See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/272027735

Development of Sulphurized SnS Thin Film

Solar Cells

Article in Current Applied Physics February 2015

DOI: 10.1016/j.cap.2015.01.022

CITATIONS READS

23 621

5 authors, including:

Vasudeva Reddy Minnam Reddy Robert W. Miles

Yeungnam University Northumbria University
16 PUBLICATIONS 46 CITATIONS 99 PUBLICATIONS 1,910 CITATIONS

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

solar cells using earth abundant materials View project

All content following this page was uploaded by Vasudeva Reddy Minnam Reddy on 20 September 2016.

The user has requested enhancement of the downloaded file. All in-text references underlined in blue are added to the original document
and are linked to publications on ResearchGate, letting you access and read them immediately.
 Current Applied Physics 15 (2015) 588e598

Contents lists available at ScienceDirect

Current Applied Physics

journal homepage: www.elsevier.com/locate/cap

Development of sulphurized SnS thin lm solar cells

Vasudeva Reddy Minnam Reddy a, b, *, Sreedevi Gedi a, b, **, Chinho Park b, Miles R.W c,
Ramakrishna Reddy K.T a
a
Solar Photovoltaic Laboratory, Department of Physics, Sri Venkateswasra University, Tirupati 517 502, India
b
School of Chemical Engineering, Yeungnam University, 280 Daehak-ro, Gyeongsan 712-749, Republic of Korea
c
School of Technology and Environment, Northumbria University, Newcastle NE1 8ST, UK

a r t i c l e i n f o a b s t r a c t

Article history: Thin lms of tin sulphide (SnS) have been grown by sulphurization of sputtered tin precursor layers in a
Received 13 July 2014 closed chamber. The effect of sulphurization temperature (Ts) that varied in the range of 150e450
C for a
Received in revised form xed sulphurization time of 120 min on SnS lm was studied through various characterization tech-
19 January 2015
niques. X-ray photoelectron spectroscopy analysis demonstrated the transformation of metallic tin layers
Accepted 20 January 2015
Available online 3 February 2015
into SnS single phase for Ts between 300
C and 350
C. The X-ray diffraction measurements indicated
that all the grown lms had the (111) crystal plane as the preferred orientation and exhibited ortho-
rhombic crystal structure. Raman analysis showed modes at 95 cm1, 189 cm1 and 218 cm1 are related
Keywords:
Tin sulphide
to the Ag mode of SnS. AFM images revealed a granular change in the grain growth with the increase of
Sulphurization Ts. The optical energy band gap values were estimated using the transmittance spectra and found to be
Structural properties varied from 1.2 eV to 1.6 eV with Ts. The Hall effect measurements showed that all the lms were p-type
Optical properties conducting nature and the layers grown at 350
C showed a low electrical resistivity of 64 U-cm, a net
Solar cell carrier concentration of 2  1016 cm3 and mobility of 41 cm2 V1 s1. With the use of sprayed
Zn0.76Mg0.24O as a buffer layer and the sputtered ZnO:Al as window layer, the SnS based thin lm solar
cell was developed that showed a conversion efciency of 2.02%.
2015 Elsevier B.V. All rights reserved.

1. Introduction
The challenge of the present photovoltaic market is to produce
electricity at very low cost using environmental friendly materials.
It has been proved recently that one such material system is the IV
e VI group of SneS semiconductors [1,2]. The SneS phase diagram
reported by Bletskan et al. [3] revealed different binary forms such
as SnS, SnS2 and Sn2S3. Among these phases, SnS and SnS2 played
promising role in the development of solar cells, electronic and
display devices [1,2,4e9].
SnS exhibits both p- and n-type conductivity depending on the
concentration of tin [10]. It has the advantage that the constituent
elements are abundant in nature and do not cause any health and
environmental hazards. It has an energy band gap of ~1.35 eV that
* Corresponding author. Present address: School of Chemical Engineering,
Yeungnam University, 280 Daehak-ro, Gyeongsan 712-749, Republic of Korea.
** Corresponding author. School of Chemical Engineering, Yeungnam University,
280 Daehak-ro, Gyeongsan 712-749, Republic of Korea.
E-mail addresses: drmvasudr@gmail.com, drmvasudr9@gmail.com
(V.R. Minnam Reddy), drsrvi9@gmail.com (S. Gedi).
lies between the band gap values of Si and GaAs with high optical
absorption coefcient of 105 cm1and quantum yield for the exited
carrier and low recombination velocity [6,11]. It has the ionization
energy of 4.7 eV [1,12], work function of 4.2 eV [12,13,14] and an
electron afnity of 3.59 eV [1]. The selection of ohmic contact for
SnS lms is easy because of its lower work function and electron
afnity compared to the other conventional absorber layers like
CdTe, CIGS and CIS [12].
Tin sulphide have been prepared using a variety of deposition
techniques, such as spray pyrolysis [6,10,15], thermal evaporation
[13,16], electronbeam evaporation [17], hot wall deposition [18],
chemical bath deposition [19], successive ionic layer adsorption
and reaction [20], RF sputtering [21], atomic layer deposition [22],
chemical vapor deposition [23], electrochemical deposition [4,24]
and sulphurization [25,26]. Among them, sulphurization is one of
the simple method that can be used to prepare SnS lms over large
area deposition at low cost with well controlled composition and it
has proved as a most promising method for producing high quality
CIGS and CIS thin lms for solar cell fabrication. In this method, the
metal precursors were sulphurized using sulphur vapor in a closed
chamber by reaction solid phase growth mechanism. Although, few

http://dx.doi.org/10.1016/j.cap.2015.01.022
1567-1739/ 2015 Elsevier B.V. All rights reserved.
 V.R. Minnam Reddy et al. / Current Applied Physics 15 (2015) 588e598 589

research groups were grown SnS layers using sulphurization

method [25,26], a detailed investigation on the properties of grown
layers using different growth conditions are meager. Therefore, a
systematic study on the suphurization conditions is required to
obtain a good quality lms as the process depends on the number
of factors such as precursor thickness, sulphurization pressure,
temperature, time and carrier gas ow rate in the sulphurization
system.
Loferski et al. [27] theoretical studies and Chandrasekharan et al.
[28] stimulations showed that solar conversion efciencies >20%
could be achieved for SnS based solar cells. Therefore, it is a po-
tential candidate that can be used as a solar absorber in thin lm
solar cells. But experimentally these cells currently demonstrated a
conversion efciency of 1.95% in homojunction type [29] and 4.4%
in inorganic heterojunction conguration [22] while organic het-
erojunction exhibited an efciency of 2.8% [30]. The reported lower Fig. 2. Wide scan XPS spectrum of SnS lms grown at a sulphurization temperature of
350
C.
efciencies for these cells might be poor crystallinity, lower thick-
ness of the lm, insufcient diffusion lengths, lattice and electron
afnity mismatches. Among these, the mismatch in the electron rotary pump and then ushed with argon gas for a few minutes to
afnity mainly inuences the cell efciency, which causes energy avoid the presence of impurities in the chamber. Thereafter, sul-
spikes to occur in the conduction band that limits the carrier phurization was performed in the temperature range of
transport across the junction. In this context, we are investigating 150e450
C for a xed time period of 120 min and then the lms
on various buffer layers to SnS in our laboratory and Zn0.76Mg0.24O were allowed to cool down naturally to room temperature. The
[31,32] is found to be suitable nontoxic buffer layer where the initial thickness of sputtered tin metal is 300 nm and after sulfu-
electron afnity could be tunable to a value close to that of SnS [33]. rization it attempts the values as follows, 150
C 386 nm,
Hence, in the present work, SnS layers were grown using sulphu- 200
C 420 nm, 250
C 480 nm, 300
C 590 nm,
rization of tin layers and the properties of the layers were analyzed 350
C 610 nm, 400
C 556 nm and 450
C 400 nm. The
and discussed. Finally, the optimized SnS layers were used for the Zn0.76Mg0.24O buffer layer of 100 nm thickness were deposited by
development of SnS based solar cell with the conguration of Mo/ chemical spray pyrolysis using at previously optimized conditions
SnS/Zn0.76Mg0.24O/ZnO:Al/Ag and initial results are reported. [32] and ZnO:Al window layer of 380 nm formed by DC reactive
magnetron sputtering. Finally, Ag was deposited by thermal evap-
2. Experimental details oration technique as the top contact.

