Structural, morphological and optical properties of iron sulfide, cobalt sulfide, copper sulfide, zinc sulfide and copper-iron sulfide nanoparticles synthesized from single source precursors

Article abstract of DOI:10.1016/j.cplett.2019.136972

Iron sulfide (1), cobalt sulfide (2), copper sulfide (3), zinc sulfide (4), and copper-iron sulfide (5) nanoparticles were prepared from [Fe(dbzdtc)₃], [Co(dbzdtc)₃], [Cu(dbzdtc)₂], [Zn(dbzdtc)₂] and [Cu(dbzdtc)₃][FeCl₄] (where dbzdtc = N,N-dibenzyldithiocarbamate), respectively. The synthesized samples 1–5 were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), UV–Vis, photoluminescence and Fourier transform infrared (FT-IR) spectroscopy techniques. In the X-ray diffraction patterns of samples 1, 3–5, sharp peaks are observed which indicates that the as-prepared metal sulfide nanoparticles, 1,3–5 are crystalline. EDAX spectra confirm the composition of the metal sulfides. The SAED spots of as-prepared copper sulfide and zinc sulfide supports the crystalline nature of the nanoparticles. UV–Vis absorption and photoluminescence spectra of the synthesized nanoparticles 1–5 show a significant blue shift compared to that of the respective bulk metal sulfide. Infrared spectral studies on metal sulfides (Samples 1,2,4 and 5) confirm the presence of capping agent ethylenediamine (en).

Full text of DOI:10.1016/j.cplett.2019.136972

Journal Pre-proofs
Research paper
Structural, morphological and optical properties of iron sulfide, cobalt sulfide,
copper sulfide, zinc sulfide and copper-iron sulfide nanoparticles synthesized
from single source precursors
E. Sathiyaraj, S. Thirumaran
PII:
S0009-2614(19)30953-4
DOI:
https://doi.org/10.1016/j.cplett.2019.136972
CPLETT 136972
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Chemical Physics Letters
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Revised Date:
Accepted Date:
17 September 2019
9 November 2019
16 November 2019
Please cite this article as: E. Sathiyaraj, S. Thirumaran, Structural, morphological and optical properties of iron
sulfide, cobalt sulfide, copper sulfide, zinc sulfide and copper-iron sulfide nanoparticles synthesized from single
source precursors, Chemical Physics Letters (2019), doi: https://doi.org/10.1016/j.cplett.2019.136972
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Structural, morphological and optical properties of iron sulfide, cobalt sulfide,
copper sulfide, zinc sulfide and copper-iron sulfide nanoparticles synthesized
from single source precursors
E. Sathiyaraja,b, S. Thirumarana*
aDepartment of Chemistry, Annamalai University, Annamalainagar-608 002, Tamilnadu,
India.
bDepartment of Chemistry, Fudan University, Jiangwan Campus, Shanghai 200438, P.R.
China.
*Address for correspondence
Dr. S. Thirumaran
Department of Chemistry
Annamalai University
Annamalainagar 608 002
Tamilnadu, INDIA
Tel: +91 9842897597
E-mail: sthirumaran@yahoo.com

Structural, morphological and optical properties of iron sulfide, cobalt sulfide,
copper sulfide, zinc sulfide and copper-iron sulfide nanoparticles synthesized
from single source precursors
E. Sathiyaraja,b, S. Thirumarana*
aDepartment of Chemistry, Annamalai University, Annamalainagar-608 002, Tamilnadu,
India.
bDepartment of Chemistry, Fudan University, Jiangwan Campus, Shanghai 200438, P.R.
China.
Abstract
Iron sulfide (1), cobalt sulfide (2), copper sulfide (3), zinc sulfide (4), and
copper-iron sulfide (5) nanoparticles were prepared from [Fe(dbzdtc)3], [Co(dbzdtc)3],
[Cu(dbzdtc)2], [Zn(dbzdtc)2] and [Cu(dbzdtc)3][FeCl4] (where dbzdtc = N,N-
dibenzyldithiocarbamate), respectively. The synthesized samples 1-5 were
characterized by X-ray diffraction (XRD), field emission scanning electron
microscopy (FESEM), transmission electron microscopy (TEM), high-resolution
transmission electron microscopy (HRTEM), UV-Vis, photoluminescence and Fourier
transform infrared (FT-IR) spectroscopy techniques. In the X-ray diffraction patterns
of samples 1, 3-5, sharp peaks are observed which indicates that the as-prepared metal
sulfide nanoparticles, 1,3-5 are crystalline. EDAX spectra confirm the composition of
the metal sulfides. The SAED spots of as-prepared copper sulfide and zinc sulfide
supports the crystalline nature of the nanoparticles. UV-Vis absorption and
photoluminescence spectra of the synthesized nanoparticles 1-5 show a significant

