In this article, organic colloidal synthesis by using
Communication
Organic Synthesis with Different
OA/EHA Ratios of Sb2S3 Nanowires
of Flower-Like Organization
and [010] Orientation
IVANA Lj. VALIDŽIĆ, NADICA D. ABAZOVIĆ,
and MIODRAG MITRIĆ
We report the first time as-synthesized antimony trisul-
fide (Sb2S3) nanowires with flower-like organization by
using different oleic acid (OA)/2-ethylhexanoic acid
(EHA) ratio. The resulting optical band-gap energy is
1.6 eV, and it is independent of the OA/EHA ratios.
Sb2S3 nanowires grow predominantly along the [010]
direction, and a significant decrease in unit cell param-
eters was observed. It seems that the shorter branched
hydrocarbon chain leads to the better structural stability
of the synthesized Sb2S3 nanowires.
DOI: 10.1007/s11661-012-1097-5
Ó The Minerals, Metals & Materials Society and ASM
International 2012
One of the most interesting sulfide materials is anti-
mony trisulfide (Sb2S3) that crystallizes in the ortho-
rhombic system (pbnm space group).[1] It is well known
that stibnite (Sb2S3) is a common mineral.[2] As a member
of V-VI group binary chalcogenides possessing good
photosensitivity and high thermoelectric power, it is
regarded as a promising material for solar energy con-
version because of its band gap that covers the range of the
solar spectrum.[3] Therefore, various methods have been
employed to synthesize this material at the nanoscale.[4–6]
Sb2S3 nanostructures with different morphologies and
architectures were prepared by some convenient meth-
ods,[6–8] but colloidal organic syntheses of antimony
trisulfide (Sb2S3) nanomaterials are rare in the scientific
papers. So far, Deng et al.[9] reported the first synthesis
of Sb2Se3 xSx nanotubes across the entire compositional
range (x = 0 to 3) via a colloidal synthetic method. We
report the first synthesis of the Sb2S3 nanorods/bars by
the modified colloidal synthetic method.[10] Until now,
the developments regarding the synthesis of this material
are few, especially related to the growth using organic
colloidal methods.
IVANA Lj. VALIDŽIĆ, Senior Scientific Associate, and NADICA
D. ABAZOVIĆ, Scientific Associate, are with the Laboratory for
Radiation Chemistry and Physics, Vinča Institute of Nuclear Sciences,
University of Belgrade, 11001 Belgrade, Serbia. Contact e-mail:
validzic@vinca.rs. MIODRAG MITRIĆ, Scientific Adviser, is with
the Laboratory for Theoretical and Condensed Matter Physics, Vinča
Institute of Nuclear Sciences, University of Belgrade
Manuscript submitted September 16, 2011.
METALLURGICAL AND MATERIALS TRANSACTIONS A
different oleic acid (OA)/2-ethylhexanoic acid (EHA)
ratio was reported for the first time. We found that all
synthesized Sb2S3 nanowires show the flower-like orga-
nization and that the optical band-gap energy is
independent of OA/EHA ratio. Also, Sb2S3 nanowires
grow predominantly along the [010] direction, and a
significant decrease in unit cell parameters a, b, and c
followed by decreasing the OA/EHA ratio was observed.
It seems that the shorter branched hydrocarbon chain in
excess leads to the better structural stability. No similar
results were found in the literature concerning the
as-synthesized Sb2S3 nanomaterial.
All chemicals (antimony [III] chloride [SbCl3] [99.0 pct
min Alfa Aesar, Ward Hill, MA], sulfur powder [S]
[99.999 pct Alfa Aesar], paraffin liquid [J.T. Baker,
Phillipsburg, NJ], OA [C18H34O2] [65 pct GC Fluka;
Sigma Aldrich, St. Louis, MO], EHA [99 pct, Alfa Aesar),
oleylamine techn. [70 pct Sigma 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 they were used without subsequent
purification.
In a typical synthesis of Sb2S3 nanowires of flower-like
organization, both the Sb(III)-complex precursor solution
and sulfur precursor solution were prepared at the same
time. The Sb(III)-complex solution was prepared by
adding 1.8 mmol of SbCl3 to a mixture containing
different OA/EHA ratios [(1) 4 mL OA and 1 mL EHA,
(2) 2.5 mL OA and 2.5 mL EHA, and (3) 1 mL OA and
4 mL EHA]. Mixture was kept at 363 K (90 °C) and
stirred for 30 minutes until Sb-fatty acid complex was
formed. The other flask was loaded with 2.7 mmol of
S powder, 2 mL oleylamine, and 25 mL of paraffin liquid.
The mixture was kept at 513 K (240 °C) for approximately
30 minutes, i.e., until transparent yellow mixture was
formed. Then, a Sb- fatty acid complex was injected swiftly
into the S-precursor solution. The mixture was maintained
at 513 K (240 °C) with continuous stirring. Immediately
after reaching the temperature of 513 K (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 513 K (240 °C)
were heated for 6 minutes from the moment when Sb-fatty
acid complex was injected. After this time, the reaction
was stopped by an injection of hexane/isopropyl mixture
(1/1, vol/vol). The resulting solid products were retrieved
by centrifugation and washed/precipitated few times with
methanol/benzene mixture, until paraffin liquid was
removed. The final products were dispersible in organic
solvents such as isopropyl alcohol.
The scanning electron microscopy (SEM) observa-
tions and measurements were performed using JEOL