2.1. Preparation of SnS lms 2.2. Characterization techniques

Metallic tin precursor layers of 300 nm were deposited on ul-
trasonically cleaned Mo-coated soda lime glass substrate by DC
magnetron sputtering process using VRSU048 sputtering system
(4N Tin target Kurt J. Lesker). The tin precursors were sulphurized
by a sulphurization system and the setup is shown in Fig. 1. The tin
layers were kept inside a graphite box together with 99.998% pure
sulphur akes (Sigma Aldrich) and then placed onto the heater in
the closed chamber. The chamber was initially evacuated using a
The chemical stoichiometry and the valance state of constituent
elements of SnS layers were explored by X-ray photoelectron
spectroscopy (XPS) (Model: VG Multilab 2000). The XPS spectra
were recorded in the binding energy range of 0e1000 eV using Al
target as the source of X-ray and the binding energies in the

Fig. 1. Experimental setup of the sulphurization. Fig. 3. Scheme of relative positions of the core level Sn3d5/2 and S2p3/2 peaks.
590 V.R. Minnam Reddy et al. / Current Applied Physics 15 (2015) 588e598
spectrometer were calibrated using carbon 1s line. The XPS spectra
of the layers were taken repeatedly at different time intervals by Ar-
ion etching to check the compositional uniformity across the
thickness of the layers. The crystal structure of the deposited lms
was identied using X-ray diffractometer (XRD) (Model: Seifert
3003 TT with monochromatic high intensity CuKa radiation
l 0.1546 nm). Raman spectroscopy measurements were per-
formed with Horiba Jobin Yvon spectrophotometer in backscat-
tering conguration with an excitation wavelength of 632 nm. The
surface topography of the lms was observed by atomic force mi-
croscope (AFM) (Model: SPA 400). The optical properties were
studied using Perkin Elmer Lambda 950 UVeViseNIR spectrom-
eter. The electrical properties were carried out by Ecopia Hall effect
measurement system (Model: HMS-3000VER 3.51.3). The illumi-
nated current density-voltage (J-V) characteristics of the pre-
liminary unoptimized solar cell device were measured using a
Keithley 2400. A Xenon ash lamp (USHIO, ash type, UA-DF1,
1000 W, 400 V) with AM 1.5 lter was used as a source of light.
3. Results and discussion
All the sulphurized SnS lms appeared smooth, homogeneous
and pinhole free by visual observation, and had good adherence to
the substrate as revealed by scratch tape test. The sulphurization
temperature had shown signicant inuence on the properties of
SnS lms, since it inuences the reaction kinetics between tin layer
and sulphur vapor. In general, if the temperature is too low no re-
action will takes place between the metal layer and sulphur vapor.
On the other hand, if the temperature is higher than the melting
point of sulphur then reevaporation may takes place from the
Fig. 4. Deconvoluted XPS spectra of Sn3d5/2, Sn3d3/2 and Sp3/2 peaks in the lms sulphurized at different temperatures.
surface of the lm owing to its high vapor pressure at such tem-
peratures. Hence, there might be an optimum temperature for the
sulphurization of the lms with desired properties. In order to
understand the formation mechanism of SnS and to optimize the
sulphurization temperature, the lms were analyzed using appro-
priate characterization techniques.
3.1. XPS analysis
In the present study, XPS was used to investigate the valence
states of the constituent elements as well as binding energies of the
SneS system. Fig. 2 showed the wide scan XPS spectrum of SnS
lms sulphurized at Ts of 350
C. The XPS spectrum conrmed the
presence of Sn, S, O and C components. The peak present at a
binding energy value of 284.8 eV and 531.3 eV are assigned to the
characteristic peak of C1s. These two peaks were present in the XPS
spectrum of the as-grown layers due to surface oxidation/
contamination that disappeared when the layers were Ar-ion
etched at regular time intervals, indicating the compositional uni-
formity across the layer thickness. The peak observed at 164.3 eV
indicates the presence of elemental sulphur [33,34]. However it
was not observed in the layers after Ts of 250
C. Generally, the
difference between the binding energies of elemental sulphur and
sulphur bonded with different oxidation states of tin are shown in
Fig. 3. If sulphur is bonded with Sn2 and Sn4 simultaneously, then
the difference between the binding energies is only 1 eV and hence
the XPS yields a broad peak for S2. Similarly, the difference in
binding energies of Sn0, Sn2 and Sn4 varied between 0.7 eV and
2.0 eV thereby overlapping of the peak occur, resulting in a broad
tin peak in the XPS spectra. Therefore, the inuence of Ts on the
 V.R. Minnam Reddy et al. / Current Applied Physics 15 (2015) 588e598
existence of different states of tin and sulphur in SnS lm was
analyzed through the deconvolution of core level Sn3d5/2 and S2p3/
2 peak and are shown in Fig. 4(a) and (b).
At lower Ts, the Sn3d3/2 peak was broad because of the presence
of mixed states and is shown in Fig. 4(a). It can be deconvoluted into
three peaks that were related to Sn0, Sn2 and Sn4, indicating that
the existence of different phases of SneS in addition to metallic tin.
With the increase of Ts, the width of the Sn3d5/2 peak was
decreased and became narrow in the Ts range, 300e350
C and
further increase of Ts, the peak was slightly shifted towards higher
binding energy side and also it became broad again. The decon-
volution of Sn3d5/2 peak at these Ts indicated the presence of two
peaks that are related to Sn2 and Sn4, corresponding to SnS and
SnS2 phases, respectively. Similarly, the deconvolution of S2p3/2
peak at lower Ts in the range, 150e250
C resulted in two main
peaks related to SeSn2 and SeSn4 and is shown in Fig. 4(b). With
the increase of Ts, the width of S2p3/2 peak was decreased and
became narrow between 300
C and 350
C and further increase of
Ts, the peak was slightly shifted towards the lower binding energy
side and made it broad. The deconvolution of S2p3/2 peak at these Ts
results in two peaks corresponding to SeSn2 and SneSn4.
Therefore, in the Ts range of 300e350
C, the narrow peaks noticed
at 485.6 eV and 161.2 eV of Sn3d5/2 and S2p3/2 were related to Sn2
and S2 in SnS [35] respectively. In addition, the Sn4 peak (at
486.3 eV) was not detected in the Sn3d5/2 peak of this Ts range,
indicating the formation of pure SnS phase with a binding energy
difference of 324.6 eV between Sn3d5/2 and Sp3/2 peaks.
For the Ts  250
C and 400
C, the peaks noticed at 486.3 eV
and 162.2 eV of Sn3d5/2 and S2p3/2 were related to Sn4 [36,37] and
S2 in Sn2S3 or SnS2 [36] respectively. Further, with the presence of
Sn2 peak (at 485.6 eV) detected in the Sn3d5/2 and Sp3/2 peaks in
Fig. 5. XRD spectra of SnS lms sulphurized at different temperatures.
591
those layers were 352.0 eV and 325.1 eV respectively that corre-
spond to Sn2S3 or SnS2 phases. As the energy difference between
these two peaks is very small, it is difcult to identify these phases
using XPS and therefore Raman analysis was carried out and dis-
cussed in the further section. The XPS analysis thus demonstrated
that the Sn precursor layers transformed into SnS phase
completely without any secondary phases only in the Ts range of
300e350
C. The possible change in the oxidation state of Sn
during the whole procedure is as follows. Usually, the reaction of
metallic tin with sulphur might depend on the oxidation state of tin
at that particular temperature in the reaction chamber apart from
the energy formation of different phases. The metallic tin might be
present in 4 oxidation state with the raise of Ts. With further rise
of Ts, it could be changed from 4 to 2 oxidation state by
capturing the electrons from the lone pair state of Sn [38]. There-
fore, at lower Ts various binary phases such as SnS and Sn2S3 were
present corresponding to 4 and 2 oxidation state of Sn. But,
when the Ts was in the range of 300e350
C. Sn might be present
only in the 2 oxidation state, leading to the formation of single
phase SnS [39,40]. However, at Ts  400
C disproportionation re-
action of Sn2 resulted with the existence on Sn4 and Sn0 states as
the nearest neighbor distance between Sn4 and S2 is shorter than
the nearest neighbor distance between Sn2 and S2 due to lattice
relaxation that depends upon the growth conditions. Hence, this
might be the cause for the observed additional phase of SnS2 along
with SnS at higher temperatures [41e45].
3.2. Structural properties
The XRD patterns of SnS lms sulphurized at different sulphu-
rization temperatures are shown in Fig. 5. The diffraction patterns
showed that all the lms are polycrystalline in nature, exhibited
several orientations such as (111), (101), (101), (112) and (042)
Fig. 6. Raman spectra of SnS lms grown at different sulphurization temperatures.
592 V.R. Minnam Reddy et al. / Current Applied Physics 15 (2015) 588e598

