Optical and Structural Properties of Tin Sulfide Nanoparticles Obtained via Solvothermal Routes

Article abstract of DOI:10.1002/zaac.201900065

The effect of using different solvothermal approaches, involving heat-up and hot-injection routes, on the phase, morphology and optical properties of tin sulfide nanoparticles using novel dibutyltin(IV) p-methylphenyl dithiocarbamate as single source prec

Full text of DOI:10.1002/zaac.201900065

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.201900065
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Optical and Structural Properties of Tin Sulfide Nanoparticles
Obtained via Solvothermal Routes
Jerry O. Adeyemi,[a,b] Opeyemi A. Oyewo,[c] and Damian C. Onwudiwe*[a,b]
Abstract. The effect of using different solvothermal approaches, in- obtained by the heat-up and hot injection routes respectively, at 220 °C
volving heat-up and hot-injection routes, on the phase, morphology and in the presence of oleylamine as surfactant, revealed the α-cubic
and optical properties of tin sulfide nanoparticles using novel
dibutyltin(IV) p-methylphenyl dithiocarbamate as single source pre-
cursor compound have been studied. Dibutyltin(IV) p-methylphenyldi-
thiocarbamate was synthesized and characterized using various spec-
phase of SnS with Herzenbergite structure. The X-ray diffraction
analysis of the nanoparticles also revealed patterns which showed pre-
ferred growth along (111) orientation; hence, favoring anisotropic
shapes which were more distinct at higher magnification images of the
TEM as a pseudo spherical morphology tending toward the formation
1
13
119
troscopic techniques (FT-IR, H, C and Sn), and elemental analy-
sis. TG analysis, studied under nitrogen, revealed tin sulfide of the rare of short rods. The optical property of the nanoparticles exhibited a
mixed-valence binary phase (Sn ) as the final residue at the end of blue shift in the bandgap energy with respect to the bulk, which is an
2 3
S
the decomposition process. The samples presented as SnS1 and SnS2
evidence of quantum confinement effect.
Introduction
Tin(II) sulfide (SnS) has a distorted rock salt structure which
is isostructural with germanium sulfide, in which six sulfur
atoms surround each tin atom, which has three short Sn–S
bonds within the layer and three long bonds attached to the
sulfur atoms in the next layer.[ These layers in SnS are joined
with weak van der Waals forces; thus, providing an intrinsic
chemically inert surface without dangling bonds and surface
Semiconductors with narrow bandgaps and near-infrared op-
[1]
tical activity have been of interest lately. In these group, tin
sulfide has received considerable attention because of its natu-
ral abundance, low cost, and environmental friendliness.[ Tin
sulfide exists in various forms; hence, possesses different
5]
1]
bandgap energies of 1.3 eV (SnS), 2.18 eV (SnS ), and
2
[6]
density. This is responsible for the surface of the SnS being
0
.95 eV (Sn S ). Due to the low toxicity of these materials,
2 3
[6]
devoid of Fermi level pinning.
they have been applied as solar energy absorber in holographic
recording and for infrared detection. The tin sulfide (SnS)
phase, possesses desirable properties such as high absorption
properties and high hole mobility, which favors its incorpora-
tion in solar cells materials for photovoltaic application.[2] Its
electronic bandgap, which lies between that of Ga and Si, has
attracted much attention.[ Furthermore, SnS has both indirect
and a direct bandgap (1.09 and 1.3 eV, respectively) in the
spectral region required of materials used as efficient collectors
of solar radiation. It has high optical absorption coefficient for
Different methods have been employed for the synthesis of
tin sulfide nanomaterials. The synthetic routes influences their
properties and determines their applications.[ The synthesis
of tin sulfide nanoparticles via the solvothermal decomposition
of single source precursor compounds is not widely reported
in literature compared to other routes such as wet chemical
7]
3]
[8]
[9]
route, modified solution dispersion method, and physical
deposition methods[ . Kergommeaux et al. have synthesized
tin sulfide nanoplatelets using the colloidal method of synthe-
sis, which involved Tin(IV) chloride pentahydrate, and
thioacetamide as the tin and sulfur precursors respectively in
oleylamine.[ Furthermore, tin sulfide obtained via a modi-
fied solution dispersion involving the direct dispersion of
10]
[4]
photons with energies greater than 1.3 eV.
Studies have shown that the nature of tin content in SnS
nanoparticles may influence its conducting properties and de-
11]
[3]
termines if the SnS will be a n-type or p-type conductor.
