Synthesis And Characterization Of Tin Sulphide Thin Films From Different Host

Solutions Using Chemical Bath Deposition Technique

Authors
Affiliation

1
Abstract:

The SnS thin films prepared by stannous chloride (SnCl 2) via chemical bath deposition
(CBD) method. Here, we used two different host solutions for synthesis of thin film as
follows; (i) thioacetamide (CH3CSNH2) and (ii) Sodium thiosulphate (Na2S2O3.5H2O).
Ethylene diamine tetra acetic acid (EDTA) also used in it as complexing agent. The grown
films were smooth, well adherent and brown in colour and were highly reproducible in the
ambient conditions. Thickness of SnS thin film determined by profilometer. As well as
concentration of SnCl2 increased in both host solutions, thickness of SnS film also increased
and colour of SnS was dark brown with increase the number of deposition cycles. SnS films
were characterized by Scanning Electron Microscopy (SEM), Atomic Force Microscopy
(AFM), X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX), UV absorption
spectra, Raman analysis. SEM images of the SnS films confirmed the films were dense,
polycrystalline and orthorhombic non-uniform nano structures having 140-164 nm diameter
in thioacetamide bath and 240-141 nm diameter in sodium thiosulphate, respectively. It also
reveal the particle size becomes larger with increased film thickness. Purity of the film
determined by EDAX analysis. UV absorption showed absorption in UV and visible region
including reveals the band gap energy 0.75 eV and 3.42 eV, respectively. Strength of the
chemical bonds between atoms determined by Raman.

Keyword: Tin sulphide, thin film, thioacetamide, sodium thiosulphate, SEM, AFM, XRD,
EDAX, Raman.

Graphical Abstract:

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Growth of SnS thin film representation.

1. Introduction

These days, due to intriguing properties nanomaterials had attracted great interest for
fabrication and also challenging subject in material science [1-4]. In the area of
semiconductors, metal chalcogenide semiconducting nanoparticles extensively studied
because of their potential use in non-linear optics, electronics, luminescence, catalysis,
energy storage and conversion etc [5-8]. The band gap of those nanoparticles were dependent
on size of particles [9]. As well size of particle become smaller, the ratio of the surface atoms
increased interiorly, and it was leading significant property of material surface [10]. From last
few decades, semi-metals of IV-VI group get great interest by chemist cause of narrow
bandgap semiconductors with high-temperature phases in various crystal structures which
transform into other structural phases at low temperature [11-15]. These materials had broad
range of applications for example thermoelectric devices, infrared (IR) lasers, and detectors.
Thin film or bulk of semiconducting materials of group IV-VI used in electronics,

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optoelectronics, solar cells, IR and near-infrared detectors and emission [16, 17].

These days in the field of photovoltaics, non-toxic tin sulphide (with orthorhombic structure)
which belongs to IV-VI group, used as cost effective material for simple fabrication of solar
cell. It abundant by nature and lead to develop environment friendly devices which accepted
by human [18, 19]. Tin sulphides had several binary compounds such as SnS, Sn 2S3, Sn3S4,
Sn4S5 and SnS2, which attracted interest because of their structural diversities [20]. Among of
these compounds, tin sulphide (SnS) had promising and very interesting optical and electrical
properties, which used in optoelectronic, technologic and photovoltaic applications [21-23]
and also could be better alternative of already developed technologies like Cu (In, Ga) Se 2
(23.35%) [24] and CdTe (22.1%) [25], which were limited with their own toxicity, scarcity
and exorbitant cost. Due to following properties of SnS films, it were able to used easily in
solar cells: i) large optical absorption coefficient > 10 4 cm-1[26] and high photoelectric
conversion efficiency (up to 25%) [27, 28]; ii) energy optical bandgap (1.2 - 1.5 eV), which
depended on deposition method and crystalline structure of the films [29], and it closed to the
optimal of solar cells (1.5 eV) [30]. The efficiency of SnS material were low that improved
by doping [31], which easily prepared by the chemical deposition method [32]. It exhibited p-
type conductivity and carrier concentration was 10 11–1018 cm-3[33], which perfectly suitable
for thin-film photovoltaic absorbers. These conductive films prepared and characterized by
several techniques namely, thermal evaporation of SnS at low vacuum leading to amorphous
films [34], vacuum evaporation of high purity SnS powder [35], cathodic electrodeposition
[32], electro chemical deposition [36], chemical bath deposition (CBD) [37], spray pyrolysis
with or without the variation of precursor concentration [32]. Among all techniques, chemical
bath deposition (CBD) was a simple technique which used to grow high quality layers over
large areas [37]. SnS thin films also applied in field‐effect transistors [38, 39], lithium‐
sodium ion batteries [40, 41], thermo-electrics [42], water splitting [43], gas sensors [44, 45],
photocatalysis [46], photodetectors [47, 48], electrochemical capacitors [49] and
supercapacitors [50] etc.

