Preparation of antimony sulfide nanostructures from single-source antimony thiosemicarbazone precursors

Article abstract of DOI:10.1080/15533174.2012.740747

Antimony sulfide nanostructures have been prepared by the decomposition of antimony(III) chloride thiosemicarbazone precursors, SbCl₃(L), [L = cinnamaldehyde thiosemicarbazone (cinnamtscz) (1) and thiophene-2-carboxaldehyde thiosemicarbazone (thioptscz) (2)] either in a furnace or in solvents (ethylene glycol or diphenyl ether). The as-prepared nanocrystallites were characterized by powder XRD, TEM, and EDAX techniques, and absorption spectroscopy. XRD shows formation of orthorhombic Sb₂S₃ in all the cases. TEM images reveal spherical shaped Sb₂S₃ nanoparticles obtained by pyrolysis method, whereas nearly spherical and rod like morphologies of Sb₂S₃ were observed for the nanoparticles obtained by solvothermal decomposition in diphenyl ether and ethylene glycol, respectively. Copyright Taylor & Francis Group, LLC.

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Preparation of Antimony Sulfide Nanostructures From
Single-Source Antimony Thiosemicarbazone Precursors
Jasmine B. Biswal a & Shivram S. Garje a
a Department of Chemistry, University of Mumbai, Vidyanagari, Santacruz (East), Mumbai,
India
Accepted author version posted online: 03 Dec 2012.Published online: 26 Feb 2013.
To cite this article: Jasmine B. Biswal & Shivram S. Garje (2013): Preparation of Antimony Sulfide Nanostructures From
Single-Source Antimony Thiosemicarbazone Precursors, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal
Chemistry, 43:4, 461-465
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:461–465, 2013
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.740747
Preparation of Antimony Sulfide Nanostructures From
Single-Source Antimony Thiosemicarbazone Precursors
Jasmine B. Biswal and Shivram S. Garje
Department of Chemistry, University of Mumbai, Vidyanagari, Santacruz (East), Mumbai, India
chalcogenides, has been extensively studied due to its inter-
esting photovoltaic properties, high photosensitivity, and high
thermoelectric power (TEP), which makes it promising for ap-
plications in solar energy conversion,[2] thermoelectric cooling
technologies, and optoelectronics in IR region television cam-
eras with photoconducting targets[3,4] and write once read many
times (WORM) kind of optical storage devices.[5] Antimony
sulfide has also been used as starting material for synthesis of
sulfoantimonates of antimony and related compounds.[6] It is a
kind of layer structured direct band gap (1.78–2.5 eV) semicon-
ductor that crystallizes in the orthorhombic system (pbnm space
group).[7] Due to its good photoconductivity and wide range of
band gap, it covers the maximum range of visible and IR region
of solar energy spectrum.[2,8,9]
Many approaches have been adopted for the synthesis of
Sb2S3 including thermal decomposition,[10] vacuum evapora-
tion,[11] hydro- or solvothermal synthesis,[12–15] refluxing,[16]
and microwave treatment of various precursors[17,18] dissolved
in polyols. Recently, few articles wherein single-source pre-
cursors, such as antimony xanthates,[19] dithiocarbamates,[19,20]
dithiophosphates,[15,19] and thiourea complex of antimony[21]
were used for the synthesis of Sb2S3 nanomaterials or thin films
have been published.
Thiosemicarbazones are significant class of nitrogen- and
sulfur-donor ligands and they form complexes with many met-
als.[22,23] Usually, sulfur atom is involved in bonding resulting
in direct metal–sulfur bond. Hence we thought it worthwhile
to use metal thiosemicarbazones as single-source precursors for
the preparation of metal-sulfide nanoparticles and thin films.