[
9]
melted tin in a sulfur-dissolved solvent has been reported. ]
Solvothermal method via single source decomposition in-
volves the decomposition of a single source precursor in high
boiling point solvents at a temperature beyond the stability of
the compound.[ These high boiling point solvents possess
coordinating groups such as thiols or amines, and act as
capping agents.
*
Prof. D. C. Onwudiwe
E-Mail: Damian.Onwudiwe@nwu.ac.za
[
[
a] Department of Chemistry
Faculty of Natural and Agricultural Science
North-West University (Mafikeng Campus)
Private Bag X2046
12]
Mmabatho 2735, South Africa
b] Material Science Innovation and Modelling (MaSIM) Research
Focus Area
Dithiocarbamate ligands have shown exceptional binding
Faculty of Natural and Agricultural Science
North-West University (Mafikeng Campus)
Private Bag X2046
ability with most metals (transition metals, main group metals,
and lanthanides) to form complexes.[
13,14]
These complexes
Mmabatho, South-Africa
have been widely applied in agriculture, industries, and medi-
cine.[ They have also proven as useful single source precur-
sor for the synthesis of metal sulfide nanoparticles because of
[
c] Department of Chemical, Metallurgical and Materials Engineering
13]
Tshwane University of Technology
Pretoria, 0001, South Africa
Z. Anorg. Allg. Chem. 0000, ᭿,0–0
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Journal of Inorganic and General Chemistry
ARTICLE
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the direct metal to sulfur bond in their structure.[14,15] Different
The 13C NMR spectrum showed a weak signal at 192 ppm,
derivatives of dithiocarbamate ligands can influence the prop- due to the carbon of the thioureide (–NCS ) group. The region
2
erties of the nanoparticles such as size and shape.[
16,17]
A
of appearance of this peak suggested the contribution of the
number of organotin(IV) dithiocarbamate complexes have double bond character of the thiureide group of the dithio-
been used to prepare different phases of tin sulfide nanopar- carbamate moiety.[ The signals due to the aromatic carbons
29]
ticles via thermal process.[
5,18–20]
However, only few reports of the ligand moiety resonated in the range 136–123 ppm,[26]
involved their use as single source precursors in the presence whereas the signal of the para-methyl carbon resonated around
21 ppm.[ The carbon signal attributed to the methylene and
29]
of coordinating solvent.
In this study, a novel complex of dibutyltin(IV) p-methyl- methyl groups in the organotin(IV) moiety were found in the
phenyldithiocarbamate was employed as single source precur- range 30–13 ppm.
The 1 Sn spectrum showed peak at –312 ppm, suggesting a
19
sor to tin sulfide nanoparticles using two methods of solvo-
thermal synthesis: the heat-up and hot-injection routes. The hexacoordinate arrangement around the Sn metal.[
complex was well characterized, and the optical and structural
21]
properties of the synthesized nanoparticles were studied using
XRD, TEM, and absorption spectroscopy.
Thermogravimetric Analysis of the Complex
The TG/DTG plot of the complex, showed three decomposi-
tion pathways as presented in Figure 1. The data obtained from
the thermogravimetric plots have been summarized in Table 1.
The first step of decomposition of the complex occurred be-
tween 98–162 °C, and this resulted into about 17.65% loss of
Results and Discussion
Synthesis of the Complex
the starting mass attributed to CH –C H from the dithiocar-
The complex preparation followed an already established
method of synthesis involving the reaction of dithiocarbamate
ligand, NaL, and dibutyltin(IV) in a 2 to 1 stoichiometric mole
3
6 4
bamate group of the complex. After this stage, the complex
further decomposed (in a second step) in the range 163–
188 °C, releasing about 20% of the starting mass which was
attributed to the butyl group from the organotin moiety and the
remaining mass was about 80% of the starting mass. This
agreed with the calculated value (81.17%) of the found mass
at this stage. This step was subsequently followed by a third
and final step in a temperature range of 211–303 °C. The mass
of the residue found was 53.97% of the starting mass and this
ratio.[21]
The reaction proceeded by the substitution of all the
available chloride ions present in the organotin(IV) chloride.
The complex was easily purified by recrystallization and the
product obtained as white precipitate, which was sparingly sol-
uble in alcohols and completely soluble in dimethylsulfoxide,
dichloromethane and chloroform. This complex was solvo-
thermally decomposed (using the heat-up and hot injection
routes), to afford dark grey precipitates which were soluble in
toluene.
agrees with the calculated value Sn S (54.80%). The phase
2
3
of tin sulfide residues observed here was similar to what has
been reported in literature for organotin(IV) pyrrolidinedithio-
carbamate complexes,[ and the phase of the residue was de-
pendent on the ligand moiety as well as temperature. Thus,
indicating their potential as a single source precursor for tin
sulfide nanoparticles.