blue shift compared to that of the respective bulk metal sulfide. Infrared spectral
studies on metal sulfides (Samples 1,2,4 and 5) confirm the presence of capping agent
ethylenediamine (en).
Keywords: metal sulfides; copper-iron sulfide; nanoparticles; solvothermal; single
source precursors; ethylenediamine
Introduction
The current research interest on the study of growth mechanism and
applications of nanoparticles is due to their size dependent physical properties and
lattice orders. Transition metal sulfide nanoparticles reveal unique size-dependent
optical, electrical, electronic and magnetic properties that are different from the bulk
material as well as their applications in catalysts [1, 2], cathode material and lithium
batteries [3], electrodes [4], light-emitting diodes [5], sensors [6], solar controller and
solar radiation absorber [7]. Almost all first row transition metals reacted with sulfur
to form metal sulfides. Metal sulfide nanoparticles with different phases and
morphologies have been prepared by various methods such as hydrothermal [8],
solvothermal [9], microwave irradiation [10], sonochemical [11] and thermolysis
methods [12] of single-source. An important method to synthesize metal sulfide
nanoparticles is the use of single source precursors, complexes where the metal
chalogen bond is already in place and simple mechanism results in the precipitation of
the semi conducting material. Single source precursor is usually safer, cheaper and more
stable than the use of two or more precursors. Metal dithiocarbamate complexes have been
widely used as single source precursors to prepare metal sulfide and metal oxide
nanoparticles [13, 14]. Suitable changes in organic moiety of dithiocarbamate ligands in

metal-dithiocarbamate complexes can affect the phase, size,shape and physical properties of
the metal sulfide nanoparticles [15-18]. In this work, we present the synthesis of some
transition metal sulfides from metal N,N- dibenzyldithiocarbamate complexes and the
characterization of metal sulfides using XRD, FESEM,, TEM, HRTEM, UV-Vis,
photoluminescence and FT-IR spectroscopy techniques.
EXPERIMENTAL
2.1. Materials and methods
Analytical grade chemical reagents were used without further
purification. The X-ray powder diffraction data were collected on a SEIFERT JHOD
DYE FLEX 2002 diffractometer with CuKα radiation (λ= 1.54178 Å). Field emission
scanning electron microscopy (FESEM, Carl Zeiss Supra 55) fitted with an energy
dispersive X-ray spectrometer (EDAX) was used to characterize the morphologies and
elemental analysis of the samples. TEM was performed using Hitachi (H-7500) at an
operating voltage of 120 kV equipped with a CCD Camera. A SHIMADZU UV-1650
PC spectrophotometer was used to record absorption spectra of nanoparticles at room
temperature. A Perkin Elmer L555 spectrometer was used to measure the
photoluminescence spectra of the nanoparticles.
2.2 Preparation of metal sulfide nanoparticles
2.2.1. Preparation of precursors
To use as single source precursors for the preparation of metal sulfide
nanoparticles, the following complexes, Tris(N,N-dibenzyldithiocarbamato-