JSM-6460LV instrument (JEOL Ltd., Tokyo, Japan).
The Sb2S3 samples were coated with a thin layer of gold
deposited by the sputtering process.
Absorption spectra of the Sb2S3 samples in isopropyl
alcohol were recorded using PerkinElmer Lambda 9 UV-
VIS-NIR Spectrophotometer (PerkinElmer, Waltham,
MA).
The X-ray powder diffraction (XRPD) patterns of
the investigated samples were obtained on a Philips
PW-1050 automated diffractometer (Philips, Amsterdam,
the Netherlands) using CuKa radiation (operated at
40 kV and 30 mA). A fixed 1 deg divergence and 0.1 deg
receiving slits were used. Diffraction data for structural
analysis were collected in the 2h range 10 deg to 120 deg,
counting for 12 seconds in 0.02 deg steps. A structure
analysis was conducted by the use of the KOALARIE
computing program (http://www.ccp14.ac.uk)[11] based
on the Rietveld full profile refinement method.[12] This
program is suitable to obtained microstructural param-
eters such as crystallite size, microstrain, R-factor, and
the preferred orientation parameter.[11] Samples for
XRPD measurements were prepared using standard
protocol.[13]
The current synthetic method is modified, well-developed
technique for colloidal synthesis established by Deng
et al. by using ‘‘green’’ and low-cost paraffin liquid as
the solvent.[14] This technique avoids the use of trioc-
tylphosphine (TOP), as TOP is unstable, hazardous,
expensive, and environmentally harmful solvent,
whereas paraffin liquid is a nontoxic, environmentally
friendly, and stable solvent with boiling point above
573 K (300 °C). Also, the synthesis can be carried out
under nitrogen or open to air. To the best to our
knowledge, this is the first colloidal synthesis of Sb2S3
nanowires where the mixture of two fatty acids (nonco-
ordinating solvents) was used and where nanowires of
flower-like organization were observed. Low-magnification
SEM micrographs of Sb2S3 nanowires and Sb2S3 nano-
wires dispersed in isopropyl alcohol are shown on
Figure 1. The initial Sb2S3 nanowires are gray-black in
color and stuck with each other, and therefore, they are
visible to the naked eye.
The morphologies of the Sb2S3 nanowires of the
flower-like organization were examined with an SEM.
Figure 2 shows the product of the as-synthesized Sb2S3
powders, which were obtained for different OA/EHA
ratios: A column (OA/EHA = 4), B column (OA/
EHA = 1), and C column (OA/EHA = 0.25); all
powders were heated for the same time and compared
at the same magnification. No significant morphological
Fig. 1—Low-magnification SEM micrograph and photographs of Sb2S3 nanowires dispersed in isopropyl alcohol.
differences were observed between the samples. The
lengths of the nanowires range from 5 to 10 lm and the
diameters ranged from 40 to 140 nm in all the samples
observed. The mixture of two fatty acids (OA:EHA =
linear:branched) provided not only the growth of Sb2S3
nanowires, but also what we strongly believe is respon-
sible for flower-like organization. In fact, the particles
that nucleated at higher temperatures have smaller radii
than those nucleated at lower temperatures. This finding
indicates that nucleation is substantially faster as the
temperature increases and that the growth kinetics is less
strongly dependent on temperature. Primacy in the
growth kinetics takes over the solvents.[15] As far as we
are aware, a more complex form than a flower-like
organization has not been obtained to date.
The Sb2S3 is a direct band gap semiconductor. Optical
absorption measurements were carried out to elucidate
information on the band gap energy, which is one of the
most important electronic parameters for semiconduc-
tor nanomaterials. Because all experimental results,
including XRPD and SEM observations, suggest that
Sb2S3 nanowires of flower-like organization are in pure,
high-quality crystalline phases, we suppose that the
absorption spectrum represents the true absorption
behavior of the Sb2S3 nanowires. The absorption spectra
of slightly turbid Sb2S3 dispersions with different OA/
EHA ratios represented in Figure 3(A) were analyzed
using the following well-known relation: a = k(hm) 1
(hm – Eg)n/2 where k is the constant, hm is the photon
energy, and n is equal to 1 for the direct band gap. Plots
of (ahm)2 vs (hm) for the Sb2S3 samples are shown in
Figure 3(B). As can be observed, all three plots are
linear. The values obtained by extrapolating the straight
portion to energy axis at zero absorption coefficients
gave the direct band gaps of 1.6 eV for all three plots,
respectively. The optical band-gap energy of the Sb2S3
nanowires of flower-like organization is independent of
the OA/EHA ratios. The band gap of the Sb2S3 varies
between 1.5 and 2.1 in the literature because of the
changes in the crystallinity, size, and shape in the nano
regime.[1,4–6,9,16] So, the direct band gap energy of each
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 2—SEM images of the as-synthesized Sb2S3 powders obtained for different OA/EHA ratios: A column (OA/EHA = 4), B column
(OA/EHA = 1), and C column (OA/EHA = 0.25) heated for the same time and compared using the same magnification.