15]
Spectroscopic Studies
Useful information was deduced from the selected FT-IR
peaks due to the wide studies on dithiocarbamate and its com-
–1
plexes. The complex showed bands around 1516 cm , which
was attributed to the partial double bond character of C–N
–
1
stretching vibration. A strong band at 1004 cm , ascribed to
C–S stretching vibration, suggested a bidentate coordination
[
22]
between the tin and the dithiocarbamate ligand.
A band ob-
–
1
served at 546 cm was ascribed to the Sn–C bond and, thus,
supports the presence of the organotin(IV) moieties.
[23]
–
1
Furthermore, a low intensity peak at 366 cm due to the pres-
[
24,25]
ence of the Sn–S bond was also observed.
1
In the H NMR spectrum, the aromatic protons were ob-
served downfield as multiplet in the region 7.47–7.12 ppm. A
signal at 2.50 ppm was ascribed to the protons of the methyl
group in the para position of the phenyl ring of the ligand
moiety. The signal observed at a higher frequency at about
5
.29 ppm, was attributed to the proton of the N–H; and the
[26,27]
position was due to the electronegative N atom.
The
signals due to the methyl and methylene protons on the
dibutyltin(IV) moiety were found in the range 2.31–
0
Figure 1. TG/DTG curves obtained in an inert atmosphere at heating
rate 10 K·min for complex [(C H ) SnL ].
4 9 2 2
.90 ppm.[
28]
–1
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Journal of Inorganic and General Chemistry
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diffraction patterns of the particles obtained via the solvother-
mal routes were similar. The patterns of the nanoparticles from
the heat-up route showed peaks indexed as (120), (021), (101),
(111), (131), (210), (002), (211), and (061), which corre-
sponded to orthorhombic phase of SnS (JCPDS no. 39–
354).[ This phase, which has a herzenbergite structure, pos-
30]
0
sesses a lattice parameter a = 4.3, b = 11.2, c = 4.0 Å, and Z
=
4. The pattern showed that the 2θ = 31.53° indexed as (111)
[
31]
was the preferred orientation growth of the nanoparticles.
The absence of peaks characteristic of other phases of tin sulf-
ide such as SnS , the oxidized form of tin, i.e SnO and atomic
2
2
tin – Sn, indicated the purity of the obtained SnS phase. Using
Debye–Scherrer equation, which shows the relationship be-
tween the size of the particle, full width at half maximum
(
(
FWHM) of the strongest peaks in SnS1 and SnS2 (indexed
111) and (040) respectively) (β) and the wavelength (λ) of the
nanoparticles, the average crystalline size (D) of the nanopar-
ticles were obtained. The sizes found were in the range 63–
65 nm for both SnS1 and SnS2. The observed orientation of
these particles suggested the growth process was controlled by
nucleation, which is in agreement with some of the studies
reported on SnS nanoparticles.[
32]
Morphology of the Synthesized SnS Nanoparticles
The images obtained from the TEM analysis of the synthe-
sized nanoparticles are presented in Figure 3a and Figure 4a.
These images showed slight agglomeration of the particles,
whose shape could be described as pseudo-spherical (with a
tendency towards the formation of short rod) is presented in
Figure 3a and Figure 4a. The particle size distributions are pre-
sented as histograms in Figure 3b and Figure 4b for SnS1 and
SnS2, respectively. The selected area electron diffraction
Figure 2. XRD pattern of tin sulfide nanoparticles obtained from
(C SnL ] using (a) heat-up route-SnS1 and (b) hot injection-
SnS2.
[
4
H
9
)
2
2
(SAED) presented as inset in Figure 3a and Figure 4a showed
the formation of circular ring, attributed to polycrystalline na-
ture of the SnS nanoparticles.[ The estimated average particle
size was found in the range of 62–66 nm for SnS1 and SnS2,
which is in agreement with the size estimation from the XRD
patterns.
8]
Table 1. Thermal analysis data of the complex.
(C SnL
Temperature range of decomposition /°C
[
4
H
9
)
2
2
]
The used capping agent, oleylamine, is a long-chain primary
alkyl-amine, which has been used widely for nanoparticle syn-
thesis as solvent for organic and inorganic compounds, reduc-
ing agent and as surfactant. Studies have shown it to produce
rods with low regularity and fewer chances for long range or-
1
2
3
st stage
nd stage
rd stage
98–162
163 –188
211–303
DTG peak temperature /°C
1
2
3
st stage
nd stage
rd stage
157
168
294
ganization which is attributed to its “cis” configuration and
[33]
buckled molecular chain.