S,S)iron(III),
tris(N,N-dibenzyldithiocarbamato-S,S)cobalt(III),
bis(N,N-
dibenzyldithiocarbamato-S,S)copper(II)
and
bis(N,N-dibenzyldithiocarbamato-
S,S)zinc(II) were prepared using the methods reported earlier (Scheme 1) [19]. N,N-
dibenzylamine was dissolved in ethanol and carbon disulfide was added drop wise
under ice cold condition (5 °C). An aqueous solution of metal salt was added. The
solid formed was filtered off and washed with cold water.
2.2.2. Preparation of metal sulfide nanoparticles (Samples 1-4)
(a). Preparation of iron sulfide nanoparticles (Sample 1)
30 mL of ethylenediamine was added into 0.5 g of tris(N,N-
dibenzyldithiocarbamato-S,S)iron(III) in a round bottom flask. The contents of the
round bottom flask were refluxed for 15 min. The precipitate obtained (Sample 1) was
filtered off and washed with methanol.
(b). Preparation of samples 2-4
A similar method to that described for the preparation of sample 1 was
adopted to prepare cobalt sulfide (sample 2), copper sulfide (sample 3) and zinc
sulfide (sample 4) from tris(N,N-dibenzyldithiocarbamato-S,S)cobalt(III) (2)
bis(N,N-dibenzyldithiocarbamato-S,S)copper(II)
dithiocarbamato-S,S)zinc(II) (4), respectively.
(3)
and
bis(N,N-dibenzyl-
2.2.3. Preparation of copper-iron sulfide nanoparticle (Sample 5)
20 mmol of bis(N,N-dibenzyldithiocarbamato-S,S)copper(II) was
dissolved in chloroform. To this solution, FeCl3 (2.0 mmol) in acetone was added with

constant stirring for 15 h. The brown solid [Cu(dbdtc)3][FeCl4] was filtered and dried
[20]. 0.5 g of [Cu(dbdtc)3][FeCl4] complex was dissolved in 30 mL of
ethylenediamine in a flask and refluxed for 15 min. The precipitate (Sample 5)
obtained was filtered off and washed with methanol.
3. Results and discussion
3.1. Characterization of metal sulfide nanoparticles
3.1.1. Powder X-ray diffraction analysis
X-ray powder diffraction patterns of as-prepared metal sulfide samples
1-5 are shown in Fig. 1. The observed sharp peaks in XRD patterns of samples 1, 3-5
indicate that the as-prepared nanoparticles 1, 3-5 are in crystalline nature. All the
peaks of the XRD pattern of sample 1 (iron sulfide) can be indexed to a pure
monoclinic phase of FeS (JCPDS card No. 89-9020) with lattice constants a=
8.1103(3), b= 5.6666(2) and c = 6.4832(2) Å. No peaks for other types of FeS are
observed in the XRD patterns, indicating the high purity of the as-prepared FeS. In the
case of sample 2, the diffraction peaks appeared at angles 2θ of 30.6, 35.3, 46.9 and
54.6 correspond to (100), (101), (102) and (110) planes of hexagonal CoS (JCPDS
card No. 042-0826). The peaks in the PXRD pattern of sample 3 can be assigned to (0
0 2), (0 0 4), (1 0 0), (1 0 1), (1 0 4), (1 0 5), (1 0 6), (1 0 7) and (1 0 8) planes of the
hexagonal phase (JCPDS card No. 78-2391, Covellite syn, CuS) and the planes (0 0
2), (1 0 2), (1 0 4), (1 0 5), (1 0 6), (1 0 8), (2 0 2) and (1 1 6) of the hexagonal phase
(JCPDS card No. 74-1234). The observed peaks in XRD pattern of sample 4

correspond to the reflections of rhombohedral (JCPDS Card No. 83-1700), cubic
(JCPDS Card No. 05-0566) and hexagonal (JCPDS Card No. 12-0688) ZnS.
3.1.2. Morphological characterization
The morphologies of the as-prepared metal sulfide nanoparticles (samples 1-5) were
investigated by SEM, FESEM, TEM and HRTEM analysis. FESEM and TEM images
of sample 1 (Fig. 2 (a) and (b)) reveal that the morphology of the iron sulfide is
shapeless flakes. The TEM image (Fig. 2 (b)) indicates that the length of irregular
shaped flake FeS nanoparticles is in the range of 80 to 550 nm and width in the range
60 to 250 nm. These flakes are obtained due to the growth of the iron sulfide nuclei
with rigidly growth-blocked (400) facet. The growth of (400) facet is blocked by
strong adsorption of ethylenediamine on them during the growth of nanocrytstals [21-
23].
SEM, FESEM and TEM images of sample 2 (cobalt sulfide) are shown in
Fig.3. From the figure, it can be seen that most of the particles are shapeless and few
particles are rod shape. FESEM image of sample 3 is shown in Fig. 4 (a). Fig. 4 (b-d)
shows the typical HRTEM images of CuS hexagonal nanosheets synthesized from
bis(dibenzyldithiocarbamato-S,S′)copper(II) complex. HRTEM image of hexagonal
nanosheet with high magnification (Fig. 4 (d)) shows the lattice fringes with a ‘d’
spacing 2.4 Å corresponding to the (1 0 2) reflection of hexagonal CuS. The selected
area electron diffraction (SAED) pattern (Fig. 4 (e)) confirms the crystallinity of
CuS hexagonal nanosheet. Shape control mechanism for the formation of different