Fig. 7. AFM images of SnS lms grown at different suphurization temperatures.

corresponding to that orthorhombic SnS with the (111) peak as the those for secondary phases. Therefore, nucleation of secondary
predominant orientation at 2q 31.5
. However, the layers showed phases occurs relatively easily compared to that of SnS at lower Ts.
various phases of Sn and S depending upon the Ts. The lms According to the thermodynamic analysis, the tendency of easy to
grown at 150
C showed trace amount of tin and sulphur along with formation of secondary phases at low Ts is well consistent with the
SnS and Sn2S3 phases. But with the raise of Ts to 250
C, only SnS degree of stabilization of compounds in their Ts. However, forma-
and Sn2S3 phases were identied, which revealed that this tem- tion and growth of SnS nuclei becomes dominant with increasing Ts
perature could accelerate the reaction to form SnS. On further in- because enough thermal energy can be provided. The detection of
crease of Ts to 300
C, single phase SnS was observed which tin sulphide secondary phases by XRD was slightly complicated due
indicates the completion of the reaction between tin, sulphur and to overlapping of SnS, SnS2 and Sn2S3 peaks. Hence, for further
the intermediate Sn2S3 phases. This type of reaction is also called as phase conrmation of sulphurized SnS lms, Raman analysis was
comproportion reaction, which was also observed by Price et al. carried out as it is more sensitive to structural and compositional
[46]. At Ts of 350
C, the recrystallization of grains was increased change of the material.
resulting in an intense narrow peak that correspond to the (111) Fig. 6 shows the room temperature Raman spectra of SnS lms
plane of SnS. that indicated distinct modes, corresponding to sulphur and
Our XRD results implied that the crystallinity of the lms could different phases of SneS. For all sulphurization temperatures, the
be improved by increasing the sulfurization temperature which is lms had SnS modes at 95 cm1, 189 cm1 and 218 cm1, which
due to the acceleration of diffusion process of sulfur atoms into Sn related to the Ag mode. Normally, the appearance of various modes
layer. It means higher sulfurization temperature accounts for depends on the incident and scattered direction of radiation
releasing of more sulfur atoms with sufcient thermal energy to
diffuse into Sn layer, hence more diffusion of sulfur into Sn layer is
possible. That results an improvement in the crystallite size with
temperature (up to 350
C) without affecting the polycrystalline
nature of the lm. This might have enhanced a high order oriented
growth for SnS along the (111) plane due to the suppression of other
lattice planes. Further, the secondary phases such as SnS2 and Sn2S3
that had low formation energies would dissociate with sulfuriza-
tion temperature, leading to the growth of SnS. Coming to device
performance, if the crystal orientation change for a material, the
surface conduction-band position is also changed. This causes the
variation in the work function, ionization potential and electron
afnity in polycrystalline thin lms, which creates a mismatch
between present SnS [47,48] absorber and ZnMgO buffer leading to
the development of energy band offset.
At higher Ts of 400
C, the SnS2 phase is also noticed, in addition
to SnS, which was due to the reevaporation of SnS and tin from the
substrate surface as vapors. For further increase in Ts  450
C, the
peak intensities of both SnS and SnS2 phases found to decrease due
to the reevaporation of either sulphur or tin or both that results in a
decrease of lm thickness. This is also evident from the thickness as
well as optical measurements.
The formation of secondary phases at lower Ts can be attributed
to the high nucleation of formation energy for SnS compared to Fig. 8. Transmittance spectra of SnS lms formed at various temperatures.
 V.R. Minnam Reddy et al. / Current Applied Physics 15 (2015) 588e598 593

paralleled to any one of the three axis (a, b, c) and the direction of
electrical polarization vector of the incident and scattered photons
[49,50]. In the present case, the appearance of Ag mode alone might
be due to the fact that incident and scattered direction of radiation
was parallel to the c-axis and the polarization of the incident and
scattered photons must be along the a-axis [50].
Among the detected modes, peak presented at 189 cm1 and
218 cm1 were assigned to the longitudinal optical (LO) mode
whereas the other at 95 cm1 to transverse optical (TO) mode. The
TO mode is due to the deviation from the rigid backscattering ge-
ometry [51]. Along with SnS mode, the modes related to Sx
(150 cm1 and 490 cm1) [52] and Sn2S3 (304 cm1) [53] phases
were also noticed upto a temperature of 200
C. When the tem-
perature is raised to 250
C, the modes related to Sx were sup-
pressed and for further increase of temperature to 300
C even the
mode corresponding to Sn2S3 phase was also absent. Thus, the
modes corresponding to SnS alone were present in the temperature
range, 300e350
C because of the reaction of tin with (S and) Sn2S3,
which led to the formation of SnS phase. Secondly, the intensity of
Raman lines were found to be high and sharp in this temperatures
range that emphasizes good crystallinity in these lms. However,
for Ts  400
C, a mode related to SnS2 phase present at 312 cm1

Fig. 9. Plot of (ahy)2 versus hy of SnS lms sulphurized at various temperatures.

[54] was noticed in addition to SnS. The appearance of various
phases in the lms sulphurized at different temperature was in
good agreement with the XRD and XPS results.

