Solar Energy 174 (2018) 373–385

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Solar Energy
journal homepage: www.elsevier.com/locate/solener

Phase optimization study of orthorhombic structured SnS nanorods from T

CTAB assisted polyol synthesis for higher efficiency thin film solar cells
Benjamin Hudson Baby, D. Bharathi Mohan*
Department of Physics, School of Physical, Chemical and Applied Sciences, Pondicherry University, R.V. Nagar, Kalapet, Puducherry 605 014, India

A R T I C LE I N FO A B S T R A C T

Keywords: Orthorhombic SnS nanorods were prepared from CTAB assisted polyol synthesis method at reaction temperature
Tin sulphide of 150 °C. In this method, the source (Sn, S) concentration ratio, CTAB concentration and reaction time were
Polyol synthesis optimized to obtain single phase SnS as evident from Raman and XPS analyses. Crystal structure from XRD along
Structural properties with SAED pattern confirmed the formation of orthorhombic SnS structure. Morphological analysis from HR-
Optical
TEM revealed the formation of SnS nanorods with improved homogeneity in size and shape by increasing the
Electrical properties
reaction time and CTAB concentration. The observed shift in the absorption band edge and absorption maxima
by varying the CTAB concentration and reaction time is very well correlated with the morphological and che-
mical structural variations. Tauc plot shows the successful tuning of band gap value to 1.5 eV which is the
optimum value of thin film solar cells, by varying the reaction time of sample with 0.025 M of CTAB. Electrical
properties were studied from the Hall measurement which showed p-type conductivity for single phase SnS
while n-type conductivity observed for mixed phases.

1. Introduction
In the field of thin film solar cells (TFSCs), Tin (II) Sulfide (SnS) is a
promising alternative p-type material as an absorber layer because of its
excellent physical, electrical and optical properties compared to the
existing absorber layer materials such as CZTS, CIGS, GaAs and CdTe
(Wang et al., 2014; Hirai et al., 2013; Green et al., 2015). Although
these materials exhibit very high efficiency, the toxicity, scarcity, and
cost associated with In, Ga, As, Te and Cd present in CIGS, GaAs and
CdTe and the complexities associated with manufacturing quaternary
compounds such as CIGS and CZTS limit their sustainability (Banu
et al., 2016; Park et al., 2015; Baby and Mohan, 2017a). While SnS is
less toxic, its constituent elements are abundant in nature and it is a
binary compound which involves simple growth chemistry compared to
quaternary compounds. It has direct a band gap value of 1.38 eV close
to the optimum value of 1.5 eV (Cheng and Conibeer, 2011). It has high
optical absorption coefficient of α > 105 cm−1 for photons with en-
ergy higher than the band gap value and this minimizes the thickness of
an absorber layer in TFSCs and hence relaxing the need of long minority
carrier diffusion length (Devika et al., 2007, 2010; Klochko et al., 2016;
Banai et al., 2016). In SnS, each Sn atom is coordinated with six sulfur
atom with three short Sn-S bonds of ca 2.7 A° and three long Sn-S bonds
of almost 3.4 A° (Lewis et al., 2014; Pejjai et al., 2017). Each unit cell
consists of two SnS layers and one of the long distance sulfur resides on
the neighboring SnS layer. This weak Sn-S interaction binds two SnS
layers together to form a double layer structure which is perpendicular
to the b axis with tin and sulfur atoms covalently bonded within the
layers and weak van der Waals bonds between the layers (Yang et al.,
2015). This van der Waals interaction between the double layers in SnS
gives a chemically inert surface with few surface states and these defect
tolerant surface reduce carrier recombination loss due to the defects at
p-n junction and at grain boundaries (Sinsermsuksakul et al., 2011;
Albers et al., 1961; Avellaneda et al., 2008). Also SnS has majority
carrier Hall mobility 90 cm2/Vs or higher and tunable majority carrier
density in the range of 1015–1018 cm−3(Sucharitakul et al., 2016; Banai
et al., 2016). It exhibit p-type conductivity due to the availability of tin
vacancy (VSn) which act as a shallow acceptor (Vidal et al., 2012). It
undergoes a phase transition from low symmetric α phase to high
symmetric β phase at 600 °C which is a second order phase transition
produced by the continuous shift of Sn and S atom along (1 0 0) axis
(Reddy et al., 2015b; Reddy, 2013).
Although the theoretical efficiency for SnS based single junction

Abbreviations: TFSCs, thin film solar cells; CZTS, copper zinc tin sulphide; CIGS, copper indium gallium sulphide; GaAs, gallium arsenide; CdTe, cadmium telluride;
NPs, nanoparticles; Rt, reaction time; CTAB, cetyltrimethylammonium bromide; CBD, chemical bath deposition; EG, ethylene glycol; UDEDM, uniform deformation
energy density model
*
Corresponding author.
E-mail address: d.bharathimohan@gmail.com (D. Bharathi Mohan).