Because of variations in band gap, SnS thin films had different fabrication technologies [32].
Here, we report the preparation of SnS thin films by chemical bath deposition using two
different host solutions (i)Thioacetamide (CH3CSNH2); (ii) Sodium thiosulphate
(Na2S2O3.5H2O). Deposition parameters which investigated through concentration of
solutions. and also characterized by XRD, SEM, EDS, AFM, RAMAN, UV absorption

4
spectroscopy. Thickness of CBD tin sulphide (SnS) also calculated by profilometer.

2. Experimental

2.1 Materials and methods

For synthesis of SnS thin film, all reagents as like SnCl 2·2H2O, ethylene diamine tetra acetic
acid (EDTA), thioacetamide (CH3CSNH2), sodium thiosulphate (Na2S2O3.5H2O), triple
distilled water were analytical grade and used directly without further purification. NH 3 also
used for pH adjustment of solution.
2.2 Synthesis
Synthesis of SnS with CH3CSNH2/Na2S2O3

1.0 gm SnCl2.2H2O dissolved in 10 ml water into a beaker, stirred well and get a clear
solution. After that added 15.0 ml (0.1M) EDTA which used as complexing agent in it. The
whole mixture stirred well by magnetic stirrer and the light yellow colour of solution formed.
Then, added 10.0 ml of CH 3CSNH2/Na2S2O3 (1 M) into solution and again stirred well. After
some time, the colour of solution converted to dark brown. After that added ammonia and
adjust the pH of solution upto 10. After that, heated microscope slides mounted in the
solution and the beaker was put into the water bath for 6 hours. After deposition slides were
removed from the bath and washed thoroughly with distilled water and dried in air.

2.3 Thickness determination

SnS films of different film thickness were grown on corning glass (75 mm x 25 mm x 2 mm)
slides by CBD. Before film deposition, the glass substrate was soaked in a solution of
detergent. The slides were scrubbed with cotton swabs and rinsing with deionized water to
remove any contamination and moisture from the substrate surface. The glass slides were
ultrasonically washed (at 60°C) [51]. Finally, the glass slides were ultrasonically washed in
deionized water and then dried (in oven at 35 °C) for 15 min. CBD technique modified and
used to grow films [52]. To deposit films on glass substrates, the starting solution was
prepared as described in previous.

2.4 Characterization

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The crystal structure and the phase of the material compositions were studied by XRD using
a “PAN alytical Empyrean” diffractometer (CuKα radiation, λ = 1.5418 Å) with a wide-angle
measurements of 2θ in the range of (20–70) ° and a step of 0.026°. The experimental data
were analyzed using the Inorganic crystals structure database (ICSD). The room temperature
vibrational characteristics of the samples were carried out with a 532 nm Nd: YAG laser
excitation using a micro-Raman spectrometer (Renishaw INVIA Raman Microscope) in a
wave number range of 300–3000 cm−1. The surface morphologies of the as-synthesized films
were studied by scanning electron microscope (SEM, EVO40-LEO, operated at an
accelerating voltage of 200 kV). The elemental analysis of the film was accessed through
EDAX (Energy-dispersive X-ray) attachment. The surface topology of the films deposit was
investigated using atomic force microscopy (AFM) type WITec alpha 300RA (WITec
GmbH, Ulm, Germany). Perkin Elmer Lambda 750 UV-VIS- NIR (ultraviolet-visiblenear-
infrared) spectrometer was used to access the UV-VIS absorption spectra. Thickness were
determined by stylus profilometer.

4. Results and discussion

4.1 Film thickness

The film thickness was very important in many application like optics, thin film deposition,
semiconductor etc. It also had strong influence on the band gap, surface roughness, optical
and electrical properties. Here, we described the thickness of chemical bath deposited (CBD)
SnS films via profilometer.

Fig. 2: Spectra of increasing thickness of SnS film with increased concentration of SnCl 2.

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The colour of SnS was dark brown with increase the number of deposition cycles. According
to Fig. 2, as well as concentration of SnCl 2 increased in both host solutions: (i) thioacetamide
and (ii) sodium thiosulphate, thickness of SnS film also increased (Fig. 3).

Fig. 3: SnS films thickness grown via increasing the number of deposition cycles.

4.2 Surface morphology

(a) Scanning SEM

Fig. 4. SEM images of SnS thin film from Thioacetamide.

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Fig.5. SEM images of SnS from sodium thiosulphate

The SEM images reflects that the surface of the substrate was covered completely. In
addition, these films were dense and non-uniform. Those nano particles were distributed
randomly over the surface of substrate. For SnS film from thioacetamide, the size of particles
exhibited randomly orientation as it varies from one to another, which is in the range 140-164
nm (Fig. 4). And for SnS film from sodium thiosulphate,the size of particles exhibited
randomly orientation as it varies from one to another, which is in the range 141-240 nm (Fig.
5).

(b) AFM

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Fig. 6. AFM image of SnS from thioacetamide.

Fig. 7. AFM images of SnS from sodium thiosulphate.

To elucidate the surface morphology, films were analysed through AFM. Fig. 6 and 7 showed
AFM images of SnS films in different host solution as follows; (1) thioacetamide and (2)
thiosulphate. AFM images reveal that the particle size becomes larger with increase in film
thickness (Fig. 6 (b) and 7(b)). Non-uniform particles observed in those thin films. AFM
images show that the films are dense and some pores also observed on surface. Particle
boundaries become more prominent with thickness of film increased with and particle size
also increased. Bigger size particles formed with increased thickness because of
agglomeration of small size particles during CBD growth.
The surface morphology, surface roughness and particle size distribution of sputtered films
observed by by AFM (Fig. 6 and 7). The particle size of SnS thin film in thioacetamide
(sample 1) and in sodium thiosulphate (sample 2), calculated over 6µm 2 and 3µm2
respectively. Particles occurs on edges did not consider in calculation. Those films exhibited

9
spherical shape of nanoparticles (NPs) (2D view) with 293 nm and 274 nm size value
respectively. The bigger size of particles because of coalescence of smaller particles in also
showed in 3D view of both samples (Fig. 6 and 7).

4.2 Crystal Structure

XRD Analysis
(a) SnS from Thioacetamid

Fig. 8. XRD spectra of nano SnS synthesized by thioacetamide host solution via chemical bath
deposition

According to Fig. 8 and 9, The XRD and EDAX spectra of SnS thin films in chemical bath
obtained from thioacetamide. Thin films were polycrystalline with orthorhombic structure
and it also matched well with standard patterns. A sharp peak in XRD pattern observed at 2θ
= 25.198º, which had orientation along (021) plane for SnS thin films. While the highest peak
identified at 2θ = 32.227º, originated from (111) plane with another short peak at 2θ = 30.444

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º, originated from (101) plane. Another peak obtained at 2θ = 60.6333º. originated from
(400) plane. There are unidentified peak at 2θ =16.033º (Fig. 8) [53-55]. EDAX spectra
showed that the films prepared from thioacetamide host solutions were nearly stoichiometric
in nature (Fig. 9).

Fig. 9. EDAX spectra of SnS which prepared from thioacetamide host solution with table of weight
percentage of elements.

(b)SnS from Sodium thiosulphate

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Fig. 10. XRD spectra of nano SnS synthesized by sodium thiosulphate host solution via chemical
bath deposition.

According to Fig. 10 and 11, The XRD and EDAX spectra of SnS thin films in chemical bath
obtained from sodium thiosulphate. Thin films were polycrystalline with orthorhombic
structure and it also matched well with standard patterns. A large and sharp peak in XRD
pattern observed at 2θ = 24.188º, which had orientation along (021) plane for SnS thin films.
There are unidentified peak at 2θ =15.614º (Fig. 10) [56, 57]. EDAX spectra showed that the
films prepared from sodium thiosulphate host solutions were nearly stoichiometric in nature
(Fig. 11). Table 1 shows different crystalline properties of as prepared material.

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Fig. 11. EDAX spectra of SnS which prepared from sodium thiosulphate host solution with table of
weight percentage of elements.

Table 1:Different crystal properties obtain via XRD studies of SnS prepared via
thioacetamide and thiosulphate

Substance 2θ of θ of the FWHM Size of d- δ ε

the intense of the spacin (dislocation strai
intense peak intense particle g density) x n x
peak (degree) peak (β) (D) nm nm 10-14 10-3
(degree) radians lines/m2

Thioacetamid 16.53 8.265 0.000624 11.18 0.536 8.0 x 10-15 10.73

Thiosulphate 16.61 8.305 0.001277 10.97 0.533 8.3 x 10-15 21.87

UV-Visible:

(a) SnS from thioacetamide

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Fig. 12. (i) UV absorption spectra of SnS thin film in thioacetamide; (ii) a direct band gap energy was
0.75 eV respectively.

The UV absorption spectra of SnS thin film prepared in thioacetamide host solution as
explained in Fig. 12 (i). Absorption versus wavelength spectra showed a maximum
transparency in 600 – 1000 nm wavelength. SnS was a direct band semiconductor. A plot of
(αhν)2 versus hν had a linear portion and the intercept of this linear portion on the energy axis
gives the band gap. It had direct band gap with 0.75 eV energy (Fig. 12 (ii)).

(b) SnS from sodium thiosulphate

The UV absorption spectra of SnS thin film prepared in sodium thiosulphate host solution as
explained in Fig. 13 (i). It showed a sharp peak at 253 nm in UV region. SnS was a direct
band semiconductor. A plot of (αhν) 2 versus hν had a linear portion and the intercept of this
linear portion on the energy axis gives the band gap. It had direct band gap with 3.42 eV
energy (Fig. 13 (ii)).

Fig. 13. (i) UV absorption spectra of SnS thin film in sodium thiosulphate; (ii) a direct band gap
energy was 3.42 eV respectively.

4.5 Raman Analysis

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Fig. 14. Raman spectra of SnS thin film in thioacetamide host solution via chemical bath deposition
process.

Raman spectrum was sensitive for crystal quality, symmetry, and strength of the chemical
bond between atoms [58]. The SnS has 21 optical vibrational modes with the irreducible
representation of Γ = 4Ag + 2B1g + 4B2g + 2B3g + 2Au + 4B1u + 2B2u + 4B3u [59, 60]. In these
phonons, two are inactive (2Au), seven are infrared-active (3B1u, 3B3u, and 1B2u), and twelve
are Raman-active (4Ag, 2B1g, 4B2g, and 2B3g) [61].

The Raman spectrum of SnS in chemical bath from thioacetamide showed three prominent
peaks at 204 cm−1 (highest intensity mode, B2g), 277 cm−1 (narrow mode, Ag), and 491 cm−1
(narrow mode, Ag). The spectrum also showed a weak Ag mode at approximately 118 cm−1
(Fig. 14).

SnS thin film from sodium thiosulphate

The Raman spectrum of SnS in chemical bath from sodium thiosulphate showed three
prominent peaks at 178 cm−1 (narrow mode, B2g), 357 cm−1 (highest intensity mode, Ag), and

15
463 cm−1 (narrow mode, Ag). The spectrum also showed a weak Ag mode at approximately
101 cm−1 (Fig. 15) [62, 63].

Fig. 15. Raman spectra of SnS thin film in chemical bath from sodium thiosulphate.

5. Conclusion

Tin sulphide (SnS) thin films had different morphologies and synthesized by chemical bath
deposition (CBD) method at room temperature. For preparation of thin films, different host
solutions used which showed polycrystalline orthorhombic structure. Morphology of films
vary with variation of host solutions. SEM images of the SnS films showed nano- spherical
with 140-164 nm diameter in thioacetamide and 240 – 141 nm diameter for SnS thin film in
sodium thiosulphate, respectively. The films from different host solutions had different
optical properties. Absorption spectra showed medium absorption in the visible region and a
decrease with higher wavelength. The band gap energy of SnS thin film at different host
solutions, thioacetamide and sodium thiosulphate was 0.75 eV and 3.42 eV respectively. SnS
thin films also characterized by XRD, EDAX, Raman and it showed crystal quality,
symmetry, and strength of the chemical bond between atoms. Thickness of films also

16
observed that as well as concentration of SnCl 2, thickness of film also increased. Elements of
the films were nontoxic and abundant in nature and also developed environment friendly
devices.

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