Recently we have reported the utilization of antimony thiosemi-
carbazones, SbCl3(L) [L = cinnamaldehyde thiosemicarbazone
(cinnamtscz) (1) and thiophene-2-carboxaldehyde thiosemicar-
bazone (thioptscz) (2)] as single-source precursors for the de-
position of Sb2S3 thin films by AACVD method.[24]
Although there are various methods discussed in the literature
for preparation of Sb2S3 nanorods,[16,20,25,26] nanoribbons,[27,28]
and nanowires,[26,29] there is only one report available for the
synthesis of Sb2S3 nanospheres[30] to the best of our knowl-
edge. Herein we report the synthesis of Sb2S3 nanospheres and
nanorods either by solvothermal decomposition of the single-
source precursors in ethylene glycol (coordinating solvent) and
diphenyl ether (noncoordinating solvent) or by pyrolysis of
Antimony sulfide nanostructures have been prepared by the
decomposition of antimony(III) chloride thiosemicarbazone pre-
cursors, SbCl3(L), [L = cinnamaldehyde thiosemicarbazone (cin-
namtscz) (1) and thiophene-2-carboxaldehyde thiosemicarbazone
(thioptscz) (2)] either in a furnace or in solvents (ethylene glycol or
diphenyl ether). The as-prepared nanocrystallites were character-
ized by powder XRD, TEM, and EDAX techniques, and absorption
spectroscopy. XRD shows formation of orthorhombic Sb2S3 in all
the cases. TEM images reveal spherical shaped Sb2S3 nanoparti-
cles obtained by pyrolysis method, whereas nearly spherical and
rod like morphologies of Sb2S3 were observed for the nanoparti-
cles obtained by solvothermal decomposition in diphenyl ether and
ethylene glycol, respectively.
Supplemental materials are available for this article. Go to the
publisher’s online edition of Synthesis and Reactivity in Inorganic,
Metal-Organic, and Nano-Metal Chemistry to view the supplemen-
tal file.
Keywords antimony sulfide, nanostructures, semiconductors, X-ray
diffraction
INTRODUCTION
The inorganic materials, particularly nanomaterials, contain-
ing same elements in same stoichiometries but having dif-
ferent morphologies exhibit surprisingly different properties.
Therefore, there is an important significance for controlling
the morphologies of nanocrystals of a particular material. The
design and synthesis of 1D semiconductor nanomaterials and
submicron materials with constructive morphologies such as
nanotubes, nanorods, nanowires, nanospheres, and nanoribbons
have fascinated substantial attention due to their unique elec-
tronic, optical, mechanical or magnetic properties, which vary
from those of bulk materials.[1]
Antimony trisulfide (stibnite, Sb2S3), an essential member of
V2VI3 (V = As, Sb, Bi; VI = S, Se, Te) type main group metal
Received 28 February 2012; accepted 11 April 2012.
The authors are thankful to UGC for financial assistance and SAIF,
IIT-Bombay, for the EDAX data, TEM images, and SAED patterns.
Also thanks are extended to TIFR, Mumbai, for the XRD data.
Address correspondence to Shivram S. Garje, Department of Chem-
istry, University of Mumbai, Vidyanagari, Santacruz (East), Mumbai
400098, India. E-mail: ssgarje@chem.mu.ac.in
461

462
J. B. BISWAL AND S. S. GARJE
single-source precursors in a furnace. The nanostructures were where L = thiosemicarbazones of cinnamaldehyde and
characterized by UV-vis spectroscopy, XRD, EDAX, TEM, and thiophene-2-carboxaldehyde.
SAED techniques.
To assess the suitability of these complexes for the prepara-
tion of antimony sulfide, their TG analyses were carried out.[24]
Both the complexes undergo single-step decomposition to af-
ford antimony sulfide. Pyrolysis of SbCl3(cinnamtscz) (1) and
SbCl3(thioptscz) (2) either in a furnace at 350◦C or in solvents
EXPERIMENTAL
Materials and Instrumentation
All the solvents used were of analytical grade and the reac- such as ethylene glycol and diphenyl ether was carried out to
tions were carried out under oxygen free nitrogen atmosphere. evaluate the potential of these complexes for the preparation of
Antimony(III) chloride (S.D. fine) was used after vacuum dis- antimony sulfide nanostructures and also assess the difference
tillation (73◦C/1–2 mm of Hg). The precursors 1 and 2 were in morphologies obtained under different conditions. Powder
synthesized and characterized as discussed previously.[24]
XRD patterns (Figures 1 and S1) of the materials obtained from
X-ray diffraction patterns of the materials were recorded us- both the precursors correspond to pure orthorhombic phase of
ing Cu Kα radiation on a Philips X’pert PRO PANalytical X-ray Sb2S3 (JCPDS: 75–1310). The sharpness of the XRD peaks
diffractometer (TIFR, Mumbai, India) with an accelerating volt- indicates the high crystallinity of the samples. The average par-
age of 45 kV at a scanning rate of 0.05◦/s. The compositional ticle sizes of the materials obtained by decomposition of 1 and
analysis of the materials obtained was carried out on EDAX 2 in a furnace, in ethylene glycol, and in diphenyl ether esti-
(Inca Energy, model of Oxford, IIT-Bombay, India) with an mated from Scherrer’s formula are 31, 53, and 26 nm for 1 and
accumulation time of 100 s. The TEM observations were con- 23, 52, and 64 nm for 2. EDAX analyses for the materials ob-
ducted on a Philips CM 200 microscope with operating voltages tained from precursor 1 matches with Sb:S ratio of 1:1.47 (in
between 20 and 200 kV. The TEM imaging and EDAX analyses furnace), 1:1.41 (in ethylene glycol), and 1:1.40 (in diphenyl
were carried out at SAIF, IIT-Bombay, India. The absorption ether) whereas EDAX analyses for the materials obtained from
spectra were recorded on a UV-2450, UV-Vis Shimadzu spec- precursor 2 matches with Sb:S ratio of 1:1.30 (in furnace), 1:1.20
trophotometer (University of Mumbai, India).
(in ethylene glycol), and 1:1.34 (in diphenyl ether).
TEM images (Figure 2) of Sb2S3 isolated from the pyroly-
sis of 1 in a furnace at 350◦C and in refluxing diphenyl ether
showed agglomerates of spherical nanoparticles with average
diameters of 27 and 130 nm, respectively whereas, the material
obtained in ethylene glycol revealed the presence of rod like
morphology having a width of 135 nm and length of few mi-
crons (Figure 2). The diameters of the nanospheres prepared in
the present investigations are smaller than the quasinanospheres
that were obtained by Sheng et al. using the microemulsion
Synthesis of Nanoparticles
Pyrolysis in a furnace
In a small quartz boat a weighed quantity of the precursors
(200 mg of 1 and 2 each) were pyrolyzed in a furnace at 350◦C
for 2 h under nitrogen atmosphere. The furnace was cooled to
room temperature and the black material obtained was collected.
Solvothermal decomposition
In a typical experiment, 300 mg of each precursor (1 and 2)
and 15 mL of ethylene glycol/diphenyl ether was taken in a
round bottom flask. The reaction mixture was refluxed for 2 h
under nitrogen atmosphere with continuous stirring. The color
of the solution changed to black and the reaction was cooled to
room temperature. The grayish black materials obtained were
dispersed in methanol and separated by centrifugation.
All the materials obtained were characterized by XRD,
EDAX, TEM, and absorption spectroscopy.
RESULTS AND DISCUSSION
In the present investigation, SbCl3(cinnamtscz) (1) and
SbCl3(thioptscz) (2) were used as single-source precursors for
the preparation of antimony sulfide nanoparticles. The precur-
sors were synthesized by simple addition reaction of SbCl3
and corresponding thiosemicarbazone ligand (Eq. 1). They were
1
characterized by elemental analysis, IR, 1H, and 13C { H} NMR
spectroscopic techniques as discussed in our earlier report.[24]
FIG. 1. XRD patterns of orthorhombic Sb2S3 (JCPDS: 75–1310) obtained
from SbCl3(cinnamtscz) (1) by (a) pyrolysis in furnace at 350◦C and solvother-
mal decomposition, (b) in ethylene glycol, and (c) in diphenyl ether.
Dry THF
SbCl3 + L −−−−→ SbCl3(L)
[1]
R. T.

PREPARATION OF ANTIMONY SULFIDE NANOSTRUCTURES
463
FIG. 2. TEM images of (a) agglomerates of nearly spherical-shaped Sb2S3 nanoparticles, (b) nanorod, and (c) nearly spherical-shaped particles obtained by
decomposition of SbCl3(cinnamtscz) (1) in a furnace at 350◦C, in refluxing ethylene glycol and diphenyl ether, respectively (inset shows the SAED patterns of the
same).
method.[30] Bright dotted SAED patterns of Sb2S3 nanocrys- of 40 nm in width and the length of few microns (ethylene gly-
tallites obtained by pyrolysis of 1 in a furnace and in ethy- col). Nanorods obtained in ethylene glycol are monodispersed
lene glycol revealed single-crystalline nature of these materials with respect to width. The SAED patterns of these nanostruc-
while SAED of Sb2S3 prepared in diphenyl ether showed disc- tures showed single-crystalline nature and also lattice planes
like pattern indicating its polycrystalline nature. The SAED (110), (111), and (221) (furnace) and (020), (101), and (121)
patterns displayed (110), (101), and (211) lattice planes of or- (diphenyl ether) corresponding to orthorhombic phase of Sb2S3
thorhombic phase of Sb2S3 (JCPDS: 75–1310) for Sb2S3 pre- (JCPDS: 75–1310).
pared in furnace. Similarly, (101), (230), and (331) lattice planes
TEM studies revealed that nanomaterials of different mor-
for Sb2S3 prepared in ethylene glycol, and (220), (331) lattice phologies were obtained by the decomposition of precursors 1
planes for Sb2S3 prepared in diphenyl ether were observed. The and 2 in different experimental conditions. The previous results
mismatches between the sizes estimated by XRD and those ob- indicate that the nature of solvent used in solvothermal decom-
tained from TEM are observed because the particle size does position method affects the morphology of the product obtained.
not determine the line width directly in XRD.[31]
Yu et al. reported that the difference in dielectric constant of sol-
The TEM images (Figure S2) of Sb2S3 prepared by the pyrol- vents plays an important role in controlling the morphology and
ysis of 2 also revealed similar morphologies that were obtained particle sizes of the nanocrystals.[32] In addition to dielectric
for Sb2S3 synthesized from 1. However, the spherical nanopar- constant, ethylene glycol being a reducing and a capping agent
ticles are well dispersed with an average diameter of 123 nm affects morphologies of nanocrystals depending on the mech-
(furnace) and 270 nm (diphenyl ether) and rods have dimensions anism involved in the formation of nanocrystals. The possible

464
J. B. BISWAL AND S. S. GARJE
gregates of Sb2S3 stick to each other by self-assembling and
further coalesce together by recrystallization process to form
1D nanowire structure. In contrast to mechanism in ethylene
glycol, decomposition of precursor in diphenyl ether involves
nucleation followed by the growth of Sb2S3 nanostructures. In
addition to the nature of solvent, the final shape of the nanocrys-
tal formation also depends on the crystalline phase of the seed
at the nucleating stage followed by the other factors for control-
ling the subsequent growth processes. The key factors include
the intrinsic surface energy of different crystallographic sur-
faces and the choice of the nanocrystal growth regime between
thermodynamic and kinetic processes.[34]
The absorption spectra of the nanomaterials obtained by the
pyrolysis of 1 (Figure 3) in a furnace and in diphenyl ether dis-
played peaks at 246 nm (λonset = 480 nm) and 255 nm (λonset
=
450 nm), respectively. Band gap of these materials estimated by
the λonset values of the respective absorption spectrum are 2.58
and 2.75 eV, respectively. There is considerable shift in band
gaps with respect to bulk band gap of Sb2S3 (Eg = 1.72 eV) in
these materials. The results are comparable to a previous report
that showed absorption peaks in the range of 270–300 nm for
the rods of an average diameter 75 nm.[35]
Similarly, absorption spectrum (Figure S3) of the
nanospheres afforded by the pyrolysis of 2 in a furnace demon-
strated a broad peak at 707 nm. The broadness of the peak
indicates the broad distribution of the nanospheres. The absorp-
tion spectrum (Figure S3) of nanorods prepared by refluxing 2
in ethylene glycol displayed maximum at 700 nm. The result is
consistent with the investigations of Chen et al.[15] that showed
absorption at 704 nm for nanorods of width 45 nm.
CONCLUSIONS
Spherical and rod-shaped nanostructures of phase pure or-
thorhombic antimony sulfide were successfully synthesized
by pyrolysis as well as solvothermal decomposition of anti-
mony(III) thiosemicarbazone precursors. Hence, it was demon-
strated that these precursors (1 and 2) can be used to fabricate
different morphological nanostructures of Sb2S3 by selecting
the appropriate experimental parameters such as solvent and
temperature.
FIG. 3. Absorption spectra of materials obtained from decomposition of
SbCl3(cinnamtscz) (1) in (a) furnace at 350◦C and (b) in diphenyl ether.
mechanisms for the formation of Sb2S3 rods by solvothermal
decomposition in ethylene glycol can be described in a similar
fashion to Yan et al., who proposed a four-step mechanism.[33]
They have used Sb2O3 as a source of antimony and Na2S as
sulfur source. It is proposed that ethylene glycol being a good
capping agent containing two hydroxyl groups, can hold Sb3+
ions tightly in the solution. When the S2− ions are introduced
into the former solution, S2− ions rapidly attract to the vicin-
ity of Sb3+ ions to form Sb2S3 products bounded by ethylene
glycol molecules. Under the direction of these surrounded ethy-
lene glycol molecules, the collision of interparticles lead to
the formation of oriented neck-like connections along special
lattice. Finally, with the prolongation of time, the oriented ag-
SUPPLEMENTARY INFORMATION
Figures S1–S3 are the XRD patterns, TEM images, and
their SAED patterns (inset) and the absorption spectra of the
nanocrystallites obtained by decomposition of precursor 2.
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