3.3. Topographical analysis

The topographical analysis was carried out using atomic force

microscope (AFM) scanned over an area of 3 mm  3 mm and is
shown in Fig. 7. The evaluated grain size is varied in the range,
90e180 nm and the lms grown at 350
C had the highest grain size
of 180 nm. These images clearly showed that the change in the
surface topography of SnS lms grown at different Ts. The lms
grown at lower Ts  200
C, showed voids between the grains
because of lower mobility of ad-atoms due to their lack of sufcient
surface thermal energy, however they were covered later by sec-
ondary nucleation at higher Ts. When the Ts was increased to
350
C, the ad-atoms move over the surface, join together and get
enlarged form subgrain collection resulting in the formation of
bigger grains with good compactness. But on further increasing in
the Ts  400
C, the generation of pinholes in the lm was observed
resulting from reevaporation of sulphur/tin atoms will form the
surface of the lm. The high surface roughness at lower Ts was
attributed to kinetic roughening. And with increase of Ts, the lm
surface tends to be smooth which lead to lower roughness, because
of high surface diffusion.

3.4. Optical properties

The wavelength dependence of optical transmittance was

studied in the wavelength range, 300e2500 nm at room temper-
ature. Fig. 8 shows the transmittance spectra of the sulphurized
lms grown at different sulphurization temperatures. The spectra
clearly showed that a signicant change in transmittance with Ts.
The lms grown at Ts of 150
C had lower transmittance (20%) and
relatively small band gap (1.2 eV) due to unreacted tin metal in the
lack of SnS lm [55]. With the increase of Ts to 200
C, the trans-
mittance also increased upto 40% with a little blue shift of the ab-
sorption edge. Further increase of Ts to 300
C resulted in sharp fall
of the absorption edge with a transmittance of 60% due to good
crystallinity and internal morphology of the lm. This implied that
the complete conversions of tin to form single phase of SnS. When
the Ts  400
C, the absorption edge started to shift towards the
lower wavelength side with a marginal change in the transmittance
594 V.R. Minnam Reddy et al. / Current Applied Physics 15 (2015) 588e598

Fig. 10. Variation of electrical resistivity, mobility and carrier concentration of SnS lms with sulphurization temperatures.

due to the formation of secondary phases and reevaporation of tin/ behavior whereas the carrier mobility varied in the range of
sulphur and SnS. This behavior was also supported by the XRD and 41e10 cm2 V1 s1with increasing Ts from 200
C to 400
C. The
Raman analysis. single phase, nearly stiochiometric SnS lms grown at the tem-
The absorption coefcient a is related to transmittance, T by the perature of 350
C had an electrical resistivity of 64 U-cm, a net
relation ln(T) at, where t is the thickness of the lm. It was carrier concentration of 2  1016 cm3 and mobility of
found that all the lms had high absorption coefcient (105 cm1). 41 cm2 V1 s1.
The dependence of the absorption coefcient (a) on the photon
energy (hy) was used for the determination of energy band gap (Eg)
3.6. Characteristics of SnS based solar cell
of SnS lms [42].
In order to demonstrate the quality of suphurized SnS layers of
ahy Bhy  Eg1=2 thickness 610 nm (grown using a tin metal thickness of 300 nm and
sulurization temperature of 350
C for a time duration of 150 min)
where B is the constant. The plot of (ahy)2 versus hy for SnS lms is
for photovoltaic conversion, SnS based thin lm solar cells with the
shown in Fig. 9. The linear nature of the curve indicates the pres-
conguration, glass/Mo/SnS/Zn0.76Mg0.24O/ZnO:Al/Ag were fabri-
ence of direct optical transition in the layers. The energy band gap
cated and the current density-voltage (JeV) measurements were
was determined by extrapolating the straight portion of the plot on
the energy axis.
The estimated band gap was increased with the increase of
sulphurization temperature from 1.2 eV to 1.6 eV. The lower and
higher band gaps are noticed might be due to the presence of Sn2S3
and SnS2 phases along with SnS respectively. The layers formed at
temperature in the range, 300e350
C had an energy band gap of
1.36 eV.

3.5. Electrical properties

Hall effect measurements were performed on the sulphurized

lms that indicated the p-type electrical conductivity. The electrical
resistivity of the lms was varied in the range, 64e210 U-cm with
the increase of sulphurization temperature and is shown in Fig. 10.
The low resistivity was observed at lower Ts (200
C) might be due
to the presence of metallic tin in the lms. When the Ts is raised to
250
C, an increase in the resistivity was observed due to the
presence of secondary phases of Sn2S3 apart the small size of the
grains. Further increase of Ts in the range, 300e350
C led to the
formation of single phase SnS in addition to improvement in the
crystallity and grain size that resulted in a decrease of resistivity in
the lms. For Ts  400
C, the resistivity was increased again due to
the reduction of the lm thickness and formation of SnS2 phase in
addition to SnS which is highly resistive. The change of carrier
concentration with Ts is opposite to that of the resistivity variation Fig. 11. JeV characteristics of SnS based solar cell.
 V.R. Minnam Reddy et al. / Current Applied Physics 15 (2015) 588e598 595

Table 1
Reported experimental and simulation efciencies of SnS based solar cells with different cell structures.

