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Review on Tin (II) Sulfide (SnS) Material: Synthesis, Properties, and Applications

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Review on Tin (II) Sulfide (SnS) Material: Synthesis,

Properties, and Applications
a b c
N. Koteeswara Reddy , M. Devika & E. S. R. Gopal
a
Center for Nanoscience and Engineering, Indian Institute of Science, Bangalore 560012,
India
b
Department of Aerospace Engineering, Indian Institute of Science, Bangalore 560012, India
c
Department of Physics, Indian Institute of Science, Bangalore 560012, India
Published online: 25 Aug 2015.

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To cite this article: N. Koteeswara Reddy, M. Devika & E. S. R. Gopal (2015): Review on Tin (II) Sulfide (SnS)
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 Critical Reviews in Solid State and Materials Sciences, 0:1–40, 2015
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DOI: 10.1080/10408436.2015.1053601
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Review on Tin (II) Sulfide (SnS) Material: Synthesis, Properties,

and Applications
N. Koteeswara Reddy*,1 M. Devika,2 and E. S. R. Gopal3
1
Center for Nanoscience and Engineering, Indian Institute of Science, Bangalore 560012, India
2
Department of Aerospace Engineering, Indian Institute of Science, Bangalore 560012, India
3
Department of Physics, Indian Institute of Science, Bangalore 560012, India

Tin (II) sulphide (SnS), a direct band gap semiconductor compound, has recently received
great attention due to its unique properties. Because of low cost, absence of toxicity, and good
abundance in nature, it is becoming a candidate for future multifunctional devices
particularly for light conversion applications. Although the current efficiencies are low, the
cost-per-Watt is becoming competitive. At room temperature, SnS exhibits stable low-
symmetric, double-layered orthorhombic crystal structure, having a D 0.4329, b D 1.1192,
and c D 0.3984 nm as lattice parameters. These layer-structured materials are of interest in
various device applications due to the arrangement of structural lattice with cations and
anions. The layers of cations are separated only by van der Waals forces that provide
intrinsically chemically inert surface without dangling bonds and surface density of states. As
a result, there is no Fermi level pinning at the surface of the semiconductor. This fact leads to
considerably high chemical and environmental stability. Further, the electrical and optical
properties of SnS can be easily tailored by modifying the growth conditions or doping with
suitable dopants without disturbing its crystal structure.
In the last few decades, SnS has been synthesized and studied in the form of single-crystals and
thin-films. Most of the SnS single-crystals have been synthesized by Bridgeman technique,
whereas thin films have been developed using different physical as well as chemical deposition
techniques. The synthesis or development of SnS structures in different forms including
single-crystals and thin films, and their unique properties are reviewed here. The observed
physical and chemical properties of SnS emphasize that this material could has novel
applications in optoelectronics including solar cell devices, sensors, batteries, and also in
biomedical sciences. These aspects are also discussed.

Keywords SnS compound, IV–VI layered semiconductor, absorber materials, narrow band gap
material, structural and optical properties, optoelectronic devices

Table of Contents

1. INTRODUCTION........................................................................................................................................... 2

2. GENERAL PROPERTIES .............................................................................................................................. 3

3. CRYSTAL STRUCTURE OF SnS.................................................................................................................... 3

3.1. Structural Transition.................................................................................................................................. 4
3.2. Lattice Geometry ...................................................................................................................................... 4
3.3. Band Structure ......................................................................................................................................... 5

4. EXPERIMENTAL PROCEDURE.................................................................................................................... 6
4.1. Powders and Single Crystals ....................................................................................................................... 6

*E-mail: dr_nkreddy@rediffmail.com
Color versions of one or more of the figures in this article can be found online at www.tandfonline.com/bsms.

1
 2 N. KOTEESWARA REDDY ET AL.

4.2. Thin Films ............................................................................................................................................... 7

4.2.1. Chemical Methods........................................................................................................................... 7
4.2.2. Electrochemical Deposition (ECD) .................................................................................................... 8
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4.2.3. Chemical Vapor Deposition (CVD).................................................................................................... 9

4.2.4. Close-Space Vapor Transport (CSVT) ...............................................................................................10
4.2.5. Atomic Layer Deposition (ALD) ......................................................................................................10
4.2.6. Spray Pyrolysis ..............................................................................................................................11
4.2.7. Physical Deposition ........................................................................................................................11

5. RESULTS AND DISCUSSION........................................................................................................................14