This may suggests the reason for
Product obtained
the obtained morphology in both nanoparticles prepared.
1st decomp.
2nd decomp.
3rd decomp.
(CH
(CH
Sn S
2 3
3
3
-Ph)H(NCS
-Ph)H(NCS
2
2
)
)
2
Sn(But)
Sn
2
2
Optical Properties
Mass of residue /mg, found (calcd.)
The optical properties of semiconductors are very important
for their application in photoconductors, near-infrared detec-
tors, and photovoltaic materials. Quantum-size effect for a
1
2
3
st stage
nd stage
rd stage
13.96 (13.96)
13.56 (13.76)
8.98 (9.29)
semiconducting material can easily be manipulated by fine-
tuning the size of the semiconductor.[
34]
In semiconductor
X-ray Diffraction Study of the Nanoparticles
nanoparticles, an abrupt increase in the absorption wavelength,
The X-ray diffraction patterns of the nanoparticles obtained which matches with the bandgap energy could result due to
from both method of synthesis is presented in Figure 2. The the optical excitation of electrons across the bandgap. This is
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Figure 4. (a) TEM images of SnS2 with the corresponding SAED
pattern (inset) and (b) the size distribution histograms.
Figure 3. (a) TEM images of SnS1 with the corresponding SAED
pattern (inset) and (b) the size distribution histograms.
known as the band edge energy.[35] The properties such as
shape, size, size distribution and types of surfactants used can
influence the shape of the absorption shoulder and the band
edge position of a nanoparticle. Thus, for semiconductors, the
size of the nanoparticles could be estimated from the position
of the absorption band edge.[ The optical properties of the
obtained SnS nanoparticles have been analyzed using absorp-
tion spectroscopy. Figure 5a and b shows the absorbance spec-
tra of the nanoparticles with their respective Tauc plots. The
spectra show absorption peak around 831 and 875 nm for SnS1
where hv is the photon energy and A is a constant, which has
different values based on different transition, n characterizes
the transition. When n = 2 and 2/3 the transition is said to be
direct allowed transition, and it is an indirect allowed transition
when n = 1/2 and = 1/3. M is the molecular weight, ρ is the
density, c is the sample concentration dispersed in toluene, l is
the path length of light. Thus, the direct bandgap energies (Eg)
of the nanoparticles were obtained by plotting the graph of
35]
2
[36]
(
αhν) against hν at the point where α = 0,
Figure 5b.
The bandgap was then estimated from the linear extrapola-
as presented in
and SnS2, respectively. The bandgap energy (E ) for these
g
nanoparticles was obtained from the spectral using the near-
[37]
tion of the plot to meet (hν) axis.
For SnS1and SnS2, the
band edge absorption relation [Equation (1) and Equation
direct bandgap observed were 1.52 and 1.40 eV respectively,
which were higher than the direct bandgap of SnS bulk
(1.3 eV). Different studies have shown dissimilar direct
bandgaps for SnS nanoparticles and films ranging from 1.3–
1.92 eV. The blue shifts of about 0.22 and 0.10 eV indicated
30]
(
2)]:[
n
(
αhν) = A(hν –E
g
)
(1)
(2)
A ρ
α =
[34]
quantum-size effect in the SnS nanoparticles.
M c l
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The 1 H, 13C and 119Sn NMR spectra (in DMSO) were either ob-
tained with a Bruker Avance III 600 MHz or a Bruker Ascend
00 MHz Avance III HD (equipped with BBO) with the later using
CH Sn as an external standard. Elemental analyses of C, H, N, and
5
(
3 4
)
S in percentages were obtained with a Elementar, Vario EL Cube,
whereas the infrared spectra, were recorded with a Bruker alpha-P FT-
IR spectrophotometer. Thermogravimetric analysis (TGA/DTG) was
carried out with a SDTQ 600 Thermal analyser, with data recording
from 50–700 °C at a heating rate of 10 °C/min. The crystalline phases
of the nanoparticles were identified by X-ray diffraction (XRD) mea-
–
1
surements, with a scanning rate of 0.0018°·min , using a R o˝ ntgen
PW3040/60 X’Pert Pro XRD diffractometer equipped with nickel fil-
tered Cu-K radiation (λ = 1.5418 Å) at room temperature. The optical
α
properties of the nanoparticles were studied using a Jobin Yvon Lab-
RAM HR 800 UV/Vis/NIR spectrophotometer using toluene as sol-
vent. The morphology of the nanoparticles was characterized using a
TECNAI G2 (ACI) TEM with an accelerating voltage of 200 kV.