Cell conguration Voc (mV) Jsc (mA/cm2) FF (%) h (%) Ref

Experimental cell parameter

ITO/CdS/SnS/Ag 120 7.000 35 0.29 [56] 1994
Al/CdS/SnS/Ag 140 8.400 38 0.50 [57] 1997
CdO/SnS/Ag 200 5.000 [58] 2001
Cd2SnO4/SnS/Ag 230 3.900 [58] 2001
SnO2:F/SnS/Ag 133 1.230 [58] 2001
CTO/SnS/Fe2/Pt 370 7.80 e 0.63 [5] 2003
SnS/CdS 500 10.00 50 2.50 [57] 2005
TCO/SnS2/SnS/Al 350 1.500 e e [59] 2006
SnO2/SnS/CdS/In 260 9.600 50 1.30 [6] 2006
ITO/Cd1 e xZnxS/SnS/In 280 4.82 34 e [60] 2007
In/ZnS/SnS/ITO 135 9.50 e e [61] 2007
ITO/CdS/SnS/In 220 2.360 35 0.22 [62] 2007
ITO/ZnCdS/SnS/In 288 9.160 50 0.71 [62] 2007
SnO2:F/CdS/SnS/Ag 380 0.170 [63] 2007
SnO2:F/CdS/SnS/CuS/Ag 310 1.000 [63] 2007
SnO2:F/CdS/SnS/Cu2SnS3/Ag 340 6.000 [63] 2007
ITO/SnS/ZnO/In 135 0.150 50 0.01 [64] 2008
ITO/CdS/SnS/Ag 274 0.301 40 0.08 [65] 2008
SnO2:F/CdS/SnS(R)/Ag 340 0.019 e [66] 2008
SnO2:F/CdS/SnS(Z)/Ag 400 0.085 [66] 2008
SnO2:F/CdS/SnS(R-Z)/Ag 400 0.016 [66] 2008
SnO2:F/CdS/SnS(Z)/SnS/Ag 560 e [66] 2008
SnO2:F/CdS/SnS(R-Z)/Ag 370 1.230 44 0.20 [67] 2009
ITO/ZnO/SnS/In 120 0.400 33 0.03 [68] 2009
ITO/PEDOT:PSS/PO/SnS/Al 940 0.055 40 2.05 [69] 2009
SnS/Si 480 8.76 50 0.7 [57] 2009
SnS/ZnO 380 0.08 40 e [57] 2009
ITO/MDMO-PPV/SnS/SnO 740 0.34 41 0.10 [70] 2010
FTO/Pt ele SnS/TiO2/FTO 471 0.300 71 0.10 [71] 2010
Mo/SnxSy/CdS/ZnO:Ga 183 2.70 34 0.17 [72] 2011
ITO/CdS/SnS/In 280 0.34 27 0.01 [73] 2011
Mo/SnS/Si/ITO 289 1.550 37 0.17 [26] 2012
Al/SnS/SnS/ITO/Ti/Al 650 7.640 39 1.95 [29] 2012
ITO/SnO2/SnS/In 40e90 1.5e9.7 e e [74] 2012
FTO/TiO2/SnS/ITO/Pt 504 2.300 15 0.20 [75] 2012
Mo/SnS/CdS/ZnO 132 3.600 29 0.5 [18] 2012
FTO/TiO2/SnS/P3HT/Ag 850 7.350 45 2.81 [30] 2012
AZO/CdS/SnS/Au 217 19.000 e 1.60 [16] 2013
Mo/SnS/In2S3/ZnO:Al/Cu/Al 110 1.980 26 0.6 [76] 2013
Mo/SnS/Si/Si/NieAl 370 2.400 e e [77] 2013
Mo/SnS/CdS/ZnO/Al:ZnO/NieAl 155 3.420 32 0.17 [78] 2013
Mo/SnS/Zn(O,S)/Al:ZnO/ITO 244 19.420 43 2.04 [79] 2013
ITO/ZnMgO/SnS/Cu 270 12.100 64 2.10 [33] 2013
CdS/SnS 400 0.061 81 1.49 [81] 2014
Mo/SnS/Si/Si/NieAl 362 2.400 e 0.42 [82] 2014
Si/SiO2/Mo/SnS/Zn(O,S)/ZnO/ITO/Ag 261 24.900 44 2.90 [84] 2014
Mo/SnS/SnO2/Zn(O,S):N/Al:ZnO/ITO 390 22.600 53 4.63 [22] 2014
Si/SiO2/Mo/SnS/Zn(O,S):N/ZnO/ITO/Ag 344 20.645 56 3.88 [47] 2014
TiO2/SnS 342 0.740 38 0.01 [86] 2014
Pt ele SnS/TiO2/FTO 462 e e e [87] 2014
Mo/SnS/Zn0.76Mg0.24O/ZnO:Al/Ag 575 9.96 36.4 2.02 Present study
Simulation cell parameter
Cu/SnS/ZnO/FTO 749 26.868 85 17.03 [80] 2014
SnS/CdS/ZnO 920 13.400 86 10.6 [83] 2014
CdS/SnS 896 26.650 25 6.03 [85] 2014
ZnS/SnS 894 31.880 57 16.26 [85] 2014
ZnO/SnS 897 31.010 27 7.53 [85] 2014
Si/SnS 893 30.670 52 14.30 [85] 2014