shapes of copper sulfide particles was reported by several authors [24-26]. The
formation CuS hexagonal nanosheets are due to the presence of excess copper in the
product [24]. In the present study, the EDS analysis shows that the product is copper
rich (Cu: S = 1:0.90). Therefore, the shape of the copper sulfide product is hexagonal
sheets. The appearance of hexagonal sheets is conjugated with the development of
facet between (010) and (100) which is (1ī0). DFT based explanation was also
reported for the formation of hexagonal copper sulfide nanosheets due to the presence
of excess copper in the product [24].
FESEM image of ZnS (sample 4) is shown in Fig. 5 (a). This reveals that the
as-prepared ZnS particles are mostly nanodisc and some nanosheets. HRTEM
images (Fig. 5 (b-d)) exhibit that most of the particles are nanosheets and a few
particles are nanorods. The diameter of the ZnS nanorods is 20 to 25 nm and length
is ≈120 nm. The SAED spots of ZnS indicate the crystalline nature of as-prepared
ZnS. Fig. 6 (a) shows FESEM image of agglomerated particles of sample 5. The size
of agglomerates is ~1 µm which is mainly assembled by nanoparticles. The sample 5
reveal that the nanoparticles are uniform in size and average size of the particles is
about 19-22 nm (Fig. 6 (b-c)).
3.1.3. Energy dispersive X-ray (EDAX) analysis
The formation of monometallic and bimetallic sulfide was confirmed
using EDAX analysis. EDAX spectra of samples 1-5 are shown in Fig. S1. Energy
dispersive X-ray spectra of samples 1-4 reveal the presence of Fe, Co, Cu and Zn,
respectively and S. In all the samples, this indicates that the samples 1-4 are iron

sulfide, cobalt sulfide, copper sulfide and zinc sulfide, respectively. The atomic ratios
of Fe/S (Sample 1), Co/S (Sample 2), and Zn/S. (Sample 4) are 0.76:1, 0.80:1 and
0.77:1, respectively. The relatively higher atomic ratio of S compared to metals in
samples 1, 2 and 4 may be due to the presence of vacant metal ion or some sulfur
dangling bonds. The atomic ratio of Cu/S is 1:0.90. This shows the presence of excess
Cu2+ in the sample 3. EDAX analysis of sample 5 was confirms the formation of
bimetallic sulfide with the composition as Fe:Cu:S in ratio of 0.54: 0.51:1.
3.1.4 Optical properties
The UV-Vis absorption spectra of as-prepared metal sulfide
nanoparticles (sample 1-5) are shown in Fig. 7. Absorption bands observed at 345 nm
(3.59 eV), 325 nm (3.81 eV), 246 nm (5.04 eV) and 264 nm (4.69 eV) for 1-4 are due
to the first exciton absorption of metal sulfide nanoparticles. The large blue shift
relative to the bulk metal sulfide band gap reveals the existence of strong quantum
confinement effect [27-30]. A shoulder is observed at 255 nm (4.86 eV) in UV-Vis
absorption spectrum of sample 5. This band reveals blue and red shift with respect to
as-prepared FeS (345 nm) and CuS (246 nm), respectively. These shifts arise from the
differences in size and shape of metal sulfide nanoparticles and due to the presence of
bimetals (Fe and Cu) in sample 5.
The observed peak at 411 nm in the photoluminescence spectra of FeS
(Fig. 8) is commonly attributed to the excitonic or band edge emission [27]. The
photoluminescence spectrum of sample 2 shows two emission peaks at 338 and 406
nm. The first peak is due to direct electron hole recombination (i.e, band edge
emission). The other emission peak (406 nm) in the photoluminescence is ascribed to
the recombination of trapped electrons/holes in some surface defects of the CoS