5.1. Physical Properties of Single Crystals .........................................................................................................14
5.1.1. Structural Properties .......................................................................................................................14
5.1.2. Electrical Properties........................................................................................................................15
5.1.3. Optical Properties...........................................................................................................................16
5.2. Physical Properties of SnS Thin Films.........................................................................................................19
5.2.1. Temperature Effect.........................................................................................................................24
5.2.2. Thickness Effect ............................................................................................................................24
5.2.3. Substrates Surface Effect ................................................................................................................25
5.2.4. Annealing Effect ............................................................................................................................27
5.2.5. Doping Effect ................................................................................................................................29
5.2.6. Metallization of SnS .......................................................................................................................30

6. DEVICE APPLICATIONS OF SnS .................................................................................................................31

6.1. Photovoltaic Applications .........................................................................................................................32
6.2. Other Applications ...................................................................................................................................34
6.2.1. Photoelectrochemical Cells..............................................................................................................34
6.2.2. Solid-State Batteries .......................................................................................................................35

7. SUMMARY WITH FUTURE ISSUES .............................................................................................................37

ACKNOWLEDGMENTS ......................................................................................................................................38

REFERENCES......................................................................................................................................................38

1. INTRODUCTION for the realization of various thin film materials. Development

The development of solid state devices has been a major
technology innovation, which has revolutionized electronics,
communication, computer hardware, and also general applica-
tions in entertainment industry and so on. It has pushed the
earlier thermionic devices to specialized pockets of applica-
tions. Semiconducting germanium (Ge), silicon (Si), gallium
arsenide (GaAs), and other materials have played a major role
in the new activities. Gallium nitride (GaN) has introduced
advances in optoelectronics. Among these materials, Si has a
special place of being applied widely in photovoltaic devices
also.1 However, the manufacturing cost of Si based devices
still remains high. From the last few decades, semiconducting
thin film technology has received much attention because of
the wider applications in various fields of science and technol-
ogy. The utilization of thin films in the fabrication of devices
drastically reduces the materials cost. Further, various deposi-
tion and characterization techniques have also been developed
of solution growth techniques has further reduced the cost of
production since these techniques are cheaper, scalable, and
simple. Nevertheless, the cost of Si-based photovoltaic sys-
tems appears to have reached a plateau and further reduction
appears to be difficult.
Over past few decades the usage of renewable energy is
gradually increasing to meet the increase of energy demand.
Among the renewable energy sources, the solar energy seems
to be the most attractive and promising alternative energy
source due to its availability, non-pollutant, and universal
nature. Cadmium telluride (CdTe), copper indium selenide
(CIS), copper indium gallium selenide (CIGS), and amorphous
silicon (a-Si) are four important thin-film technologies often
used in photovoltaic (PV) solar cells.2,3 No doubt, the develop-
ment of binary and ternary thin film materials has created path-
ways compared to the Si-dependent technology, due to the
favorable properties and simplicity in their synthesis.
 REVIEW ON TIN SULFIDE MATERIAL
However, in real practice these materials failed to achieve
expected goals due to their toxicity, high cost, and lack of
reproducibility. Efforts are still continuing at various laborato-
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ries to identify and develop new class-materials for PV device
applications where the constituent materials are not toxic and
are readily available in a low cost manner. The factors that
should be considered in developing new semiconductor mate-
rials include (1) a suitable energy band gap, (2) the ability to