https://doi.org/10.1016/j.solener.2018.09.019
Received 28 June 2018; Received in revised form 5 September 2018; Accepted 10 September 2018
Available online 20 September 2018
0038-092X/ © 2018 Elsevier Ltd. All rights reserved.
B.H. Baby, D. Bharathi Mohan
Fig. 1. Schematic diagram of CTAB assisted polyol synthesis method for the preparation of SnS NPs.
solar cell is 24% predicted by Prince-Loferski, the conversion efficiency
of SnS based solar cells increased from 1.3% to 3.88% by using CdS as a
buffer layer and 4.36% using Zn(O,S) as a buffer layer by following
thermal evaporation and atomic layer deposition techniques respec-
tively (Loferski, 1956; Reddy et al., 2006; Steinmann et al., 2014;
Sinsermsuksakul et al., 2014). This far discrepancy between the theo-
retical predictions and experimental results may be due to the presence
of intrinsic defects and impurity phases and also due to poor device
fabrication (Malone et al., 2014; Sinsermsuksakul et al., 2014; Burton
et al., 2013; Baby and Mohan, 2017b).
The different shape of SnS nanostructures were prepared by sol-
vothermal, hydrothermal, PVP assisted, CTAB assisted and surfactant
free micro emulsion methods and the phase formation was studied
through XRD (Ren et al., 2012; Tarkas et al., 2017; Sohila et al., 2011a;
Biswas et al., 2007; Panda et al., 2006; Yue et al., 2009; Peng et al.,
2007; Yang et al., 2015; Lu et al., 2013; Reddy et al., 2013; Chaki et al.,
2014). It is always difficult to prove single phase formation by probing
through XRD because it cannot give information about any particular
phase if it was present with less than 5% (Baby and Mohan, 2017a,
2017b). Many other researchers studied the single phase SnS formation
by characterizing with Raman spectrometer exciting at wavelengths
514 and 532 nm (Sohila et al., 2011b; Ali et al., 2017; Bhorde et al.,
2018). However, Raman active modes of Sn2S3 phase cannot be excited
with laser wavelengths 514 and 532 nm Baby and Mohan (2017a). Liu
et al. (2003) confirmed the formation of single phase SnS by following
CTAB and oxalic acid assisted DI water based reaction for 10 h. Gedi
et al. (2016) prepared orthorhombic structured single phase SnS by
following CBD method with tartaric acid was used as a complexing
agent. Chalapathi et al. (2016) prepared cubic structured SnS by fol-
lowing CBD method with EDTA was used as the complexing agent. Baby
and Mohan (2017a) reported the phase optimization study of SnS NPs
prepared by PVP assisted polyol synthesis method. According to the
best of our knowledge, it is very clear that a detailed analysis to confirm
the phase purity of orthorhombic structured SnS NPs using surfactant
(CTAB) without the formation of secondary phases such as SnS2 and
Sn2S3, with a band gap ∼1.5 eV along with the support of Hall mea-
surement study were not clearly investigated so far which are indeed
important aspects towards enhancing the efficiency of SnS. In this work,
CTAB assisted polyol method is followed for the synthesis of single
phase SnS NPs. It involves ethylene glycol (EG) as the reducing agent
and cetyltrimethylammoniumbromide (CTAB) as the cationic surfac-
tant, controls the formation growth and agglomeration of NPs.
The main objectives of this work are following, 1. To synthesis
single phase SnS with an energy band gap near to 1.5 eV using a simple
wet chemistry route by tailoring certain parameters such as (a) Sn:S
source concentration ratio, (b) CTAB concentration and (c) Reaction
time. 2. To investigate the single phase formation and the possibility of
formation of secondary phases by XRD, Raman, XPS, EDAX, and
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Solar Energy 174 (2018) 373–385
UV–Vis-NIR spectrophotometer. 3. To study the electrical property of
the semiconductor SnS NPs with the effect due to the presence of SnS2
and Sn2S3 phases from Hall effect measurement.
2. Experimental procedure
SnS nanoparticles were synthesized using ethylene glycol (EG)
(Qualigens Fine Chemicals) as the reaction medium as well as the re-
ducing agent for salts and CTAB as the cationic surfactant. For the re-
action, high pure (reagent grade) SnCl2 and Na2S salts used as tin and
sulfur sources, obtained from Merck (Merck Specialties Pvt. Ltd,
Mumbai.) and Fischer Scientific (Thermo Fischer Scientific India Pvt.
Ltd, Mumbai) respectively. Initially, 0.1 M of SnCl2, 0.6 M of Na2S
prepared in 10 ml of EG separately. Then Na2S solution added drop by
drop into SnCl2 solution placed in silicon oil bath at 150 °C and after the
addition, the solution color changes to dark brown indicating the for-
mation of Sn-S phase. Then solution was collected and quenched in a
water bath after 10 min. This colloidal solution was washed several
times using centrifuge at 5000 rpm and then Sn-S NPs were collected by
removing supernatant. Then, a thick (few microns) film of Sn-S was
prepared by a simple drop casting technique. Following the above
procedure a set of experiment was carried out by varying the ratio
between SnCl2 and Na2S from 1:6 to 1:15 M to optimize the source
concentration ratio between Sn:S in the formation of single phase of
SnS.
The role of CTAB as a cationic surfactant in the structural and
morphological properties of SnS is studied by varying the concentration
of CTAB from 0.01 M to 0.5 M. Initially, 0.1 M of SnCl2, 1.2 M of Na2S
and 0.01 M of CTAB is prepared in 10 ml of EG separately. Then by
following the similar experimental setup as explained above, CTAB and
Na2S solutions were added drop by drop into SnCl2 solution and as a
result the solution color changes to dark brown. Then reaction is
stopped after 10 min, washing several times with methanol and then a
thick film is prepared using drop casting technique. Then the experi-
ment is repeated by increasing the concentration of CTAB as 0.025,
0.05, 0.1, 0.15, 0.2, 0.3 and 0.5 M. The effect of reaction time (Rt) is
also studied by varying the Rt as 10, 20, 40 and 60 min. The complete
experimental procedure is drawn as a schematic diagram as shown in
Fig. 1.
The chemical structure of as deposited drop casted films were stu-
died by using confocal Raman spectrometer (ReinshawinVia Raman
Microscope, UK) with an excitation wavelength of 514 and 785 nm
using Ar+ and semiconductor lasers respectively. Raman analysis was
carried out in the scan range of 50–350 cm−1 with acquisition time and
power as 30 s and 1.25mW for 514 nm and 150 s and 0.0025 mW for
785 nm excitation wavelengths respectively. The crystal structure of as
deposited drop casted films were studied by using X-ray diffraction
(XRD) (Panalytical-X’Pert PRO). The surface morphology and electron
B.H. Baby, D. Bharathi Mohan
diffraction patterns of as prepared samples were studied by using high
resolution transmission electron microscope (HR-TEM) (JEOL/JEM
2100). The elemental composition of the samples were studied by EDAX
analysis by using VEGA 3, TESCAN. The oxidation states of Sn and S
and the chemical bonding of SnS were analysed using X-ray photo-
electron spectroscopy (XPS) (PHI 5000 Versa Probe II, FEI Inc) in the
binding energy range of 0–1000 eV and the binding energies in spec-
trometer were calibrated using C 1s line. The absorbance spectra of the
colloidal solutions prepared after dispersing the NPs in the methanol
medium was studied using UV–Vis-NIR spectrophotometer (Shimadzu
UV-3600 Plus) from the wavelength range of 300–1200 nm. The
emission spectra of the prepared colloidal solutions were recorded with
an excitation wavelength of 520 nm using spectrofluorometer (FLUO-
ROLOG-FL3-11), equipped with Xenon lamp-450 W. The electrical re-
sistivity, mobility, carrier concentration, etc. were studied using Agilent
device analyser-B1500A Hall measurement system.
3. Results and discussions
3.1. Chemical structural analysis
Raman spectroscopy is an efficient, sensitive and nondestructive
technique to study the phase formation of different tin sulphide phases
such as SnS, SnS2 and Sn2S3 by their distinct Raman shift. The pre-
dominant Raman active modes of SnS are Ag (40, 95, 192 and
218 cm−1), B2g (70, 85 and 290 cm−1) and B3g (49 and 164 cm−1)
(Chandrasekhar et al., 1977). Similarly the Raman active modes of
Sn2S3 is observed at 63, 183, 154 and 308 cm−1 and for SnS2 205 and
315 cm−1 (Chandrasekhar and Mead, 1979; Smith et al., 1977).
Fig. 2(a) and (b) shows the Raman spectra of as deposited samples
prepared by varying the source concentration ratio of Sn:S from 1:6 M
to 1:15 M for a Rt of 10 min without any surfactants, using an excitation
wavelength of 514 and 785 nm respectively. For samples prepared with
Sn:S molarity ratio up to 1:9 M, Raman analysis confirmed the forma-
tion of SnS2 and Sn2S3 (314.4 and 64.7 cm−1) as secondary phases
Fig. 2. Raman spectra of as deposited sample prepared by varying Sn:S ratio from 1:6 to 1:15 M for the reaction time of 10 min without CTAB using excitation
wavelength of (a) 514 nm and (b) 785 nm.
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Solar Energy 174 (2018) 373–385
along with SnS. By increasing to 1:12 M leads to the complete absence
of the peak at 314.4 cm−1 confirming the complete suppression of SnS2
phase. Also by increasing Sn:S ratio from 1:6 to 1:12 M leads to a blue
shift in the Raman peak from 64.7 to 66 cm−1 corresponds to Sn2S3
phase whereas the Raman peak corresponds to SnS is observed at
70 cm−1. Further increase in the Sn:S ratio to 1:15 M leads to a red shift
in the Raman peak towards 64.7 cm−1 corresponds to Sn2S3 phase.
Hence for Sn:S source concentration ratio of 1:12 M, chemical structural
analysis shows a trend to form single phase of SnS, which is not com-
pletely achieved in the absence of any surfactant. Also it can be clearly
seen that Raman modes of SnS2 is highly active with an excitation
wavelength of 514 nm whereas Raman modes of SnS and Sn2S3 phases
are highly active by using an excitation wavelength of 785 nm (Baby
and Mohan, 2017a).
The effect of surfactant in the single phase formation of SnS is
studied by varying the concentration of CTAB from 0.01 to 0.3 M by
keeping Sn:S molarity ratio 1:12 M for a Rt of 10 min using 514 and
785 nm as excitation wavelength as shown in Fig. 3(a) and (b) re-
spectively. By using 514 nm as an excitation wavelength, formation of
SnS2 (∼314 cm−1) as a secondary phase is confirmed for samples
prepared with higher concentration of CTAB (> 0.15 M) while single
phase of SnS is obtained for lower concentration (up to 0.1 M). By using
785 nm as an excitation wavelength, single phase of SnS is obtained for
samples prepared with 0.025 M of CTAB while increasing the CTAB
concentration leads to the formation of Sn2S3 (∼63 cm−1) as a sec-
ondary phase along with SnS. Hence chemical structural analysis con-
firmed the formation of single phase of SnS for samples prepared with
0.025 M of CTAB whereas by increasing the CTAB concentration up to
0.1 M leads to the formation of Sn2S3 as an additional phase along with
SnS and further increase results in the formation of both SnS2 and Sn2S3
as an additional phase along with SnS.
The influence of Rt on the single phase formation of SnS is studied
by varying the Rt as 10, 20, 40 and 60 min as shown in Fig. 4. By
increasing the Rt to 20 min (Fig. 4(a)), the secondary phases are de-
creasing for sample prepared with 0.025 M of CTAB and all the peaks
B.H. Baby, D. Bharathi Mohan Solar Energy 174 (2018) 373–385