particles [31]. Fig. 8 shows a broad emission peak centered at 406 nm due to the
vacancies near the valence band [32]. An emission peak is observed at 364 nm for
sample 4, which is markedly blue shifted compared to that of bulk ZnS (440 nm) [33].
This is attributed to the quantum confinement effect. PL spectrum of bimetallic sulfide
nanoparticles (sample 5) reveals a broad emission peak at 416 due to the band edge
emission. The emission peak of sample 5 was observed at lower wavelength compared
to all other as-prepared monometallic sulfides. Generally, it is known that the
photoluminescence properties of nanoparticles are affected by several factors such as
particle shape, size and crystallinity etc.
3.1.5. IR spectral studies
Infrared spectra of samples 1-5 are shown in Fig. S2-S6. Samples 1-5
were recorded to confirm the presence of capping agent ethylenediamine (en). The
bands appeared in the region 2850-2950 cm-1 for samples 1-5 (except sample 3) CuS
are assigned to the aliphatic C–H symmetric and asymmetric stretching vibrations of
ethyl group. IR spectra of all the samples 1-5 except 3 show bands around 3160 and
3290 cm-1, which are due to the N–H stretching vibrations of ethylenediamine. The N–
H deformation of ethylenediamine is appeared around 1600 cm-1 [34]. These indicate
that ethylenediamine is present in the metal sulfide nanoparticle samples (1, 2, 4, 5)
and serving as capping agent for the metal sulfide nanoparticles. This study also
reveals that the absence of capping agent in copper sulfide (sample 3). The lack of
bands due to the aromatic C–H and N–CS2 stretching vibrations in the FT-IR spectra
of all the metal sulfide nanoparticles (samples 1-5) confirms the absence of N,N-

dibenzyldithiocarbamate ligand in metal sulfide nanoparticles. The IR finger prints of
en remain evident indicating that en is present on the surface of the nanoparticles (1, 2,
4, 5) and serving as a capping agent for the latter [35].
Spherical iron sulfide nanoparticles were synthesized through chemical
reduction method using Na2S and FeSO4.7H2O as S and Fe sources, respectively and
trisodium citrate as a reducing agent [36]. Fe3S4 rectangular nanoplates with average
size 58 x 38 x 10 nm were prepared from tris(N,N-diisobutyldithiocarbamato-
S,S’)iron(III) [37]. In this paper, we reported the preparation of iron sulfide flakes
using tris(N,N-dibenzyldithiocarbamato-S,S’)iron(III) as single source precursors.
Krishnamoorthy et.al., demonstrated a hydrothermal method to prepare cubic cobalt
sulfide nanoparticles using cobalt chloride and thiourea [38]. Spherical, rod and ring
shaped nanoparticles were prepared from cobalt (III) dithiocarbamate complexes by
solvothermal method [39]. Nanorods and shapeless nanoparticles were obtained using
tris(N,N-dibenzyldithiocarbamato-S,S’)cobalt(III). Ajibade et.al have prepared
spherical hexagonal phase CuS nanoparticles from various Cu(II) dithiocarbamates as
single source precursors by solvothermal decomposition method [40, 41]. Herein we
report the preparation of hexagonal shape, 3-38 nm hexagonal phase copper sulfide
nanoparticles from bis(N,N-dibenzyldithiocarbamato-S,S’)copper(II). Spherical zinc
sulfide nanoparticles were prepared by biogenic method using Na2S with Zn(NO3)
[42]. Selvaganapathy et al., have synthesized ZnS nanoparticles from bis(N,N-di(4–
fluorobenzyldithiocarbamato-S,S’)zinc (II) by solvothermal method. It was observed
that spherical nanoparticles with diameter in the range 36-100 nm [43]. Abullah et.al,