Values in bold indicate experimentally obtained highest values of inorganic heterojunction solar cell parameters.
596 V.R. Minnam Reddy et al. / Current Applied Physics 15 (2015) 588e598
performed. Fig. 11 shows the JeV characteristics of the cell that
shows the highest conversion efciency of 2.02% with the open
circuit voltage (Voc) 575 mV, short-circuit current density
(Jcs) 9.96 mA/cm2 and ll factor (FF) 36.4%. The obtained results
were compared with reported experimental and simulation values
using Table 1, which shows device parameters such as Voc, Jsc, FF
and efciency of SnS-based solar cells in year wise pattern. The
value of Jsc acquired in the present work is low compare to the
reported value by Sinsermsuksakul et al. [22] and Steinmann et al.
[48]. This indicates a reduction in the recombination (low Jsc) levels,
which could lead to high Voc. A more detailed analysis of the
junction behavior is required to assess the performance of the de-
vice, which is under progress. From the table it was also noticed
that SnS-based solar cells in different form of junctions exhibited
high Voc values such as 650 mV; unstable 560 mV, stable 500 mV;
simulated 897 mV and 850 mV in the form of homo, hetero and
bulk junctions respectively. The following lines gave the reasons
with supporting references for getting high Voc. Further, by
considering the highest inorganic heterojunction solar cell pa-
rameters (Voc 575 mV, Jsc 24.9 mA/cm2 and FF 81% from the
Table 1) that were achieved using different window/buffer layers
with SnS as an absorber, it will be possible to realize a SnS-based
solar cell with solar conversion efciencies around 12%. An opti-
mization of the device parameter will denitely led to efciencies
close to 15% in the future.
Generally in thin lms solar cells Voc arises from difference in
the Fermi levels of p- (absorber layer) and n- (buffer/window layer)
type materials. It mainly depends on parameters such as recom-
bination at the junction, doping level, back contact barrier and front
contact/buffer. In addition, it also depends on the thickness, grain
size, band gap, electron afnity, crystal structure, electrical nature,
doping and deposition technique of the absorber and buffer/win-
dow layers. Hasan et al. [81] reported an improvement in Voc from
140 mV to 400 mV with the increase of thickness from 100 nm to
300 nm, indicating that the dependence of Voc on thickness. Ikuno
et al. [33] reported a Voc of 270 mV in case of ZnMgO/SnS solar cell
with SnS thickness of 50 nm. In our case, the thickness of SnS layer
is much higher (610 nm) than this. So the higher thickness of SnS
may lead to enhancement of built-in potential, which results an
improvement in Voc. Harvard group [22,48,79] reported 244 mV of
Voc initially and it enhanced 128 mV by oxidizing SnS surface.
Duenow et al. [88] reported high Voc by incorporating O2 in CdTe
solar cells. These reports showed that dependence of Voc on
incorporation of oxygen content in absorber layers. In the present
case, the buffer layer was grown by solution based chemical spray
pyrolysis in an open atmosphere, which might have incorporated
small amount of oxygen at the junction region that results in a high
value of Voc. Secondly, Ichimura group [4,60e62,64,74] studied
different n-type partners such as ZnO and ZnCdS, which showed
different values of Voc such as 135 mV and 288 mV respectively
that indicted dependence of Voc on the nature of buffer layer. The
buffer layer investigated in the present study is different from
others, who reported different low Voc values. This might be the
other reason for getting different Voc values than others.
4. Conclusions
Single phase polycrystalline SnS were successfully synthesized
using sulphurization of tin precursors. A detailed analysis of the
properties of SnS lms were investigated as a function of sulphu-
rization temperature. The change in the ionic states of tin with
sulphurization temperature that led to the formation of different
phases was discussed using the XPS analysis with the possible lm
formation mechanism. The XRD and Raman measurements sup-
ported this behavior with the presence of Sn2S3 phase at lower
temperature (<300
C) and SnS2 phase at higher temperature
(400
C). But, the lms sulphurized between 300
C and 350
C
had single phase with stoichiometry and good crystallinity. The
lms showed a low electrical resistivity of 64 U-cm grown at the
temperature of 350
C with an energy band gap of 1.36 eV. The
conversion efciency achieved in our study was 2.02%. Further
simple sulphurization technique used to grow the layers might be
advantageous for large scale production of SnS lms at low cost.
Acknowledgments
The authors wish to acknowledge the nancial support from the
University Grants Commission (UGC), New Delhi (No.F.5-99/
2007(BSR)) in the form of a Research Fellowships in Science for
Meritorious Students. This work was also supported by the New &
Renewable Energy Program (No. 20143030011950) and the Human
Resources Development Program (No. 20124030200100) of the
Korea Institute of Energy Technology Evaluation and Planning
(KETEP) grant funded by the Korean Ministry of Trade, Industry and
Energy (MOTIE). The authors also wish to thank the DST-UKIERI,
New Delhi for the award of collaborative project that provides
travel assistance to carry out some of the measurements at
Northumbria University, Newcastle NE1 8ST, UK.
References
[1] L.A. Burton, D. Colombara, R.D. Abellon, F.C. Grozema, L.M. Peter, T.J. Savenije,
G. Dennnler, A. Walsh, Synthesis characterization and electronic structure of
single crystal SnS, Sn2S2 and SnS2, Chem. Mater. 25 (2013) 4908e4916.
[2] L.A. Burton, A. Walsh, Phase stability of the earth abundant tin suldes SnS,
SnS2 and Sn2S3, J. Phys. Chem. C 116 (2012) 24262e24267.
[3] D.I. Bletskan, Phase equilibrium in binary systems AIVBVI, J. Ovonic Res. 1
(2005) 61e69.
[4] N. Sato, M. Ichimura, E. Araia, Y. Yamazaki, Characterization of electrical
properties and photosensitivity of SnS thin lms prepared by the electro-
chemical deposition method, Sol. Energy Mater. Sol. Cells 85 (2005) 153e165.
[5] B. Subramanian, C. Sanjeeviraja, M. Jayachandran, Photoelectrochemical
characteristics of brush plated tin sulde thin lms, Sol. Energy Mater. Sol.
Cells 79 (2003) 57e65.
[6] K.T. Ramakrishna Reddy, N. Koteswara Reddy, R.W. Miles, Photovoltaic
properties of SnS based solar cells, Sol. Energy Mater. Sol. Cells 90 (2006)
3041e3046.
[7] L. Amalraj, C. Sanjeeviraja, M. Jayachandran, Spray pyrolysised tin disulphide
thin lm and characterization, J. Cryst. Growth 234 (2002) 683e689.
[8] C. Khwelia, K. Boubaker, T. Ben Nasrallah, M. Amlouk, S. Belgacem, Morpho-
logical and thermal properties of b -SnS2 sprayed thin lms using boubaker
polynomials expansion, J. Alloy. Compd. 477 (2009) 461e467.
[9] H.S. Kim, Y.H. Chung, S.H. Kang, Y.E. Sung, Electrochemical behaviour of car-
bon coated SnS2 for use as the anode in lithiumion batteries, Electrochim. Acta
54 (2009) 3606e3610.
[10] T.H. Sajeesh, A.R. Warrier, C.S. Karta, K.P. Vijaykumar, Optimization of pa-
rameters of chemical spray pyrolosis technique to get n- and p-type layers of
SnS, Thin Solid Films 518 (2010) 4370e4374.
[11] G. Ham, S. Shin, J. Park, H. Choi, J. Kim, Y.A. Lee, H. Seo, H. Jeon, Tuning the
electronic structure of tin suldes grown by atomic layer deposition, Appl.
