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Materials Letters 99 (2013) 138–141

Contents lists available at SciVerse ScienceDirect

Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Very narrow In2S3 nanorods and nanowires from a single source precursor
Ahmed Lutfi Abdelhady a,b,1, Karthik Ramasamy a,b,2, Mohammad A. Malik a,b, Paul O’Brien a,b,n
a
The Schools of Chemistry and Materials, The University of Manchester, Oxford Road, Manchester M13 9PL, UK
b
Manchester Materials Center, The University of Manchester, Oxford Road, Manchester M13 9PL, UK

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

Article history: Ultra-thin (o 1.0 nm) nanorods or nanowires of b-In2S3were synthesized from the thermolysis of the
Received 8 November 2012 indium(III) complex of 1,1,5,5-tetra-iso-propyl-2-thiobiuret in hot oleylamine.
Accepted 14 February 2013 & 2013 Elsevier B.V. All rights reserved.
Available online 21 February 2013

Keywords:
Indium sulfide
Single source precursor
Ultra-thin nanorods
Nanowires

1. Introduction solvothermal [10,13], arrested precipitation [14], sonochemical

One-dimensional (1D) nanostructures such as wires, rods and
tubes are proven to be showing enhancement in electrical or
thermal transport as compared to zero-dimensional nanostruc-
tures [1,2]. These structures (1D) are involved in the fabrication of
electronic, optoelectronic and electrochemical devices [2]. Indium
sulfide is a semiconductor which exists in different stable forms,
specifically, InS, In2S3, and In6S7 [3]. InS is orthorhombic and In6S7
is monoclinic, whereas, In2S3 has three different structures: a
defect cubic (a-In2S3), cubic or tetragonal defect spinel (b-In2S3)
and layered structure (g-In2S3) [3–5]. b-In2S3is stable at room
temperature and up to 420 1C, with a high degree of vacancies
ordering [5,6]. Above 420 1C the In atoms become randomly
distributed as the a-In2S3 is formed and above 754 1C the trigonal
layered structure g-In2S3 becomes the stable phase [7]. The beta
form has been used in green or red phosphors for color televisions
[8], as buffer layer instead of toxic CdS in CuInSe2-based solar
[15] and thermal decomposition in hot coordinating solvent [16].
However, the synthesis of In2S3 nanowires and/or nanorods with
high aspect ratio is limited. The applicability of indium sulfide
nanowires and nanorods can indisputably be augmented if they
can be synthesized in narrow size distribution with large surface
area. Very few reports are available on the use of single source
precursor for the synthesis of monodispersed indium sulfide
nanostructures. Although we have previously used single source
precursors for the deposition of indium sulfide thin films [17].
Examples of the single source precursor explored for the synthesis
of indium sulfide nanoparticles include: [In(S2CNEt2)3] and the
polymeric complex [MeIn(SCH2CH2S)]n which produced InS and
In2S3, respectively [18,19]. Herein we report the facile synthesis of
ultra-thin ( o1.0 nm) nanorods or nanowires of b-In2S3with large
Relative Intensity (a. u.)

cells [9] and as an electrode material in lithium ion batteries

[10]because of its high defects and band gap (2.0–2.3 eV) [11].
(440)
(311)

Various synthetic methods have been used for the preparation

(400)

of indium sulfide nanostructures including: hydrothermal [12],

n
Corresponding author at: The School of Chemistry, The University of Manchester,
Oxford Road, Manchester M13 9PL, UK. Tel.: þ44 161 275 4653;
fax: þ44 161 275 4598.
E-mail addresses: a_l_abdelhady@mans.edu.eg (A. Lutfi Abdelhady),
kramasamy@mint.ua.edu (K. Ramasamy), 10 20 30 40 50 60
paul.obrien@manchester.ac.uk (P. O’Brien).
1
Present address: Department of Chemistry, Faculty of Science, Mansoura 2 Theta (deg.)
University, Egypt.
2
Present address: Center for Materials for Information Technology, Fig. 1. P-XRD pattern of b-In2S3nanorods prepared from a 5 mM solution of the
The University of Alabama, Tuscaloosa, AL, USA. precursor in OLA at 200 1C. Inset shows the crystal structure of b-In2S3.

0167-577X/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2013.02.061
 Author's personal copy

A. Lutfi Abdelhady et al. / Materials Letters 99 (2013) 138–141 139

surface area from the thermolysis of the single source precursor
[In(SON(CNiPr2)2)3] [20] in hot oleylamine. To the best of our
knowledge this work reports the thinnest indium sulfide nanor-
ods and nanowires to date.
2. Experimental details
All preparations were performed under an inert atmosphere of
dry nitrogen using standard Schlenk techniques. The complex was
prepared as described in our previous report [20]. A solution of
di-iso-propylcarbamoyl chloride (1.0 g, 6 mmol) and sodium thio-
cyanate (0.49 g, 6 mmol) in acetonitrile (25 mL) was heated to
reflux with continuous stirring for 1 h, during which time a fine
precipitate of sodium chloride formed. The cooled reaction
mixture was added to di-iso-propylamine (1.49 mL, 12 mmol)
followed by stirring for 30 min and addition of indium(III)
chloride (0.45 g, 2 mmol) gave the product as white powder
which was dried under vacuum for 24 h before use.
The nanowires and nanorods were synthesized by thermal
decomposition of the single source precursor [In(SON(CNiPr2)2)3].
Thermolysis experiments were carried out under different condi-
tions; using three different concentrations of the precursor (5, 10
and 20 mM) at 200 1C, three different temperatures (200, 240 and
280 1C) at the concentration of 5 mM and different solvent/
capping agent combinations. In a typical experiment, oleylamine