Fig. 3. Raman spectra of as deposited samples prepared by varying the concentration of CTAB from 0.025 to 0.3 M for a recation time of 10 min using excitation
wavelength of (a) 514 and (b) 785 nm.

observed matching with SnS phase. Further increase in CTAB con-
centration leads to a red shift in these two peaks showing the formation
of Sn2S3 phase. Hence Raman analysis confirmed the formation of
single phase of SnS only for sample with 0.025 M of CTAB. However
further increase in reaction time towards 40 and 60 min leads to the
formation of single phase of SnS irrespective of variation in the CTAB
concentration (Fig. 4(b) and (c)). The FWHM value is decreasing sys-
tematically by increasing the Rt from 10 to 60 min indicating the im-
proved crystallinity of the sample. Chemical structural analysis con-
firmed that improved phase stability of SnS is achieved by increasing
the Rt. Also by increasing the Rt from 10 min to 60 min, the Raman
peak at 164 cm−1 corresponds to the B3g (c(ab)c) mode become pro-
minent indicating the predominant vibration of Sn atom against S atom
(Chandrasekhar et al., 1977; Baby and Mohan, 2017a). The peak at 95,
190 and 220 cm−1 corresponds to the Ag (c(aa)c) mode which arise due
to the incident and scattered direction of radiation parallel to c - axis
and the polarization of incident and scattered photons along a axis
(Chandrasekhar et al., 1977; Baby and Mohan, 2017a). The high intense
peak at 220 cm−1 corresponds to the vibration of Sn atom against the S
atoms (Chandrasekhar et al., 1977; Baby and Mohan, 2017a). The less
intense peaks at 95 cm−1 and 190 cm−1 corresponds to the ‘breathing’
and ‘waving’ modes of the layer (Chandrasekhar et al., 1977; Baby and
Mohan, 2017a). The less intense peak at 285 cm−1 corresponds to the
B2g (b(ac)b) mode which arise due to the vibration of Sn atom against S
atom (Chandrasekhar et al., 1977; Baby and Mohan, 2017a). The ob-
served Raman peak at 74 cm−1 for samples with Rt of 40 min is also

Fig. 4. Raman spectra using an excitation wavelength of 785 nm for as deposited samples prepared by varying the concentration of CTAB from 0.025 to 0.2 M for a
recation time of (a) 20 min (b) 40 min and (c) 60 min.

376
B.H. Baby, D. Bharathi Mohan
Fig. 5. XRD pattern of 350 °C annealed samples prepared with 0.025 and 0.2 M
of CTAB with reation time of 10 and 40 min.
corresponds to B2g mode appeared due to the compressive mode of the
layer along c axis (Chandrasekhar et al., 1977; Baby and Mohan,
2017a).
3.2. Crystal structural analysis
The crystal structure of the drop casted films were studied using
XRD technique after annealed the samples under vacuum (10−3 mbar)
at 350 °C for 90 min as shown in Fig. 5. As the same peak orientation
was observed for all samples prepared by varying the CTAB con-
centration from 0 to 0.2 M and Rt as 10, 20 and 40 min, only a couple of
important results were included in Fig. 5 whereas the microstructural
properties were discussed for other samples and enclosed in Table 1. All
the diffraction peaks were compared with the standard JCPDS card No.
00-039-0354 and indexed as (1 1 0), (1 2 0), (1 0 1), (1 1 1), (1 3 1),
(2 1 0), (0 0 2), (2 1 1), (1 1 2), (1 2 2), (2 3 1), (0 4 2), (2 5 1) and (1 5 2)
confirming the formation of single phase polycrystalline SnS NPs with
orthorhombic crystal structure. The preferred orientation along (1 1 1)
plane predicts the formation of Sn rich SnS NPs (Baby and Mohan,
2017a).
The lattice constants of orthorhombic structure SnS phase can be
calculated using the equation
1 h2 k2 l2
= 2 + 2 + 2
d2 a b c
and the values are enclosed in Table 1 which is compared with the
std JCPDS card no 00-039-0354. Increasing the Rt as well as the CTAB
concentration results an expansion in the a and b direction and com-
pression along c direction. The crystallite size of these samples were
studied from XRD analysis using Debye-Scherer formula
Kλ
D=
βcosθ
where D is crystallite size, K is shape factor (∼0.9), λ is wavelength of
Cukα radiation and β is full width at half maximum (in radians) and the
calculated values are enclosed in Table 1. The crystallite size is slightly
decreased in CTAB based reaction as compared to EG based reaction,
whereas by increasing the Rt from 10 to 60 min leads to a slight in-
crease in the crystallite size. Micro strain of the samples, which arise
due to dislocations, grain boundary triple junction, contact or sinter
stresses, stacking faults, coherency stresses, etc. is calculated from XRD
using the following equation (Mote et al., 2012; Baby and Mohan,
2017a; Gedi et al., 2016),
β cosθ
Strain(ε) =
4 (3)
Solar Energy 174 (2018) 373–385
And the calculated values are enclosed in Table 1.
Williamson-Hall relation given by (Williamson and Hall, 1953)
β cosθ K 4ε sinθ
= +
λ D λ (4)
For an orthorhombic crystal, young’s modulus related to their
elastic compliances Sij as
1
= S11 l14 + (2S12 + S66 ) l12 l 22 + S22 l 24 + (2S23 + S44 ) l 22 l32 + S33 l34
E
+ (2S13 + S55) l12 l32
where l1, l2 and l3 are direction cosines (Wen et al., 2017). S11, S12, S66,
S22, S23, S44, S33, S13 and S55 are the elastic compliances of SnS which can be
calculated from the elastic constants (Lubarda and Chen, 2008; Koc et al.,
2015; Kafashan, 2018). The calculated values for the elastic compliances
of SnS are S11 = 13.549 × 10−12, S12 = −0.129 × 10−12, S13 =
−6.5665 × 10−12, S33 = 15.8052 × 10−12, S44 = 27.5710 × 10−12 and
S66 = 25.9538 × 10−12 (TPa−1).
The energy density of a crystal can be calculated using uniform
deformation energy density model (UDEDM). In UDEDM, the aniso-
tropic nature of the crystallite is considered with the assumption that
the deformation energy is uniform in all crystallographic direction. For
an elastic systems that follows hooks law, the energy density u can be
calculated as u = ε2Yhkl/2 (Aly et al., 2017; Zak et al., 2011). Then equ.
4 can be rewritten as
1/2
β cosθ K 4sinθ ⎛ 2u ⎞
= + ⎜ ⎟
λ D λ ⎝ Yhkl ⎠ (6)
Then the anisotropic energy density (u) can be calculated from the
slop of the graph plotted between 4sinθ/(Yhkl/2)1/2 vs βcosθ and the
crystallite size from the y intercept as shown in Fig. 6 and the calculated
values are enclosed in Table 2. Stress is calculated from the Hook’s law,
keeping the linear relation between stress and strain given by, σ = Yε,
where σ is the stress of the crystal, ε is anisotropic micro strain which
will depend upon the crystallographic directions and Y is the young’s
modulus (Y = 105.3 GPa) (Aly et al., 2017; Mote et al., 2012; Koc et al.,
2015).
The observed micro strain could be possibly due to the presence of
the above mentioned intrinsic defects in the polycrystalline sample.
Crystallite size calculated from W-H method, increases with increasing
Rt due to increase in crystallization of SnS structure. The dislocation
density is related with the crystal growth defects and it is defined as the
length of dislocation line per unit volume which can be calculated from
the crystallite size using Williamson and Smallman’s formula
(1)
δ = 1/D2 (7)
where D is the crystallite Size and the values are enclosed in Table 2
which is well agreement with the reported values. Increasing the Rt as
well as the CTAB concentration enhance the crystallisation of the
sample which in turn decrease the Dislocation density as evident from
Fig. 5 (Chaki et al., 2014). The number of unit cells in SnS nanocrystals
can be calculated using the following equation (Aly et al., 2017),
(2)
n = πD3 /(6V) (8)
where V is the unit volume and the calculated values are enclosed in
Table 2. Increase in the Rt as well as CTAB concentration results an
increase in the crystal size number per unit volume which is due to the
slight increase in the crystallite size by increasing the Rt and CTAB
concentration.
3.3. XPS analysis
Fig. 7 shows a wide range XPS spectra of SnS NPs synthesized with
0.025 M of CTAB, attributed to the presence of C, O, Sn and S. The
observed XPS peaks were calibrated using C1s at 284.5 eV. The XPS
spectra shows characteristic peaks of Sn 4d, S 2p, S 2, C 1 s, Sn 3d, O 1 s,
377
B.H. Baby, D. Bharathi Mohan Solar Energy 174 (2018) 373–385

Table 1
2θ, FWHM, d-spacing, crystallite size, micro strain, lattice parameters and unit cell volume values obtained from the XRD analysis of annealed SnS samples.
Sample code 2theta (°) FWHM (β) d (A°) D (nm) D average (nm) ε * 10−3 ε average * 10−3 a (A°) b (A°) c (A°) V = abc (A°)3

00-039-0354 4.3291 11.1923 3.9838 193.03

Sn:S – 1:12 26.03 0.52836 3.4204 15 15 2.3209 2.2877 4.2966 11.2992 3.9861 193.52
31.59 0.56242 2.8291 15 2.3595
38.98 0.55101 2.3088 15 2.2647
51.09 0.51803 1.7863 16 2.0378
48.74 0.61831 1.8668 14 2.4556

CTAB 0.025 M – 10 min 25.95 0.59348 3.4204 14 14 2.5048 2.39 4.2932 11.3180 3.9903 193.89
31.55 0.59302 2.8299 14 2.4403
38.93 0.57628 2.3105 15 2.3597
51.09 0.62682 1.7863 15 2.3445

CTAB 0.025 M – 20 min 25.98 0.5806 3.4269 17 16 2.3568 2.3626 4.3079 11.3111 3.9837 194.11
31.49 0.5535 2.8317 15 2.3225
38.81 0.54712 2.311 16 2.2676
48.84 0.6038 1.8632 14 2.3971
51.09 0.632 1.7863 16 2.4715

CTAB 0.025 M – 40 min 25.97 0.45139 3.4282 19 17 1.9177 2.4397 4.3109 11.3318 3.9733 194.10
31.49 0.54121 2.8291 15 2.2538
38.94 0.4261 2.311 20 3.5033
51.08 0.5384 1.7866 19 2.1268
48.68 0.6034 1.8689 14 2.3970

CTAB 0.2 M – 10 min 30.54 0.6281 2.9248 12 13 2.7675 2.4164 4.2999 11.2869 3.99 193.64
31.52 0.5745 2.8369 12 2.411
38.91 0.6286 2.3128 13 2.6211
51.02 0.6375 1.7886 13 2.5309
64.1 0.6492 1.4516 14 2.3992

CTAB 0.2 M – 20 min 26.01 0.61472 3.423 13 14 2.6114 2.5728 4.2970 11.3244 3.9886 194.09
31.60 0.65858 2.8291 13 2.7629
38.95 0.5822 2.3105 14 2.3932
48.78 0.63499 1.8654 14 2.5215

CTAB 0.2 M – 40 min 31.43 0.63859 2.8299 13 15 2.6807 2.6906 4.3065 11.3520 3.9781 194.45
38.91 0.62867 2.3128 14 2.6211
51.02 0.63757 1.7886 15 2.5309
64.1 0.64922 1.4516 15 2.3992

Sn 3p and Sn 3 s. The observed peaks at 285 and 531 eV correspond to
C1s and O1s respectively due to the surface contamination during drop
casting (Reddy et al., 2015a). Fig. 8(a) and (b) shows the high resolu-
tion XPS spectra of Sn 3d and S 2p states of CTAB 0.025 M – 10 min. The
observed separation of 8.5 eV between the Sn3d5/2 and Sn3d3/2 is well
matching with standard values (Reddy et al., 2015a; Baby and Mohan,
2017a). Among different phases of tin sulphides, SnS has Sn3d5/2 peak
at 485.9 eV and S2p3/2 peak at 161 eV attributed to the presence of
Sn2+ oxidation state and S-Sn2+ bonding respectively, SnS2 has Sn3d5/2
peak at 487 eV and S2p3/2 peak at 162 eV indicate the presence of Sn4+
oxidation state and S-Sn4+ bonding respectively and Sn2S3 has both
Sn2+ and Sn4+ oxidation states (Reddy et al., 2015a; Baby and Mohan,
2017a). Hence the observed Sn3d5/2 peaks at 486 and 161 eV attributed
to the presence of Sn2+ oxidation state and S-Sn2+ bond formation
which confirms the formation of single phase of SnS without any sec-
ondary phases which is in good agreement with Raman and XRD re-
sults. Fig. 8(c) and (d) shows Sn 3d and S 2p states high resolution XPS
spectra corresponds to sample CTAB 0.05 M – 10 min. The observed
doublet at 485.4 and 486.4 eV confirms the presence of Sn2+ and Sn4+
oxidation states respectively. High resolution XPS spectra of S2p3/2

Fig. 6. The plot between (β cosθ) vs (4 sinθ/(Ehkl/2)1/2) for samples prepared with CTAB 0.025 M for reaction time of (a) 10 min and (b) 40 min.

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B.H. Baby, D. Bharathi Mohan Solar Energy 174 (2018) 373–385

Table 2
Calculated crystallite size (D), micro strain (ε), Stress (σ), and energy density (u) of SnS nanoparticles obtained using Williamson-hall method.
Sample code D (nm) ε UDEDM δ * 10−3 (nm−2) n

−3
D (nm) ε σ (Mpa) U (KJm )

CTAB 0.025 M – 10 min 14 2.39 14 1.7640 186 163 5.40 6.79

CTAB 0.025 M – 40 min 17 2.4395 18 2.2612 238 269 3.02 16.25

Fig. 7. A wide range XPS spectra for sample CTAB 0.025 M – 10 min. Fig. 9. HR-TEM image shows surface morphology of Sn-S NPs prepared in EG
based reaction with the molarity ratio of 1:12 (Sn:S).

Fig. 8. High resolution XPS spectra of (a) and (c) for Sn3d and (b) and (d) for S2p oxidation states for sample CTAB 0.025 M – 10 min and CTAB 0.15 M – 10 min
respectively.

379
B.H. Baby, D. Bharathi Mohan
Fig. 10. HR-TEM images show surface morphology of SnS NPs prepared using 0.025 M of CTAB for Rt of (a) 10 min and (c) 40 min. (b) SAED pattern of poly-
crystalline SnS NPs of sample CTAB 0.025–10 min. (d) High resolution image of CTAB 0.025–40 min shows the inter planar spacing of SnS NPs.
consist of 2 peaks at 161 and 161.7 eV which attributed to the bond
formation of S-Sn2+ and S-Sn4+ respectively. Hence XPS analysis
confirms the formation of Sn2S3 and SnS2 as secondary phases along
with SnS for sample CTAB 0.05 M – 10 min as evident from Raman
analysis.
3.4. Surface morphology
Fig. 9 shows the surface morphology of SnS NPs prepared in EG
without CTAB for Rt of 10 min. It shows highly inhomogeneous size
formation of SnS nanorods with length and width ranging from 60 to
100 nm and 10–15 nm respectively with an average aspect ratio ∼ 6.6.
Whereas in EG-CTAB based reactions, with 0.025 M of CTAB for Rt of
10 min (Fig. 10(a)), the formation of SnS nanorods (with length
250 nm, width ∼ 35 nm and aspect ratio ∼ 5.5) and spherical shape of
particles (with size of 150 nm in diameter) is confirmed. By increasing
Rt to 40 min, the reaction leads to the formation of highly homogenous
SnS nanorods with length 220–250 nm, width 25–35 nm and average
aspect ratio 8 (Fig. 10(c)). By increasing CTAB concentration to 0.2 M
and with Rt 10 min leads to the formation of SnS nanorods with length
180–200 nm, width 10–12 nm and aspect ratio ∼ 9.2 (Fig. 11(a)).
Further increase in Rt to 40 min leads to the formation of highly
homogenous SnS nanorods with length 220–240 nm, width 25–30 nm
and aspect ratio ∼ 9.6 (Fig. 11(c)). The high resolution image
(Fig. 10(d)) shows that the observed nanorods have 0.28 and 0.35 nm
as the interplanar spacing corresponds to hkl planes (1 1 1) and (1 2 0)
as the preferential growth direction respectively confirming the or-
thorhombic crystal structure of SnS as evident from XRD analysis (Pol
et al., 2008). It is already discussed that SnS exhibit layered structure
with each Sn atom is coordinated six S atoms results an highly distorted
octahedral geometry which leads to three short and three long SneS
bonds with ∼0.27 and ∼0.34 nm respectively (Lewis et al., 2014;
Suryawanshi et al., 2014). The observed two lattice fringes in HRTEM
image may arise due to this distorted octahedral geometry (Reddy et al.,
2015b). The selected area electron diffraction pattern (SAED) images
confirmed the formation of single phase orthorhombic polycrystalline
SnS NPs for sample prepared with EG-CTAB based reactions with CTAB
0.025–10 min (Fig. 10(b)) and CTAB 0.2 M – 40 min (Fig. 11(d)) after
Fig. 11. HR-TEM images shows the surface morphology of Sn-S NPs prepared using 0.2 M of CTAB for Rt of (a) 10 and (d) 40 min. SAED pattern of polycrystalline Sn-
S NPs of samples (b) CTAB 0.2 M – 10 min and (d) CTAB 0.2 M – 40 min. The symbol * indicates for the sample CTAB 0.2 M – 10 min corresponds to Sn2S3 phase.
380
Solar Energy 174 (2018) 373–385
comparing with JCPDF card No. 00-039-0354. While for sample with
CTAB 0.2 M – 10 min (Fig. 11(b)) confirmed the formation of Sn2S3
[JCPDF card No. 01-073-0031] as a secondary phase along with SnS as
evident from Raman analysis.
Surface morphology analysis confirmed the improved homogeneity
in size and shape of as prepared SnS NPs by using CTAB as cationic
surfactant, compared to EG base reaction and it is further enhanced by
increasing the CTAB concentration from 0.025 M to 0.2 M. Also by in-
creasing the CTAB concentration from 0.025 to 0.2 M, length and width
of the NRs is decreasing from 250 to 180 nm and 30 to 10 nm respec-
tively with an increase in aspect ratio from 5.5 to 9.2, indicating more
controlled growth process by increasing the CTAB concentration due to
the improved stabilization of NPs by increasing the surfactant con-
centration which enables the effective surfactant adsorption on NPs
surface prevents their unlimited growth (Niu and Li, 2014). Whereas by
increasing the Rt from 10 to 40 min leads to the formation of highly
homogenous NRs with increase in length and width from 180 to 220 nm
and 10 to 25 nm respectively with a slight increase in aspect ratio from
9.2 to 9.6. Hence surface morphology analysis confirmed that CTAB
concentration and Rt has a significant effect in the formation of highly
homogenous size and shape SnS NPs.
3.5. Formation mechanism of NRs
In SnS, Sn is having +2 oxidation state with sterically active and
chemically inactive inert lone pair in 5 s orbital (Burton and Walsh,
2012; Tripathi and Mitra, 2013). This inert lone pair of Sn(II) forces the
crystal to grow in the [1 0 1] direction with successive layers between
two SnS molecule along one direction which leads to the formation of
NRs (Tripathi and Mitra, 2013). The surface energies (σ) low indexed
lattice planes of orthorhombic SnS crystal structure increases in the
order of σ(100) < σ(001) < σ(010) < σ(111) (Reddy, 2013). As a result,
in order to obtain lowest free energy, crystal growth is maximum along
low energy facets and minimum along high energy facets. XRD analysis
confirmed the preferential growth direction of SnS along [1 1 1] plane
with [1 0 0] and [0 0 1] as the base planes due to the low surface energy
of these planes (Reddy, 2013). Hence, atoms are added along the [1 0 0]
and [0 0 1] direction with a tampering end to minimize lattice face
B.H. Baby, D. Bharathi Mohan
Fig. 12. Growth mechanism of SnS nanorods.
surface energy. Initial nucleation of SnS monoatomic layers happens
along the [1 0 1] axis direction. Due to the layered structure of SnS
perpendicular to [0 1 0] direction with van der Waals interaction be-
tween the layers induces slowest growth rate along [0 1 0] direction,
leads to the formation of rod like structure as shown in Fig. 12 (Tan
et al., 2016).
3.6. Elemental composition
The quantitative elemental analysis of samples CTAB 0.025 M –
40 min and CTAB 0.15 M – 10 min were carried out using EDAX. EDAX
mapping analysis as shown in Fig. 13(a) shows Sn/S ratio 1 for sample
CTAB 0.025 M – 40 min indicating the formation of single phase of SnS
NPs as evident from Raman analysis (Burton et al., 2013). EDAX
mapping analysis of sample CTAB0.15 M – 10 min as shown in
Fig. 13(c) shows the formation of sulphur rich SnS phase with Sn/S
ratio 0.89 predicting the formation of Sn2S3 as a secondary phase along
with SnS for sample CTAB 0.15 M – 10 min as observed from Raman
analysis (Burton et al., 2013). Fig. 13(b) and (d) shows EDAX point
analysis of samples CTAB 0.025 M – 40 min and CTAB 0.15 M – 10 min
which is in good agreement with EDAX mapping analysis.
Fig. 13. (a) EDAX mapping and (b) elemental analyses (both qualitative and quantitative) of SnS NPs prepared with 0.025 M of CTAB for a Rt of 40 min (CTAB
0.025 M – 40 min) reveals Sn/S ratio equal to 1. (c) EDAX mapping and (d) elemental analyses (both qualitative and quantitative) of Sn-S NPs prepared with 0.15 M
of CTAB for the Rt of 10 min (CTAB 0.15 M – 10 min) shows Sn/S ratio equal to 0.89. The insert table shows the calculated weight and atomic percentage of Sn and S.
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Solar Energy 174 (2018) 373–385
3.7. Optical properties
The optical absorbance spectra of all samples dispersed in methanol
were studied in the wavelength range of 300–1200 nm using UV–Vis-
NIR absorption spectrophotometer. Fig. 14 shows the absorption
spectra of the samples prepared in (a) EG and (b) CTAB based reaction
for Rt of 10 min. Fig. 15(a), (b) and (c) shows the absorption spectra of
samples prepared in CTAB based reaction for Rt of 20, 40 and 60 min
respectively. For samples prepared from EG based reactions without the
addition of CTAB, by increasing Sn:S source concentration ratio from
1:6 to 1:12 M, the absorption maxima is red shifted from 415 to 450 nm
and the absorption band edge is shifted as 680, 662 and 747 nm which
may be due to the complete absence of SnS2 (Eg = 2.2 eV) phase and
also due to the suppression of Sn2S3 (Eg = 1.78 eV) phase as evident
from Raman analysis (Baby and Mohan, 2017a). The band gap of SnS
(Eg = 1.38 eV) is very low as compared to the values of other secondary
phases (Burton et al., 2013). Further increase of Sn:S ratio to 1:15 M
leads to a blue shift in the absorption maxima and band edge as 430 and
714 nm respectively, may be due to the formation of larger quantity of
Sn2S3 NPs along with SnS phase.
Whereas the incorporation of CTAB (0.025 M) as a cationic surfac-
tant in the reaction leads to a red shift in the absorption maxima to
455 nm as shown in Fig. 14(b) due to the controlled growth of SnS NPs
as evident from surface morphological analysis. Further increase in Rt
as 20, 40 and 60 min as shown in Fig. 15(a), (b) and (c), leads to a
systematic red shift in the absorption maxima as 465, 473 and 549 nm
respectively showing the improved homogeneity in size and shape of
the prepared NPs. For samples prepared with Rt of 10 and 20 min, by
varying CTAB concentration from 0.025 M to 0.2 M, the absorption
band edge is blue shifted from 800 to 740 nm and 850 to 810 nm re-
spectively. The observed drastic blue shift in the absorption band edge
by increasing the CTAB concentration from 0.025 M can be correlated
B.H. Baby, D. Bharathi Mohan Solar Energy 174 (2018) 373–385

Fig. 14. Optical absorption spectra of Sn-S NPs prepared in (a) EG based reaction and (b) EG-CTAB (0.025–0.2 M) based reaction for the Rt of 10 min.

Fig. 15. Optical absorption spectra of Sn-S NPs prepared in EG-CTAB (0.025–0.2 M) based reaction for the Rt of (a) 20 min (b) 40 min and (c) 60 min. (d) Tauc plot
shows the energy band gap of SnS NPs prepared with 0.025 M of CTAB by varying the Rt from 10 to 60 min.

with the variation in particle size as well as due to the formation of with Rt of 40 and 60 min, the absorption band edge is slightly blue
Sn2S3 as an additional phase along with SnS as evident from chemical shifted from 895 to 870 nm and 1035 to 1010 nm respectively. Che-
structural analysis (Guo et al., 2015). Whereas for samples prepared mical structural analysis confirmed the formation of single phase of SnS

382
B.H. Baby, D. Bharathi Mohan Solar Energy 174 (2018) 373–385

Table 3 secondary phases such as SnS2 and Sn2S3. By increasing Rt from 10 to

Calculated direct band gap energy values. 60 min, band gap value is systematically decreasing which is attributed
Sample code Band gap (eV) to the variation in particle size as evident from morphological analysis.
Chemical structural analysis confirmed the formation of single phase of
10 min 20 min 40 min 60 min SnS for all samples prepared using Rt of 40 and 60 min and hence band
gap of single phase SnS NPs were successfully tuned to 1.5 eV by
Sn:S – 1:6 M 2.15 – – –
Sn:S – 1:9 M 2.30 – – – varying Rt and CTAB concentration.
Sn:S – 1:12 M 1.92 – – – Fig. 16 shows emission spectra in the range of 700–900 nm for the
Sn:S – 1:15 M 1.98 – – – sample CTAB0.025 M – 10 min with an excitation wavelength of
CTAB 0.025 M 1.69 1.59 1.45 1.34 520 nm. The observed sharp red emission peak at 782 nm may be at-
CTAB 0.05 M 2.05 1.72 1.58 1.51
tributed to the free carrier or excitonic band edge transition between
CTAB 0.1 M 2.02 1.84 1.75 1.49
CTAB 0.15 M 2.18 1.88 1.76 – the valence band and conduction band (Baby and Mohan 2017b; Devika
CTAB 0.2 M 2.2 1.82 1.72 – et al., 2010; Kafashan et al., 2016) which is in good agreement with the
CTAB 0.3 M 1.92 1.72 1.6 – direct energy band gap value obtained from the Tauc plot.

3.8. Electrical properties

The electrical properties of CTAB0.15 M – 10 min and CTAB

Fig. 16. The emission spectra of sample CTAB0.025 M – 10 min shows the band
edge emission of SnS in the range of 700–900 nm with an excitation wavelength
of 520 nm.
for all these samples irrespective of the CTAB concentration. And hence
the observed slight blue shift in the absorption band edge is only due to
the variation in particle size.
Direct band gap value of all the samples were calculated from x-
intercept of Tauc plot and the values are enclosed in Table 3. Fig. 15(d)
shows Tauc plot of samples prepared with 0.025 M of CTAB by varying
Rt from 10 to 60 min. The observed high band gap value for samples
prepared without CTAB is due to the formation of SnS2 and Sn2S3
phases along with SnS phase as evident from chemical structural ana-
lysis. By increasing the Sn:S ratio to 1:12 M, band gap value is red
shifted from 2.3 to 1.92 eV due to the complete suppression of SnS2
phase which is having comparatively higher band gap value among
different tin sulphide phases. Whereas by using CTAB as a surfactant,
for Rt of 10 min, band gap value is red shifted to 1.69 eV due to the
formation of single phase of SnS which is having comparatively low
band gap value among different tin sulphide phases. The observed blue
shift of 0.31 eV as compared to bulk band gap value of SnS could be
attributed to the quantum confinement effect (Nair et al., 2005; Baby
and Mohan, 2017a). Whereas further increase in CTAB concentration
leads to an increase in band gap value due to the formation of
0.025 M – 40 min were studied using Hall effect experiment on a thick
film prepared with the thickness of 5 µm using drop casting technique.
The drop casted films were annealed under vacuum at temperature
200 °C for 60 min and the values of resistivity, carrier concentration,
mobility and polarity were calculated as shown in Table 4. Chaki et al.
(2014) prepared different shaped SnS NPs using wet chemical route and
obtained resistivity 659 × 103 Ω cm for NPs, 406 × 103 Ω cm for nano
whiskers and 690 × 102 Ω cm for nanoribbons with carrier concentra-
tion of 5.20 × 1011, 8.43 × 1011 and 4.99 × 1012 cm−3 respectively.
Guneri et al. (2010) prepared SnS NPs with needle shape like structure
by CBD method and obtained resistivity of 253 × 103 Ω cm. Chalapathi
et al. (2016) prepared cubic structured SnS NPs with resistivity and
carrier concentration in the range of 105 × 102 Ω cm and
7.93 × 1012 cm−3 respectively. Gedi et al. (2016) reported resistivity
value of 38 Ω cm and carrier concentration 3.4 × 1015 cm−3 for SnS
films prepared by CBD method. In this work, sample CTAB0.025 M –
40 min showed the formation of single phase SnS NRs, exhibiting p type
conductivity with resistivity 272 × 102 Ω cm and carrier concentration
1.14 × 1013 cm−3 and hall mobility 20.31 cm2 V−1 S−1. The value is
found to be slightly higher as compared to Gedi et al. work could be
attributed to the formation of SnS nanorods and however comparable
with the value of nanoribbons prepared by Chaki et al group. For the
sample CTAB 0.05 M – 10 min where Raman and XPS analysis con-
firmed the presence of SnS2 and Sn2S3 as additional phases along with
SnS, showing n-type conductivity with resistivity value of 13,860 Ω cm,
carrier concentration 0.45 × 1013 cm−3 and electron mobility
100.21 cm2 V−1 S−1.
4. Conclusion
The optimization study towards the formation of single phase of SnS
NRs from CTAB assisted polyol synthesis method, by varying the Sn:S
source concentration, CTAB concentration and reaction time has been
investigated for the first time. Raman and XPS analyses showed the
formation of single phase SnS with 0.025 M of CTAB and lead to form
SnS2 and Sn2S3 for the higher CTAB concentration. The single phase of
SnS is observed irrespective of CTAB concentration with the reaction
time of 40 min. XRD and SAED analyses confirmed the formation of
polycrystalline orthorhombic SnS for 0.025 M of CTAB. The structural
properties such as crystallite size, strain, stress and energy density

Table 4
Electrical properties of Sn-S NPs.
Sample Code Resistivity × 102 (Ω cm) Polarity(p/n) Carrier concentration × 1013 (cm−3) Mobility (cm2 V−1 S−1) Phase present

CTAB 0.15 M – 10 min 138.6 n 0.45 100.21 SnS, Sn2S3, SnS2

CTAB 0.025 M – 40 min 272 p 1.14 20.31 SnS

383
B.H. Baby, D. Bharathi Mohan
values are calculated from Williamson-Hall analysis by using UDEDM.
HR-TEM analysis confirmed the formation of SnS nanorods with an
improved homogeneity in size and shape with the increase of CTAB
concentration and Rt. EDAX mapping showed Sn/S ratio as 1 and 0.89
for CTAB concentration of 0.025 and 0.15 M respectively, which is
corroborating with Raman and XPS analyses. Band gap calculations
showed the successful tuning by varying the reaction time for 0.025 M
of CTAB, which is close to the optimum value of 1.5 eV. Hall mea-
surement showed p-type conductivity with resistivity 27,200 Ω cm for
pure SnS whereas n-type conductivity is observed when the secondary
phases present along with SnS phase.
Acknowledgements
The authors acknowledge SERB-DST, India (SR/FTP/PS-131/2012
& EEQ/2016/000228) for the financial support. Authors thank ACMS-
IIT Kanpur for providing XPS facility. Authors are grateful to Dr. D.
Selvakumar, Scientist-F, DEBEL (DRDO), Bangalore for EDAX analysis.
Authors thank STIC-CUSAT, Kochi for providing HR-TEM facility.
Authors thank CeNSE –IISC, Bangalore for providing Hall Measurement
facility. BHB sincerely thanks UGC-BSR for providing research fellow-
ship.
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