deposit the material using a low-cost deposition technique,
and (3) abundance of the elements.
Dittrich et al. surveyed many materials in view of their pos-
sible PV applications and suggested that the sulfosalts are
more promising candidates for future solar cell devices.4,5
Among these sulfosalts, tin mono sulfide (SnS) is one of the
best compounds suitable for various applications particularly
for fabrication of solar cell devices due to its unique physical
properties. Contrary to the lack of abundancy of indium and
gallium elements for CIS and CIGS devices, the constituent
elements of SnS are abundant in the Earth’s crust. As com-
pared to the perceived toxicity problems (Cd, Se) associated
with the usage of CdTe, CIS, and CIGS, Sn and S are safe in
view of environment as well as lives of human-beings. As a
result, SnS has evolved as a safe and sustainable semiconduct-
ing material. In particular, SnS has attracted some attention
because its band gap lies in between those of Si (1.12eV) and
GaAs (1.43 eV). Today, the cadmium selenide (CdSe) is one
of the most commonly known photoconductors due to its enor-
mous photoconductivity to dark conductivity ratio. The toxic-
ity and hazardous nature of Cd and Se elements is shadowing
its applications in the field of optoelectronics. In this view, the
SnS can fulfill the above requirements as an alternative to
CdSe for photo-conducting applications. The growth process-
ing of SnS is almost pollution-free and moreover, the cost,
availability, toxicity, and stability of SnS are seen to be highly
appropriate not only for solar cell applications but also as coat-
ing material for heating mirrors.6
2. GENERAL PROPERTIES
In this section we summarize the physical properties (struc-
tural, optical, and electrical properties), structural transitions
(room temperature phase to high temperature and high pres-
sure phases), crystal structure, and band structures (of all the
phases) of SnS.
SnS is one of the binary compound belongs to IV–VI group.
It is a layer-structured compound like germanium sulfide
(GeS), germanium selenide (GeSe) and tin selenide (SnSe),
etc. Owing to their layered structures, SnS also exhibits strong
anisotropic vibrational properties7,8 and therefore these struc-
tures show significant differences in their physical properties
when measurements are made along their crystallographic
axes. Further, the layers in SnS compound are coupled with
weak van der Waals forces. The presence of week forces in
SnS provides intrinsically a chemical inert surface without
3
dangling bonds and surface density states.9,10 As a result, the
surface of SnS becomes free from Fermi level pinning. This
fact makes SnS to be chemically and environmentally inert.11
At normal temperature and pressure (NTP), the SnS compound
usually possesses orthorhombic disorder crystal-structure with
a space group of Pbmn .D16 2h / having a D 0.432, b D 1.12 and
12
c D 0.398 nm (JCPDS card No: 39-0354) as lattice parame-
ters. Further, SnS exhibits chemical stability in acidic solu-
tions,13 high melting and boiling points of 880 and 1230
C. At
room temperature (RT), the work function and dissociation
energies of SnS are »4.214 and 4.5 eV,15 respectively.
The crystal structure of SnS is stable over a range of
compositions for which Sn : S ffi 1 : 1 C x. Generally, the
excess of non-metallic atoms induces the proportionate Sn
vacancy sites (VSn), and thus, every anion would introduce
two positive holes in SnS lattice and thereby the material
becomes a positive-type (p-type) conductor.15 Upon increas-
ing the temperature or pressure, the SnS undergoes a struc-
tural transition from disorder to order structure. The pressure
coefficient of energy gap (dE/dP) of SnS is observed as
¡1.3 § 0.1£10¡4eV/MPa. This value is almost twice larger
than that of the other layered-structure compounds.16 Under
NTP conditions, SnS has dual band gaps: indirect and direct.
Depending on the growth technique and stoichiometry, the
indirect band gap of SnS varies between 1.07 and 1.25 eV
and direct band gap located at slightly higher energies, varies
between 1.30 and 1.39 eV with high fundamental absorption
coefficient larger than 104 cm¡1, which is greatly higher than
that of presently existing materials like CdTe, CIS or CIGS.
Further the refractive index of SnS single crystals increases
from 3.3 to 3.7 with the increase of incident photon energy
from 0.5 to 2.0 eV.17
The electrical and optical properties of SnS material can be
tailored by doping with suitable dopants like Ag, Sb, Cl, and
N.18 It is also known that depending on the content of tin, the
SnS can change its conductivity type from p-type to n-type.
Apart from these properties, over the last few decades SnS is
attracting the world-wide scientists as low-toxicity and cost-
effective material in the field of semiconductor science and
technology hese unique properties make SnS as an appropriate
candidate for various applications including photovoltaic devi-
ces, solid-state lubricants, near-infrared detectors, lithium ion
batteries, and sensors, which will be described in later sec-
tions. In addition, SnS is also expected as an excellent holo-
graphic register system in view of its remarkable optical
properites.
3. CRYSTAL STRUCTURE OF SnS
In 1935, Hoffman invented the crystal structure of SnS as
orthorhombic and assigned a D 0.398, b D 0.433, and c D
1.118 nm as lattice parameters of unit cell.12 In virtual view,
structure of SnS is slightly disordered NaCl-type structure
since the highly electronegative S atoms draw electron pair
 4 N. KOTEESWARA REDDY ET AL.

