sb2S3 nanorods/bars by the
modified colloidal synthetic method. We found that the optical band
gap energy and unit cell dimensions slightly decreases with increasing
the heating time. Also, Sb2S3 nanorods/bars predominantly grow
along the [010] direction and the preferred orientation parameter (τ)
is quite high for all three samples observed. No similar results were
found in the literature concerning the structure of the as-synthesized
Sb2S3 material.

2. Experimental

All chemicals (SbCl3 (99.0 % min Alfa Aesar), S powder (99.999%

Alfa Aesar), paraffin liquid (PL) (J. T. Baker), palmitic acid (PA) (95%

⁎ Corresponding author. Tel.: +381 118066428; fax: +381 113408607. Fig. 1. Synthetic scheme and photographs of Sb2S3 nanorods/bars dispersed in
E-mail address: validzic@vinca.rs (I.Lj. Validžić). isopropyl alcohol.

0167-577X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.03.032
1920 I.Lj. Validžić, M. Mitrić / Materials Letters 65 (2011) 1919–1922

Alfa Aesar), oleylamine (OA) techn. (70% Aldrich), hexan (J. T. Baker),
isopropyl alcohol (IA) (J. T. Baker), methanol (J. T. Baker) and benzene
(J. T. Baker)) were of the highest purity available and they were used
without further purification.
In a typical synthesis of Sb2S3 nanorods/bars, both the Sb(III)-
complex precursor solution and sulfur precursor solution were
prepared in the same time. Firstly, Sb(III)-complex solution was
prepared by adding 0.6 mmol of SbCl3 to 3.21 g PA in a flask and kept
at 80 °C and stirred for 30 min until a uniform mixture was formed.
Secondly, sulfur solution was prepared in a separate flask, where
0.9 mmol of S powder was mixed with 2 ml OA, 25 mL PL and kept at
220 °C, then stirred for 30 min. Thirdly, S-precursor solution was
swiftly poured into the Sb(III)-complex precursor. The mixture was
maintained at 240 °C with continuous stirring. Immediately after
reaching the temperature of 240 °C, the color of the mixed solution
turned from orange–yellow to gray black, indicating the formation of
the Sb2S3 species. The as-synthesized Sb2S3 precipitates at 240 °C
were heated for different times (0, 5 and 10 min). After the reaction,
hexane and IA were added, and the resulting solid products were
retrieved by centrifugation with constant washing with mixture of
methanol and benzene.
The scanning electron microscopy (SEM) observations and
measurements were performed using JEOL JSM-6460LV instrument
(Tokyo, Japan).
Absorption spectra of the Sb2S3 samples in methanol were recorded
using Perkin Elmer Lambda 9 UV/VIS/NIR Spectrophotometer.
The X-ray Powder Diffraction (XRPD) patterns were obtained on a
Philips PW-1050 using CuKα radiation with a fixed 1° divergence and
0.1° receiving slits. Diffraction data were collected in the 2θ range 10–
90°, counting for 12 s in 0.02° steps. Structure analysis was done by
the use of the KOALARIE computing program based on the Rietveld
full profile refinement method.