Mater. Interfaces 5 (2013) 8889e8896.
[12] L.A. Burton, A. Walsh, Band alignment in SnS thin lm solar cells, possible origin
of the low conversion efciency, Appl. Phys. Lett. 102 (2013), 132111 (1-3).
[13] M. Devika, N. Koteswara Reddy, F. Patolsky, K.R. Gunasekhar, Ohmic contacts
to SnS lms selection and estimation of thermal stability, J. Appl. Phys. 104
(1008) 124503 (1-6).
[14] A.R.H.F. Ettema, R.A.D. Groot, C. Haas, T.S. Turner, Electronic structure of SnS
deduced from photoelectron spectra and band structure calculations, Phys.
Rev. B 46 (1992) 7363e7373.
[15] M.R. Fadavieslam, N. Shahtahmasebi, M.R. Roknabadi, M.M.B. Mohagheghi,
A study of the photoconductivity and thermoelectric properties of SnxSy op-
tical semiconductor thin lms deposited by the spray pyrolysis technique,
Phys. Scr. 84 (2011), 035705 (1-8).
[16] A. Schneikart, H.J. Schimper, A. Klein, W. Jaegermann, Efciency limitations of
thermally evaporated thin lms SnS solar cells, J. Phys. D Appl. Phys. 46
(2013), 305109 (1-7).
[17] J. Henry, K. Mohanraj, S. Kannan, S. Barathan, G. Sivakumar, Structural and optical
properties of SnS nanoparticals and electron beam evaporated SnS thin lms,
J. Exp. Nanosci. (2013), http://dx.doi.org/10.1080/17458080.2013.788226.
[18] S.A. Bashkirov, V.F. Greemenok, V.A. Ivanov, V.V. Lazenka, K. Bente, Tin sulde
thin lms and Mo/p-SnS/n-CdS/ZnO heterojunctions for photovoltaic appli-
cations, Thin Solid Films 520 (2012) 5807e5810.
 V.R. Minnam Reddy et al. / Current Applied Physics 15 (2015) 588e598
[19] A. Gomez, H. Martinez, M.C. Rodriguez, D. Avellaneda, P.G. Reyesa, O. Flores,
Modication of optical and electrical properties of chemical bath deposited
SnS using O2 plasma treatments, Appl. Surf. Sci. 275 (2013) 273e277.
[20] B. Ghosh, M. Das, P. Banerjee, S. Das, Fabrication of SnS thin lm by the
successive ionic layer adsorption and reaction method, Semicond. Sci. Tech-
nol. 23 (2008), 125013 (1-6).
[21] K. Hartman, J.L. Johnson, M.I. Bertoni, D. Recht, M.J. Aziz, M.A. Scarpulla,
T. Buonassisi, SnS thin lms by RF sputtering at room temperature, Thin Solid
Films 519 (2011) 7421e7424.
[22] P. Sinsermsuksakul, L. Sun, S.W. Lee, H.H. Park, S.B. Kim, C. Yang, R.G. Gordon,
Overcoming efciency limitations of SnS-based solar cells, Adv. Energy Mater.
(2014), 1400496 (1-7).
[23] J. Park, M. Song, W.M. Jung, W.Y. Lee, J. Lee, H. Kim, I.W. Shim, Preparation of
SnS thin lms by MOCVD method using single source precursor, bis(3-
mercapto-1-propanethiolato) Sn(II), Bull. Korean Chem. Soc. 33 (2012)
3383e3386.
[24] M.M. Kamel, M.M. Ibrahim, Electrochemical deposition and characterization
of SnS thin lms, J. Solid State Electrochem. 15 (2011) 683e688.
[25] K.T. Ramakrishna Reddy, P. Puranadhara Reddy, Structural studies on SnS
lms grown by a two-step process, Mater. Lett. 56 (2002) 108e111.
[26] F. Jiang, H. Shen, W. Wang, L. Zhang, Preparation of SnS lm by sulfurization
and SnS/a-Si heterojunction solar cells, J. Electrochem. Soc. 159 (2012)
H235eH238.
[27] J.J. Loferski, Theoretical considerations governing the choice of optimum
semiconductor for photovoltaic solar energy conversion, J. Appl. Phys. 27
(1956) 777e784.
[28] R. Chandrasekharan, Numerical Modeling of Tin Based Absorber Devices for
Cost Effective Solar Photovoltaics, the Graduate School John and Willie Leone
Family Department of Energy and Mineral Engineering, The Pennsylvania
State University, May 2012.
[29] G. Yue, Y. Lin, X. Wen, L. Wang, D. Peng, SnS homojunction nanowire based
solar cells, J. Mater. Chem. 22 (2012) 16437e16441.
[30] W. Guo, Y. Shen, M. Wu, T. Ma, Highly efcient inorganic organic hetero-
junction solar cells based on SnS sensitized spherical TiO2 electrodes, Chem.
Commun. 48 (2012) 6133e6135.
[31] K.T. Ramakrishna Reddy, K. Ramya, G. Sreedevi, T. Shimizu, Y. Murata,
M. Sugiyama, Studies on the energy band discontinuities in SnS/ZnMgO thin
lm heterojunction, Energy Procedia 10 (2011) 172e176.
[32] P. Pratap, A. Suryanarayana Reddy, G. Ramachandra Reddy, R.W. Miles,
K.T. Ramakrishna Reddy, Characterization of novel sprayed Zn1-xMgxO lms
for photovoltaic application, Sol. Energy Mater. Sol. Cells 94 (2010)
1434e1436.
[33] T. Ikuno, R. Suzuki, K. Kitazumi, N. Takahashi, N. Kato, K. Higuchi, SnS thin lm
solar cell with Zn1-xMgxO buffer layers, Appl. Phys. Lett. 102 (2013), 193901 (1-4).
[34] M.M. Hyland, G.M. Bancroft, An XPS study of gold deposition at low tem-
peratures on sulphide minerals reducing agents, Geochim. Acta 53 (1989)
367e372.
[35] H. Peisert, T. Chasse, P. Streubel, A. Meisel, R. Szargan, Relaxation energies in
XPS and XAES of solid sulfur compounds, J. Electron Spectrosc. Relat. Phenom.
68 (1994) 321e328.
[36] H. Zhang, C. Hu, X. Wang, Y. Xi, X. Li, Synthesis and photosensitivity of SnS
nanobelts, J. Alloys Compd. 513 (2012) 1e5.
[37] D. Chen, G. Shen, K. Tang, S. Lei, H. Zheng, Y. Qian, Microwave assisted polyol
synthesis of nanoscale SnSx (x1,2) akes, J. Cryst. Growth 260 (2004) 469e474.
[38] M. Satish, S. Mitani, T. Tomai, I. Honna, Ultra thin SnS2 nanoparticals on
grapheme nanosheets synthesis characterization and Li ion storage applica-
tions, J. Phys. Chem. C 116 (2012) 12475e12481.
[39] N. Koteswara Reddy, K. Ramesh, R. Ganesan, K.T. Ramakrishna Reddy,
K.R. Gunasekhar, E.S.R. Gopal, Synthesis and characterization of coevaporated
tin sulphide thin lms, Appl. Phys. A 83 (2006) 133e138.
[40] K. Biswas, S. Lany, A. Zunger, The electronic consequence of multivalent ele-
ments in inorganic solar absorbers, multivalence of Sn in Cu2ZnSnS4, Appl.
Phys. Lett. 96 (2010), 201902 (1-3).
[41] K. Mishra, K. Rajeshwar, A. Weiss, M. Murley, R.D. Engelken, M. Slayton,
H.E. Mc Cloud, Electrodeposition and characterization of SnS thin lms,
J. Electrochem. Soc. 136 (1989) 1915e1923.
[42] C.C. Huang, Y.J. Lin, C.Y. Chuang, C.J. Liu, Y.W. Yang, Conduction type control of
SnSx lms prepared by the sol gel method for different sulfur contents,
J. Alloys Compd. 553 (2013) 208e211.
[43] S. Lopez, S. Granads, A. Ortiz, Spray pyrolysis deposition of Sn2S3 thin lms,
Semicond. Sci. Technol. 11 (1996) 433e436.
[44] A. Melenaar, Autocatalytic deposition of gold and tin, Electrochem. Soc. Ext.
Abstr. 84 (2) (1984) 634.
[45] A.S. Juarez, A. Ortiz, Structural peoperties of SnxSy thin lms prepared by
plasma enchanced chemical vapour deposition, J. Electrochem. Soc. 147
(2000) 3708e3717.
[46] L.S. Price, I.P. Parkin, A.M.E. Hardly, R.J.H. Clark, Atmospheric pressure
chemical vapor deposition of tin suledes on glass, Chem. Mater. 11 (1999)
1792e1799.
[47] V. Stevanovic, K. Hartman, R. Jaramillo, S. Ramanathan, T. Buonassisi, P. Graf,
Variations of ionization potential and electron afnity as a function of surface
orientation: the case of orthorhombic SnS, Appl. Phys. Lett. 104 (2014),
211603 (1-4).
[48] V. Steinmann, R. Jaramillo, K. Hartman, R. Chakraborty, R.E. Brandt,
J.R. Poindexter, Y.S. Lee, L. Sun, A. Polizzotti, H.H. Park, R.G. Gordon,
597
T. Buonassisi, 3.88% Efcient tin sulde solar cells using congruent thermal
evaporation, Adv. Mater. 26 (2014) 7488e7492.
[49] J.D. Wiley, W.J. Buckel, R.L. Schmidt, Infrared reectivity and Raman scattering
in GeS, Phys. Rev. B 13 (1976) 2489e2496.
[50] H.R. Chandrasekar, R.G. Humphreys, U. Zwick, M. Cardona, Infrared reectivity
and Raman spectra of the IV e VI compounds SnS and SnSe, Phys. Rev. B 15
(1977) 2177e2183.
[51] M. Devika, N. Kotewara Reddy, M. Prashantha, K. Ramesh, S. Venkataraana