sample at 1.6 eV corresponds to the optical transitions structure, where all diffraction peaks could be indexed to
expected for Sb2S3 in the literature. a pure phase of Sb2S3 (JCPDS 03-065-2432). The
The refinement of the diffraction data showed that structure refinements were done in the space group Pnma
Sb2S3 powder belongs to the orthorhombic type of (no.62). The results of the final Rietveld refinements for

METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 3—Ultraviolet-Vis absorption spectra (A) and plots for determination of Eg (B) of the Sb2S3 nanowires dispersed in isopropyl alcohol and
obtained for different OA/EHA ratio: a (OA/EHA = 4), b without column (OA/EHA = 1), and c without column (OA/EHA = 0.25), heated
for the same time.

Fig. 4—Final Rietveld plots of Sb2S3 powders obtained for different OA/EHA ratios: A without column (OA/EHA = 4), B without column
(OA/EHA = 1), and C without column (OA/EHA = 0.25), heated for the same time, with corresponding planes (JCPDS 03-065-2432).

METALLURGICAL AND MATERIALS TRANSACTIONS A

all three samples with different OA/EHA ratios are
depicted in Figure 4. The structure of antimony trisul-
fide was refined down to the R-factor of 10.76 pct
(Figure 4(a)), 10.87 pct (Figure 4(b)), and 10.49 pct
(Figure 4(c)). The values of estimated standard devia-
tions as well as reliability factors confirmed that these
data are reliable and that the structure was well refined
(not shown). The unit cell parameters are as follows:
a = 1.13230 nm, b = 0.38438 nm, and c = 1.12426 nm
(Figure 4(a)); a = 1.13192 nm, b = 0.38418 nm, and
c = 1.12389 (Figure 4(b)); and a = 1.13191 nm,
b = 0.38415 nm, and c = 1.12384 nm (Figure 4(c)).
As can be observed, the unit cell parameters (a, b, and
c) decrease with a decreasing OA/EHA ratio, implying
that the smaller unit cell dimensions are more energy
favorable. At the same time, it is obvious that an excess
of EHA fatty acid with the shorter branched hydrocar-
bon chain better stabilizes the system than linear OA
fatty acid. Also, a decrease of the OA/EHA ratio leads
to a reduction of unit cell volume that is in accordance
with the previous observation. The results of the
Rietveld refinements also show that the Sb2S3 nanowires
grow predominantly along the [010] direction, which
agrees with the fact that in the Pnma setting, the rods
and wires are parallel to the [010] direction.[17] However,
Sb2S3 develops in nature as ramified crystals or wire
structures, which often are elongated along [001].[18] So,
it should not be unusual that the seed crystals can be
synthesized to behave in a similar fashion. The same
high values of the preferred orientation parameter (s)
refined against experimental data (1.60) were observed
for all three samples. In principle, the nonrandom
particle orientations (when the shapes are anisotropic,
for example, platelet like or needle/wires like) are called
the preferred orientation effects and are addressed by
introducing the preferred orientation factor (Thkl) and
the preferred orientation parameter refined against
experimental data (s).[10,19] It has been observed[10] that
the orientation parameters s have the highest value for
the longest and thinnest Sb2S3 rods/bars and decrease
with the heating time for shorter and thicker rods/bars.
In this study, we did not find any significant morpho-
logical differences in the samples, and the preferred
orientation parameter (s) is high and has the same
values for all the samples observed.
In summary, antimony trisulfide (Sb2S3) nanowires
with a flower-like organization were synthesized suc-
cessfully by an organic colloidal synthetic method for
the first time using mixture of OA and EHA acids with
METALLURGICAL AND MATERIALS TRANSACTIONS A
different ratios precipitated at 513 K (240 °C). We also
presented that Sb2S3 nanowires with flower-like organi-
zation grow predominantly along the [010] direction and
that an excess of EHA fatty acid with the shorter
branched hydrocarbon chain better stabilizes the system
structurally than linear OA fatty acid.
Financial support for this study was granted by
the Ministry of Science and Technological Develop-
ment of the Republic of Serbia (Project 172056 and III
45015).
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