reported the preparation of spherical ZnS nanoparticles with diameter between 6nm
and 11 nm from zinc(II) N-ethylcyclohexyldithiocarbamate [44]. The preparation of
ZnS nanodisc and nanosheets from bis (N,N-dibenzyldithiocarbamato-S,S’)zinc(II)
was reported in this manuscript. Preparation of spherical CuFeS2 nanoparticles from
solvothermal decomposition of mixture of two complexes, [Cu(S2CNiBu2)2] and
[Fe(S2CNiBu2)3], was reported [45]. But in this paper, single complex was used as
precursor for the preparation of CuFeS2.
Two different compounds were used as source for metal and sulfur to prepare
metal sulfide nanoparticles. However in this manuscript, single metal dithiocarbamate
complex was used as single source precursor for the preparation of metal sulfide. In
addition the comparison of size, shape and phase of metal sulfide nanoparticles in the
manuscript with those prepared from various metal dithiocarbamate complexes reveals
that the various size, shapes and phases of metal sulfide nanoparticles can be prepared
from metal dithiocarbamate complexes.
4. Conclusion
A simple and versatile method for the synthesis of monometallic sulfide
(metal= Fe, Co, Cu and Zn ) and bimetallic sulfide (copper-iron sulfide) nanoparticles
using metal dithiocarbamate complexes in a single pot low temperature process was
reported. As-prepared nanoparticles were characterized by XRD, FESEM, TEM,
HRTEM, UV-Vis, photoluminescence and FT-IR spectroscopy. This study indicated
that the metal-dithiocarbamates were found to be effective single source precursors for

the preparation of the metal sulfide nanoparticles via solvothermal method.
Ethylenediamine was used as a solvent for the preparation of the metal sulfide
nanoparticles and it acts as a capping agent.
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Scheme and figure captions
Scheme 1. Preparation of metal (M= Fe, Co, Cu and Zn) dibenzyldithiocarbamate
complexes and synthesis of metal sulfide nanoparticles (samples 1-5).
Fig. 1. PXRD pattern of (a) sample 1 (FeS, JCPDS 89-9020), (b) sample 2 [* (CoS,
JCPDS 042-0826); ≠ (S, JCPDS 34-0941)], (c ) sample 3 [+-hexagonal (JCPDS: 78-
2391), *-hexagonal (JCPDS: 74-1234) CuS and ≠-S (JCPDS:72-0410)],
(d) sample 4 [+-cubic (JCPDS Card No: 05-0566), *-hexagonal (JCPDS Card No: 12-
0688) and ≠- rhombohedral ZnS (JCPDS Card No: 83:1700)] (JCPDS Card No:
83:1700)], (e ) sample 5.
Fig. 2. (a) FESEM and (b) TEM image of sample 1
Figs. 3. (a)SEM and (b) FESEM and (c-d) TEM images of sample 2
Fig. 4. (a) FESEM , (b-d) HRTEM images and (e) SAED pattern of sample 3
Fig. 5. (a)FESEM, (b-d) HRTEM images and (e) SAED pattern of sample 4
Fig. 6. (a) FESEM and (b-c)TEM images of sample 5
Fig. 7. UV-Vis absorption spectrum of samples 1-5
Fig. 8. Photoluminescence spectrum of samples 1-5

GRAPHICAL ABSTRACT
nanoflake
s
nanorod
(2)
(1)
20 nm
(4)
500 nm
(3)
nanodiscs
nanosheets
500 nm
200 nm

Highlights




Metal sulfides (M=Fe,Co.Cu,Zn) and copper-iron sulfide nanoparticles were
prepared
They were characterized using XRD, FESEM, HRTEM, UV-Vis, PL and FT-
IR spectroscopy
UV-Vis spectral studies reveal the existence of strong quantum confinement
effect
Metal-dithiocarbamates were found to be effective single source precursors

Scheme. 1

(b)
(a)
(c)
(d)
(e)

Fig. 1.
(b)
(a)
200 nm
500 nm
Fig. 2.

(b)
(c)
(a)
20 µm
100
(d)
(b)
1 µm
20

Fig.3.
(a)
100 nm
(b)
(c)
(e)
(d)

Fig.4
(a)
200 nm
(c)
(b)
(d)