Synthesis of Sodium p-Methyl-phenyldithiocarbamate (NaL): The
preparation of the ligand (NaL) was achieved by slightly modifying
[
29]
a previously reported procedure.
p-Methylaniline (0.01 mol) was
dissolved in 10 mL tetrahydrofuran and reacted with a 20 mL tetra-
hydrofuran solution of NaOH (0.01 mol) in a nitrogen atmosphere.
Carbon disulfide (0.01 mol) was added dropwise via a syringe into the
solution. This mixture was stirred for 4–5 h at room temperature and
filtered. The residue obtained was washed with diethyl ether to afford
pale yellow solids, which were dried under vacuum.
Synthesis of the Dibutyltin(IV) p-Ethylphenyldithiocarbamate
Complex [(C H ) SnL ]: Dibutyltin(IV) chloride (0.005 mol) was
4 9 2 2
dissolved in 10 mL cold ethanol and added dropwise to the freshly
prepared ethanol solution of NaL. The solution was stirred for about
2
h in an ice bath. White precipitates were formed, flitered, washed
with excess ethanol and dried under vacuum for 24 h. Recrystallization
to obtain pure samples was achieved in a mixture of dichloromethane
and ethanol. Yield: 2.63 g (73.66%); M.p.: 190–191 °C. FT-IR
Figure 5. (a) UV/vis/NIR spectra and (b) TAUC plot of SnS2 and
SnS1 nanoparticles.
(
selected bands) ν˜ = 1516 (C=N), 1261 (C
–CH), 3085 (=CH), 3148 (N–H) 546 (Sn–C), 366 (Sn–S) cm . H
), 2.50 (s, 6 H,
CH CH CH ), 1.81
2
–N), 1004 (C=S), 2957
–
1 1
(
NMR (DMSO): δ = 7.47–7.12 (m, 8 H, N-C
6 4
H
Conclusions
Ar–CH ), 5.29 (s, 2 H, N-H), 2.31 (t, 4 H, Sn-CH
3
2
2
2
3
The single source precursor, dibutyltin(IV) p-methylphenyl- (m, 4 H, Sn-CH CH CH CH ), 1.36 (m, 4 H, Sn-CH CH CH CH ),
2
2
2
3
2
2
2
3
1
3
dithiocarbamate complex, was successfully synthesized and 0.90 (t, 6H Sn-CH
2
CH
2
CH
2
CH
3
) ppm. C NMR (DMSO): δ = 192
), 20.4 (Ar–CH ),
CH CH ), 25.8 (Sn–
) ppm.
Sn (598.06): calcd. C, 48.24;
(
2
–NCS
7.5 (Sn–CH
CH CH CH CH
CDCl ): δ = –312.0 ppm. C24
2
), 136.9, 133.2, 129.1, 123.5 (–C
CH CH CH ), 26.1 (Sn–CH CH
), 13.4 (Sn–CH CH
6
H
5
3
used for the solvothermal synthesis of oleylamine (OLA)
capped SnS nanoparticles. The two methods of solvothermal
synthesis used in this work (heat up and hot-injection) resulted
in different optical properties and sizes of the nanoparticles.
The decomposition of the precursor complex in nitrogen atmo-
sphere and in the absence of a capping agent resulted in a
mixed oxidation-state phase of Sn S . The structural property
revealed a herzenbergite structure of SnS with a pseudo spheri-
cal morphology which tends toward the formation of short rod
in both methods of synthesis used. An average size of about
2
2
2
3
2
2
2
3
1
19
2
2
2
3
2
CH
2
CH
2
3
Sn NMR
(
3
H
34
N
2
S
4
H, 5.74; N, 4.69; S, 21.47%; found: C, 47.84; H, 6.04; N, 4.19; S,
2.00%
2
2
3
Keywords: Organotin(IV) dithiocarbamate; Tin; Sulfide;
Nanoparticles; Optical properties
65 nm was estimated from the TEM analysis, while the optical
property indicated quantum effect. The results from the analy-
sis of the samples obtained from both approaches showed that
the hot injection method gave more suitable SnS useful as a
semiconductor.
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
J. O. Adeyemi, O. A. Oyewo, D. C. Onwudiwe* .............. 1–7
Optical and Structural Properties of Tin Sulfide Nanoparticles
Obtained via Solvothermal Routes
Z. Anorg. Allg. Chem. 0000, 0–0
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim