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Analysis of Chemically Deposited SnS Thin Film for

Solar Cell Application


Arindam Basak1 3*, Saswat Soumya Mishra1, Udai P. Singh1, Anup Mondal2
1
Thin Film Photovoltaics Lab, School of Electronics Engineering, KIIT University, Bhubaneswar, Odisha.
2
Department of Chemistry, IIEST, Shibpur, Howrah, West Bengal.
3
CEGESS, IIEST, Shibpur, Howrah, West Bengal.

* abasakfet@kiit.ac.in

thin films for the application of solar cell must have compact
Abstract—SnS is a promising material for solar cell absorber structure. Furthermore thin film for photovoltaic application
layer application due to its low cost, easy availability and less must have low electrical resistivity as high electrical
toxicity than other semiconductor material used for the same resistivity of film deteriorates solar cell performance [10].
purpose. SnS thin films as an absorber layer for photovoltaic Here in this work SnS thin films are deposited using
application are deposited using chemical bath deposition (CBD)
having a thickness of 550 nm from a solution containing
chemical bath technique at elevated temperature for 22 hours.
SnCl2.2H2O, TEA, TA and NH3OH. NH3OH is used to control The main focus of this work is to study the structural (SEM
the pH of the solution which is maintained at 5. The surface and XRD analysis), optical (transmittance and bandgap) and
morphology of the deposited film has been examined using X- electrical (Carrier Concentration, mobility, resistivity,
Ray diffraction and scanning electron microscopy. The optical conductivity) properties of deposited thin film using CBD
as well as electrical properties of deposited film have been technique suitable as absorber material for photovoltaic
characterized using UV-Vis spectrophotometer and hall effect devices. Results confirm that SnS can be a good choice for
measurement system respectively. Results show that films use as an absorber layer in photovoltaics.
deposited in this process have amorphous crystal structure and
have good adherence to the substrate. The bandgap obtained is II. EXPERIMENT DETAILS
1.4eV which is very suitable for its use as absorber material for
thin film solar cell. In the present work the depositions are done on glass
substrates. Glass substrates are first cleaned with soap
Keywords: SnS thin film, Chemical bath deposition, X-ray solution and followed by cleaning ultrasonically in acetone
diffraction, Hall Measurement and de-ionized water. Finally the glass slide was dried using
blowing N2.
I. INTRODUCTION In this work first a solution of 1g tin salt (SnCl2·2H2O)
In recent days new semiconductor materials are growing and 5 ml of acetone(C3H6O) was prepared. Another 100 ml
interest among the researchers for the application in solution of 12 ml of 3 M triethanolamine (TEA), 8 ml of 1.5
photovoltaics [1]. SnS is one of IV-VI group semiconductor M thioacetamide (TA) and 10 ml of 5 M ammonia, NH3(aq),
material having direct bandgap value 1.3-1.5 eV and a high 70 ml of distilled water is prepared. While preparing the
absorption coefficient as compared to other materials like solution thioacetamide was added in the solution very slowly
GaAs and CdTe. It has shown great potential as an absorber using a dropper to avoid the precipitation. Next 95 ml of 2nd
material for photovoltaic application [2][3]. Another added solution is mixed with the 1st solution to make a new solution
advantage for SnS is the abundance of its constituent of 100 ml. This mixed solution is stirred for some time to
materials in nature with less toxicity [4]. have a uniform mixture and then set at 310 K with glass slides
Several researchers have deposited SnS thin film using in the solution placed at 450 angles. A deep brown thin film is
various deposition techniques like sputtering [5], electro- deposited on the glass slides in about 22 hour. After
deposition [6], SILAR method [7], co-evaporation [8], spray completion of deposition, the deposited films were rinsed in
pyrolysis [9] and chemical bath deposition [10]. Among the distilled water and dried by direr. It is observed that the films
above methods chemical bath deposition(CBD) is the low are uniform and had better adherence on glass substrate.
cost and simple method for deposition of thin films where Structural characterization of the deposited films is
thin film layers grow over surface areas [10]. investigated by scanning electron microscope (SEM) and by
Different crystal structures have been found for deposited X- ray diffraction (XRD) using Cu-Kα radiation. The optical
SnS: orthorhombic structure, zinc blende structure and NaCl characterization ie. transmittance and absorbance was
structure. Mainly deposited SnS thin films are of measured using UV-Vis spectrophotometer having
orthorhombic structure though several researchers have wavelength range of 300 nm-900 nm (Shimadzu 2450). The
reported about zinc blende and NaCl crystal structure. SnS thickness of the film was measured using Film metrics F-10.

978-1-4799-4445-3/15/$31.00 ©2015 IEEE


Before the measurement of transmittance and absorbance, [12]. It is found that the calculated value and the standard
deposited film on backside of the substrate was cleaned value obtained from JCPDS Card are matching.
carefully with cotton swabs using dilute HCl and then by
distilled water. The reference was clean glass slide. The
electrical properties were determined using Hall Effect
measurement system (Ecopia HMS 3000).

III. RESULTS AND DISCUSSION


The deposition of SnS films using CBD technique is
precipitation free, which indicates that this deposition
mechanism of SnS is an ion-by-ion process [11]. The
measured thickness of the film was 550 ± 5 nm

Fig. 2 shows the SEM images of the deposited SnS

film. From the figure it can be seen that orthorhombic SnS


thin film is dense and consists of short cylinder rods. Some
nanosized island can also be seen in the surface structure.
The reason for this may be the long deposition time where
the islands growth mode gradually begins to work during the
deposition process as SnS films grows following a layer-by-
layer mode [11]. This type of phenomenon is also observed
in the deposition of Cu2S films [13].
Fig. 1: XRD pattern of SnS film prepared by CBD
TABLE 2: STRUCTURAL PARAMETERS FOR SnS FILM
Fig. 1 shows the XRD analysis of the deposited film. The
The Interplaner The Lattice Constant Micro
spectra clearly show that the deposited films are amorphous in Spacing (d) [Å] (a) [Å] Strain
nature. From the XRD pattern it is clear that the diffraction
2.89 5.01 0.07
peaks are observed at 2θ = 30.930, 26.650, 25.250 and 33.60 Fig. 3 shows the optical transmittance spectra of
which are assigned to (1 1 1), (0 2 1), (1 1 0) and (1 2 1) deposited orthorhombic SnS films at different wavelength in
planes respectively of orthorhombic primitive type lattice
structure of SnS (JCPDS NO. 65-3766). the range 300-900nm. The interference fringe at the high
wavelength region corroborates the fact that the film
TABLE 1: XRD DATA OF SnS FILM PREPARED BY CBD deposited is orthorhombic and smooth [14].
Angle d- Val FWHM h k l With the help of Urbach relation the optical bandgap is
30.93 2.88 0.02 1 1 1
calculated[15]:

(αhυ)m = A(hυ-Eg) (2)


Table 1 shows the dominant peak XRD data of the SnS films
deposited by chemical bath technique. The inter-atomic Where α is optical absorption coefficient of the deposited
spacing among the planes is 2.88 nm and the Miller indices film, hυ is the photon energy, A is constant
come (1 1 1) which indicates that the crystal axis are uniform.
The average crystallite size can be estimated by Scherrer’s
formula:

D= (1)
β cosθ

where K is as shape factor its value nearly 0.89 and it is


dimensionless, λ=0.154 nm and is the X-ray wavelength of
CuKα radiation, β is experimental full-width half-maximum
of the respective diffraction peak and measured in radians
and θ is the Bragg diffraction angle. By using above relation
crystallite size was calculated and found 4.84 nm. The
interplaner spacing, lattice constant and micro strain for the Fig. 2: Transmission spectra for thin film SnS on glass substrate using CBD
deposited film has been calculated using the formula
described by Y.P. Venkata Subbaiah, P Prathap, KT Reddy
and m=2 for direct allowed bandgap, m=1/2 for allowed References:
indirect bandgap. Here we take m=2 correspond to allowed
1
direct bandgap. The relation between (αhυ)2 vs eV has been Eric C. Greyson, Jeremy E. Barton, TeriW. Odom, “Optical
plotted in fig 4. The slope of the plotted graph cut the eV axis properties of surface-patterned nanostructures”, Talanta, Volume
at 1.5 eV which determines that the allowed bandgap value 67, Issue 3, 15 September 2005, Pages 507-513.
for chemical deposited SnS film comes around 1.5 eV which 2
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characterization of SnS thin films by electrodeposition technique”, Optica
Fig. 3: Plot of (αhυ)2 vs (hυ) for thin film SnS on glass substrate using CBD
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and previously reported optical bandgap value[16]. 7
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layer for solar cell applications. • 8
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absorber thin films by co-evaporation: Optimization of the growth rate and
TABLE 3: ELECTRICAL PROPERTIES OF SnS FILM influence of the annealing”, Thin Solid Films, 2014.
Carrier
Mobility Resistivity Conductivity
Concentration 9
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(cm2/Vs) (ohm-cm) -3 (mho-cm)
(cm )
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IV. CONCLUSION
10
Deposition of SnS thin film was carried out on glass Chao Gao, Honglie Shen, “Influence of the deposition parameters on the
substrate using chemical bath deposition technique. A properties of orthorhombic SnS films by chemical bath deposition”, Thin
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and electrical properties have been done. It has been observed 11
Chao Gao, Honglie Shen, Lei Sun, Zhou Shen, “Chemical bath deposition
that the deposited film is compact having orthorhombic
of SnS films with different crystal structures”, Materials Letters 65 (2011)
structure and have an orientation around the (1 1 1) plane with
a small grain size. The bandgap value for the deposited film is 1413–1415.
found to be 1.5 eV having good transmittance characteristics 12
YP Subbaiah, P Prathap, KT Reddy, “Structural, electrical and optical
which indicates that SnS can be used as a good absorber properties of ZnS films deposited by close-spaced evaporation”, Applied
material for solar cell application. Hall Effect measurement Surface Science, 2006.
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electrical resistivity which makes it suitable for the use in
solar cell as absorber material. transparent conducting CuS thin film and its application in dye-sensitized
solar cell” Applied Physics Letter, 2008, 93, 132106–3.
ACKNOWLEDGEMENT 14
A. Akkari, C. Guasch, N. Kamoun-Turki, “Chemically deposited tin
The authors like to acknowledge CEGESS, IIEST, Shibpur
sulphide”, Journal of Alloys and Compounds 490, 2010, 180–183.
for providing use of experimental facility and DST for 15
financial support through grant # DST/TM/SERI/2K11/42 J. Tauc, F. Abeles (Eds.), Optical Properties of Solids, IOP Publishing
Ltd., North Holland, Amsterdam, 1970, p. 903.
16
ATanusevski, “Optical and photoelectric properties of SnS thin films
prepared by chemical bath deposition”, Semiconductor Science Technol. 18
,2003, 501–505.

The following comments from reviewers end.


1. Full form of CBD not mentioned.
2. Give proper Equation numbers for all the equations.
3. Write down all the equations properly by equation editor.
4. No explanation for Fig.4 then what is the importance of
Fig.4?
5. Give latest reference.