Fig. 2. (a, b, and c) TEM of In2S3 nanorods synthesized at 200 1C using 5 mM, 10 mM and 20 mM, respectively. (d and e) TEM of In2S3 nanowires synthesized using 5 m M at
240 1C and at 280 1C, respectively. (f) SAED of (d). All scale bars, 20 nm.
 Author's personal copy
140 A. Lutfi Abdelhady et al. / Materials Letters 99 (2013) 138–141
Fig. 3. (a, b, and c) TEM of In2S3 nanorods after 5, 30 and 60 min, respectively. All scale bars, 20 nm.
OLA (15 mL) was degassed under reduced pressure at 100 1C for 30
min and then heated to the desired temperature under nitrogen. The
required amount of the precursor [In(SON(CNiPr2)2)3] was dispersed
in OLA (5 mL) and injected into the hot OLA. The reaction tempera-
ture was maintained for 1 h. The mixture was then cooled to
approximately 70 1C before adding an excess of methanol to give a
yellowish precipitate which was separated by centrifugation. After
several washings with methanol, the solid was redispersed in toluene
for further characterization.
The crystallographic phase of nanowires or nanorods was
confirmed by X-ray diffraction studies on a Bruker AXS D8
diffractometer using Cu-Ka radiation. The morphology and
dimensions of nanowires or nanorods were identified using
Tecnai F30 FEG transmission electron microscopy (TEM), operat-
ing at 300 kV, all samples deposited over carbon coated copper
grids. The absorption spectra were recorded on a UV–vis spectro-
photometer (Thermo Spectronic Helios Beta) in the wavelength
range of 350–750 nm.
3. Results and discussion
p-XRD pattern of indium sulfide nanocrystals prepared from a
5 mM solution of the precursor in OLA at 200 1C (Fig. 1) corre-
spond to b-In2S3 (ICDD card no. 32-0456). The broad peaks in the
pattern suggest the ultra-small diameter of nanorods or the
nanowires as was confirmed by TEM images (Fig. 2). The absence
of the (220), (422) and (511) peaks indicates a preferred growth
direction, resulting in the 1D nanorods/nanowires structure. All
these results are consistent with previously reported very thin
one-dimensional nanocrystals [21–23].
TEM images revealed that the material synthesized at 200 1C,
is composed of very thin nanorods. The width and length of the
nanorods decreased on increasing the concentration of precursor.
The nanorods prepared at 5 mM had dimensions of 0.970.1 nm
and 11.8 73.5 nm, which decreased to 0.7 70.1 nm and
7.172.6 nm at 10 mM. A further decrease in dimensions to
0.6 70.1 nm and 5.871.6 nm was observed at 20 mM (Fig. 2(a–
c)). Increasing the growth temperature from 200 1C, at the lowest
concentration (5 mM), to 240 1C produced nanowires without any
change in the width (0.970.1 nm) but with a significant change
in the length (Fig. 2(d)). A further increase (280 1C) in the growth
temperature resulted in a considerable increase in the diameter of
the nanowires with a broader distribution (1.470.4 nm) (Fig. 2(e)).
Ultra-thin indium sulfide nanowires and nanotubes were
previously reported as oriented nanoplates [22,23]. In our results,
there was no evidence of the formation of any plates, which
makes our indium sulfide nanorods/nanowires, to the best of our
knowledge, the thinnest prepared. The deposition of these nanor-
ods can only be possible by oriented attachment mechanism.
The SAED of the nanowires prepared from a 5 mM solution of
the precursor in OLA at 240 1C confirmed the formation of
b-In2S3with strong diffraction rings matching the (311) and the
(440) planes (Fig. 2(f)). Unfortunately, due to the ultra-thinness of
the nanorods/nanowires, HRTEM could not produce images to
determine their lattice spacing or the growth direction [22].
Progress of the reaction time was investigated by withdrawing a
couple of drops from the reaction mixture at different time intervals
(5, 30 and 60 min) for the sample prepared at 200 1C using the lowest
concentration (5 mM) of precursor. The width of the nanorods
increased slightly from 0.670.2 nm to 0.770.1 and finally
0.970.1 nm, whilst the nanorods length showed a more rapid
growth from 7.772.3 nm to 10.272.6 nm and 11.873.5 nm after
5, 30 and 60 min from the injection, respectively (Fig. 3). Injecting an
ODE solution of the precursor into hot OLA or an OLA solution into
hot DDT also produced ultra-thin nanorods of b-In2S3 (Supporting
information).
The absorption spectra of all nanorods or nanowires dispersed in
toluene showed almost no difference in the band edge. Absorption
spectra of samples obtained after different reaction times (UV–vis
spectra is given in supporting information) showed the little differ-
ence, which suggests only small changes in the width of the rods/
wires. The step like shape of the absorption spectra is because of the
conduction to valence band transition as observed previously
[21,22,24].
4. Conclusion
In conclusion, we report the facile synthesis of b-In2S3 nanorods or
nanowires of extreme thinness (o1.0 nm) from the thermolysis of
the single source precursor [In(SON(CNiPr2)2)3] in hot oleylamine.
Acknowledgment
A. L. A. gratefully acknowledges financial support from the
Egyptian Cultural Affairs and Missions Sector. KR thankful to ORS,
UK. The authors also thank EPSRC, UK for the grants to POB that
have made this research possible.
Appendix A. Supporting information
Supplementary data associated with this article can be found
in the online version at http://dx.doi.org/10.1016/j.matlet.2013.
02.061.
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