Fig. 2. SEM images of the as-synthesized Sb2S3 powders, obtained for different heating times: a and b (0 min), c and d (5 min) and e and f (10 min).
 I.Lj. Validžić, M. Mitrić / Materials Letters 65 (2011) 1919–1922
Fig. 3. UV/Vis absorption spectra of the Sb2S3 products dispersed in isopropyl alcohol
and obtained for different heating times: a (0 min), b (5 min) and c (10 min). Inset:
plots for determination of Eg and enlarged comparison of the slight differences in the Eg.
3. Results and discussion
As shown in Fig. 1 the current synthetic method is modified on the
already modified well-developed technique for colloidal synthesis
developed by Deng et al., by using “green” and low-cost paraffin liquid
as the solvent [7]. The initial Sb2S3 nanorods/bars dispersed in
isopropyl alcohol are gray black in color (Fig. 1).
The morphologies of Sb2S3 nanorods/bars were examined with a
SEM. Fig. 2a and b shows the product heated for 0 min, from the
moment of appearance of the Sb2S3 precipitate at 240 °C, and contains
Fig. 4. Final Rietveld plots of Sb2S3 powders a (0 min), b (5 min), c (10 min), d (the standard pattern of Sb2S3 with corresponding planes), and the values of the preferred orientation
parameters τ.
1921
a rods/barslike material. The lengths of the product range from 2 to
5 μm and diameters from 30 to 100 nm. Further, Fig. 2c and d shows
the product heated for 5 min, and contains rods/barslike materials,
that became shorter and thicker with heating. The lengths of the
product range from 1 to 4 μm and diameters from 200 to 400 nm.
Finally, Fig. 2e and f shows the product heated for 10 min, and
contains the thickest rods/barslike (diameters N 400 nm) and irregu-
larly shaped materials.
The optical absorption experiments reported in Fig. 3 were carried
out to determine the band gap energies (Eg) of our samples.
Absorption spectrum of slightly turbid Sb2S3 dispersions (see Fig. 1)
with different heating times was analyzed using the following well-
known relation: α = k(hν)−1(hν − Eg)n / 2 where k is the constant, hν
is the photon energy and n is equal to 1 for direct band gap. Plots of
(αhν)2 vs. (hν) for the Sb2S3 are shown in Fig. 3 (inset). As can be
seen, all three plots are quite linear. The values obtained gave the
direct Eg of 1.54, 1.50 and 1.47 eV, respectively. This is quite
comparable to the values reported for nanorods of comparable
dimensions [3]. Decrease of the optical Eg of the Sb2S3 nanorods/
bars may be due to the difference in morphology (term “morphology”
is related with the form that the materials have) of the products
obtained in all three cases, and it has been reported earlier in the case
of nanorods and flowers morphology of Sb2S3 [8]. Also, the decrease in
the optical band gap can be attributed to improved growth of grain
size and/ or decrease in defect level. In our case with the increasing
heat treatment time the diameters of rods/barslike material increases,
causing the decrease in the band gap energy. Eg of the Sb2S3 varies
between 1.5 and 2.1 in the literature due to the changes in
crystallinity, size, and shape [1,3–6,8]. The value of the Eg of bulk
Sb2S3 is larger than we found (1.7 eV [9]), but the nanorods/bars in
our dimension range do not show a quantum confinement effect
[3,10]. This may be attributed to the lower Bohr’s radius for this
material. However, the obtained Eg values are at the red part of the
solar spectrum, meaning that the experimental values of Eg are in the
optimum value for photovoltaic conversion.
1922 I.Lj. Validžić, M. Mitrić / Materials Letters 65 (2011) 1919–1922
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). The structure refinements were
done in the space group Pnma (no.62), and results for all three samples
are depicted in Fig. 4. The structure of Sb2S3 was refined down to the
R-factor of 9.57(a), 5.43(b) and 6.19(c) %. The unit cell parameters are:
(a) a = 1.13224 nm, b = 0.38420 nm and c = 1.12403 nm, (b)
a=1.13176 nm, b=0.38396 nm and c=1.12368, (c) a=1.13183 nm,
b=0.38385 nm and c =1.12376 nm. The unit cell parameter b perma-
nently decreases with increasing the heating time, implying that the
smaller unit cell dimensions are energy more favorable. Results of the
refinements also show that the Sb2S3 nanorods/bars predominantly grow
along the [010] direction, that is in accordance with the fact that in the
Pnma setting the rods are parallel to the [010] direction [11]. In other
words, in reflection mode all the major (h0l) planes are of relatively
higher intensity compared to their reported values (see Fig. 4). In
principle, when the shapes of crystallites are isotropic, random
distribution of their orientations is not a problem, and deviations from
an ideal sample are usually negligible. However, quite often the shapes are
anisotropic (needle/rod-like) and this result in distinctly nonrandom
crystallite orientations. The nonrandom orientation is called preferred
orientation and is addressed by the preferred orientation factor (Thkl) and
the preferred orientation parameter refined against experimental data (τ)
[12]. The radial March–Dollase function (as a part of KOALARIE computing
program) that describes the anisotropic distribution as a function of angle
φhkl is represented in the form: Thkl =(τ2 cos2 φhkl +(1/τ) sin2 φhkl)−3/2.
In the case of platelet-like particles, the function is stretched along
T∥(T∥ N T⊥), while in case of needles/rods, it is stretched along T⊥(T∥ N T⊥).
Therefore, τ b 1 describes preferred orientation of the platelets and τN 1
describes preferred orientation of the needles/rods [12]. Fig. 4 (a, b and c)
shows the high values of the preferred orientation parameter (1.42, 1.21
and 1.19) (τ), for all three samples. The orientation parameter τ has the
highest value for the longest and thinnest rods/bars as we expected, and
decreases with the heating time for shorter and thicker rods/bars.
4. Conclusions
In summary, Sb2S3 nanorods/bars were synthesized by a modified
colloidal synthetic method. We also presented that the optical Eg
slightly decreases with increasing the heating time, and that Sb2S3
nanorods/bars predominantly grow along the [010] direction. The
preferred orientation parameter (τ) is quite high for all three samples
observed and decreases with the heating time. Also, decrease in cell
parameter b with increasing the heating time was found.
Acknowledgment
Financial support for this study was granted by the Ministry of
Science and Technological Development of the Republic of Serbia
(Project 172056 and III 45015).
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