Reddy, Y.B. Hahn, K.R. Gunasekhar, The physical properties of SnS lms grown
on lattice match and amorphous substrates, Phys. Status Solidi A 207 (2010)
1864e1869.
[52] V. Toniazzo, C. Mustin, J.M. Portal, B. Humbert, R. Benoit, R. Erre, Elemental
sulfur at the pyrite surface speciation and quantication, Appl. Surf. Sci. 143
(1999) 229e237.
[53] Y. Jayasree, U. Chalapathi, P. UdayBhaskar, V. Sundara Raja, Effect of precursor
concentration and bath temperature on the growth of chemical bath depo-
sition tin sulde thin lms, Appl. Surf. Sci. 258 (2012) 2732e2740.
[54] N.R. Mathews, H.B.M. Anaya, M.A.C. Jacome, C.A. Chavez, J.A.T. Antonio, Tin
sulde thin lms by pulse electrodeposition structural morphological and
optical properties, J. Electrochem. Soc. 157 (2010) H337eH341.
[55] F. Jiang, H. Shen, C. Gao, B. Liu, Z. Shen, Preparation and properties of SnS lm
grown by two stage process, Appl. Surf. Sci. 257 (2011) 4901e4905.
[56] H. Noguchi, A. Setiyadi, H. Tanamura, T. Nagatomo, O. Omoto, Characterisation
of vacuum evaproated tin sulphide lm for solar cell materials, Sol. Energy
Mater. Sol. Cells 35 (1994), 325-321.
[57] K.T. Ramakrishna Reddy, P. Pratap, R.W. Miles, Thin sulphide lms for solar
photovoltaic application, in: H. Tanaka, K. Yamashita (Eds.), Photovoltaics:
Development, Applications and Impact, Nova Science Publishers Inc., 2010,
pp. 1e27.
[58] M. Ristov, G. Sinadinovski, M. Mitreski, M. Ristova, Photovoltaic cells based on
chemically deposited p-type SnS, Sol. Energy Mater. Sol. Cells 69 (2001) 17e24.
[59] A. Sanchez-Juarez, A. Tiburcio-Silver, A. Ortiz, Fabrication of SnS2/SnS heter-
ojunction thin lm diodes by plasma enhanced chemical vapor deposition,
Thin Solid Films 480e481 (2005) 452e456.
[60] M. Gunasekaran, P. Ramasamy, M. Ichimura, Preparation of ternary Cd1-xZnxS
alloy by photochemical deposition (PCD) and its application to photovoltaic
devices, Phys. Status Solidi C. 3 (2006) 2656e2660.
[61] T. Miyawaki, M. Ichimura, Fabrication of ZnS thin lms by an improved
photochemical deposition mehod and application to ZnS/SnS heterojunction
cells, Mater. Lett. 61 (2007) 4683e4686.
[62] M. Gunasekaran, M. Ichimura, Photovoltaic cells based on pulsed electro-
chemically deposited SnS and photochemically deposited CdS and Cd1-xZnxS,
Sol. Energy Mater. Sol. Cells 91 (2007) 774e778.
[63] D. Avellanneda, G. Delgado, M.T.S. Nair, P.K. Nair, Structural and chemical
transformations in SnS thin lms used in chemically deposited photovoltaic
cells, Thin Solid Films 515 (2007) 5771e5776.
[64] M. Ichimura, H. Takagi, Electrodeposited ZnO/SnS heterostructures for solar
cell application, Jpn. J. Appl. Phys. 47 (2008) 7845e7847.
[65] B. Ghosh, M. Das, P. Banerjee, S. Das, Fabrication of vacuum-evaporated SnS/
CdS heterojunction for PV applications, Sol. Energy Mater. Sol. Cells 92 (2008)
1099e1104.
[66] D. Avellaneda, M.T.S. Nair, P.K. Nair, Polymorphic tin sulde thin lms of zinc
blende and orthorhombic structures by chemical deposition, J. Electrochem.
Soc. 155 (7) (2008) D517eD525.
[67] D. Avellaneda, M.T.S. Nair, P.K. Nair, Photovoltaic structures using chemically
deposited tin sulde thin lms, Thin Solid Films 517 (2009) 2500e2502.
[68] B. Ghosh, M. Das, P. Banerjee, S. Das, Fabrication of the SnS/ZnO hetero-
junction for PV applications using electrodeposited ZnO lms, Semicond. Sci.
Technol. 24 (2009), 025024 (1-7).
[69] Z. Wanga, S. Qu, X. Zeng, J. Liu, C. Zhang, F. Tan, L. Jin, Z. Wang, The application
of SnS nanoparticles to bulk heterojunction solar cells, J. Alloys Compd. 482
(2009) 203e207.
[70] Z. Wang, S. Qu, X. Zeng, J. Liu, F. Tan, Y. Bi, Z. Wang, Organic/inorganic hybrid
solar cells based on SnS/SnO nanocrystals and MDMO-PPV, Acta Mater. 58
(2010) 4950e4955.
[71] Y. Wang, H. Gong, B.H. Fan, G.X. Hu, Photovoltaic behavior of nanocrystalline
SnS/TiO2, J. Phys. Chem. C 114 (2010) 3256e3259.
[72] J. Malaquias, P.A. Fernandes, P.M.P. Salome, A.F. da Cunha, Assessment of the
potential of tin sulphide thin lms prepared by sulphurization of metallic
precursors as cell absorbers, Thin Solid Films 519 (2011) 7416e7420.
[73] B. Ghosh, S. Chowdhury, P. Banerjee, S. Das, Fabrication of CdS/SnS hetero-
structured device using successive ionic layer adsorption and reaction
deposited SnS, Thin Solid Films 519 (2011) 3368e3372.
[74] J.J.M. Vequizo, M. Ichimura, Fabrication of electrodeposited SnS/SnO2 heter-
ojunction solar cells, Jpn. J. Appl. Phys. 51 (2012), 10NC38 (1e4).
[75] K.G. Deepa, J. Nagaraju, Growth and photovoltaic performance of SnS quan-
tum dots, Mater. Sci. Eng. B 177 (2012) 1023e1028.
[76] G.R. Gopinath, K.T. Ramakrishna Reddy, Growth of polycrystalline In2S3 thin
lms by chemical bath deposition using acetic acid as a complexing agent for
solar cell application, ISRN Condens. Matter Phys. 2013 (2013), 140230 (1-6).
[77] F. Jiang, H. Shen, J. Jiao, Formation of photoconductive SnS thin lms through
reaction of Sn-metal lms in sulfur-vapor, ECS J. Solid State Sci. Technol. 2 (11)
(2013) P478eP484.
[78] M. Steichen, R. Djemour, L. Gutay, J. Guillot, S. Siebentritt, P.J. Dale, Direct
synthesis of single-phase p-type SnS by electrodeposition from a dicyanamide
598 V.R. Minnam Reddy et al. / Current Applied Physics 15 (2015) 588e598
ionic liquid at high temperature for thin lm solar cells, J. Phys. Chem. C 117
(2013) 4383e4393.
[79] P. Sinsermsuksakul, K. Hartman, S.B. Kim, J. Heo, L. Sun, H.H. Park,
R. Chakraborty, T. Buonassisi, R.G. Gordon, Enhancing the efciency of SnS
solar cells via band-offset engineering with a zinc oxysulde buffer layer,
Appl. Phys. Lett. 102 (2013), 053901 (1-5).
[80] A. Verma, P. Asthana, Modeling of thin lm solar photovoltaic based on ZnO/
SnS Oxide-absorber substrate conguration, J. Eng. Res. Appl. 4 (2014) 12e18.
[81] B.A. Hasan, Photovoltaic structures using thermally evaporated tin sulde thin
lms, Int. J. Adv. Res. Eng. Technol. 5 (2014) 91e99.
[82] F. Jiang, H. Shen, J. Jiao, Effect of the thickness on the optoelectronic properties
of SnS lms and photovoltaic performance of SnS/i-a-Si/n-a-Si solar cells,
Appl. Phys. A, DOI 10.1007/s00339-014-8640-8.
[83] H. Ullah, B. Mari, Numerical analysis of SnS based polycrystalline solar cells,
Superlattices Microstruct. 72 (2014) 148e155.
[84] H.H. Park, R. Heasley, L. Sun, V. Steinmann, R. Jaramillo, K. Hartman, R.
View publication stats
Chakraborty, P. Sinsermsuksakul, D. Chua, T. Buonassisi, R.G. Gordon, Co-
optimization of SnS absorber and Zn(O,S) buffer materials for improved so-
lar cells, Prog. Photovolt. Res. Appl., DOI: 10.1002/pip.2504.
[85] J. Xu, Y. Yang, Study on the performances of SnS heterojunctions by numerical
analysis, Energy Convers. Manag. 78 (2014) 260e265.
[86] Y. Oda, H. Shen, L. Zhao, J. Li, M. Iwamoto, H. Lin, Energetic alignment in
nontoxic SnS quantum dot-sensitized solar cell employing spiro-OMeTAD as
the solid-state electrolyte, Sci. Technol. Adv. Mater. 15 (2014), 035006 (1-8).
[87] M. Patel, A. Ray, Magnetron sputtered Cu doped SnS thin lms for improved
photoelectrochemical and heterojunction solar cells, RSC Adv. 4 (2014)
39343e39350.
[88] J.N. Duenow, R.G. Dhere, D. Kuciauskas, J.V. Li, J.W. Pankow, P.C. Dippo,
C.M.D. Hart, T.A. Gessert, Oxygen incorporation during fabrication of substrate
CdTe photovoltaic devices, in: IEEE Photovoltaic Specialists Conference, Aus-
tin, Texas, June 3e8, 2012, 2012.