from Sn and becomes [Ne] 3s2 3p6 and [Kr] 4d10 5S2 5p0. Fur-
ther, the nonbonding 5s lone pair electrons of the Sn strongly
distort the lattice from a rock-salt structure to distorted ortho-
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rhombic layered structure. In these disorder-layered structures

each “Sn” atom is coordinated by six “S” atoms with three
short Sn–S bonds (»0.266 nm) within the layer, i.e., intralayer
and three long Sn-S bonds (at distances »0.338 nm) in the
next layer, i.e., interlayer (Figure 1). The lines connecting Sn
with intralayer S-atoms are approximately mutually perpen-
dicular and the same is true for the inter-layer S-atoms. It
implies that these layered-structures are connected along c-
axis with weak van der Waal’s forces. As a result, the layers FIG. 2. The crystal structure of (a) b-SnS and (b) a-SnS
of SnS compound can be easily cleaved perpendicular to its c- (Strong Sn-S bonds are indicated by lines). (Ó American Phys-
axis. ical Society. Reprinted with permission from American Physi-
cal Society.14 Permission to reuse must be obtained from the
3.1. Structural Transition rightsholder.)
At NTP, the SnS exhibits a stable low-symmetric phase,
i.e., a-SnS phase. Upon increasing temperature, it under-
goes λ-type phase transition to high-symmetric phase, i.e., to b-phase, two stronger bonds in a-phase changes to four
b-SnS. In crystallographic view, orthorhombic SnS changes rather weak bands in the b-phase. At the phase transition
to tetragonal one.19 The lattice parameters of the tetragonal temperature (Tc D 878 K), the axial ratio of lattice-parameter
phase are a D 0.423 and c D 1.151 nm. The low tempera- “a” and “c” decreases continuously from a/c >1 to a/c <1.22
ture phase crystallizes in germanium sulfide (GeS) type The crystal and band structures of these SnS phases are
structure (B16) with the space group Pbnm .D16 described below based on the earlier reports.14,19,23
2h /, whereas
the higher temperature phase crystallizes in thallium iodide
(TlI) type structure (B33) with the space group Cmcm .D17 2h /. 3.2. Lattice Geometry
Here, the Pbnm .D16 2h / is a subgroup of C mcm .D 17
2h / of index
The structure of low-temperature phase (<878 K) consists
2,20 i.e., Pbnm retains half of symmetry elements of Cmcm.
of slabs with two atoms width (Figure 2a). The intra-layer
The a!b transition in SnS is a second-order transition as per
Sn-S bond length perpendicular to the slabs is small
the usual classification.21 Further, upon transition of a-phase
(»0.263 nm). However, two of the interlayer Sn-S bonds are
shorter and stronger than those of intra-layer bonds and other
two bonds are much weaker. Hence, the coordination number
of Sn-S atoms is 3 (2 C 1), which results the a-phase SnS
obtaining a highly distorted octahedral crystal structure.23 The

FIG. 1. Schematic of diagram of double-layered structured FIG. 3. Dispersion of the energy bands in a-SnS. (Ó Ameri-
SnS. (Ó Cambridge University Press. Reprinted with permis- can Physical Society. Reprinted with permission from Ameri-
sion from Cambridge University Press.30 Permission to reuse can Physical Society.14 Permission to reuse must be obtained
must be obtained from the rightsholder.) from the rightsholder.)
 REVIEW ON TIN SULFIDE MATERIAL 5

4 eV and a large part of Sn 5s states occupies the bottom of

VB. The middle of VB mainly contains S 3p and Sn 5p states,
which are fairly oriented in slabs between Y-T-Z planes. It
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indicates that these energy states are probably not contributing

FIG. 4. Dispersion of the energy bands in b-SnS. (Ó Ameri-
can Physical Society. Reprinted with permission from Ameri-
can Physical Society.14 Permission to reuse must be obtained
from the rightsholder.)
crystal structures of b-phase SnS is shown in Figure 2b and it
appears like NaCl-type slabs.14. In this case, the Sn atoms are
slightly pushed out of the slabs and the interlayer Sn-S bond
lengths in the plane of the slabs are equal to 0.296 nm and the
intra-layer Sn-S bond length perpendicular to the plane of the
slabs is 0.263 nm. These structures have the coordination
number of the atoms as 4 C 1.
3.3. Band Structure
The energy bands distribution along selected directions in
the Brillouin zone (BZ) of a-SnS is shown in Figure 3.14 It
clearly reveals that the S 3s energy states are residing far from
the other energy states of the valence band (VB) with a gap of
in the bonding of Sn and S atoms along X-direction but, these
are responsible for the building of Sn-S bonds along the slabs
of Y–Z plane. In the upper part of the VB there are a large
number of Sn 5p orbitals, which strongly mixed with S 3p
orbitals. All these states contribute in the formation of strong
covalent bonds along the X-direction (perpendicular to the
slabs). On the other hand, the conduction band (CB) states
along the Z–U line have nearly the same energy. This figure
clearly represents that the CB minimum occurs at G, whereas
the maximum of the VB is not at G.24 Thus, there is an indirect
gap between the VB and CB of 1.6 eV (0.79 eV24) and a direct
gap is 1.8 eV (1.77 eV24). The nature of energy band over the
G! X line clearly indicates that at the lowest energies of the
CB the charge carrier mobility is drastically increased,
whereas, it is decreased at highest energies of the VB. These
are probably due to the presence of strong anisotropy of the
system along G! X direction.25 Along G plane, the spreading
and crossing of bands along the mostly hybridized directions
are increased.
The dispersion of the energy bands along selected direc-
tions of b¡SnS is shown in Figure 4. The lowest bands
belonging to S 3s orbitals are well separated from the other
bands with the energy gap of »3.5 eV. The S 3s bands have
nearly the same energy in large part of the BZ and are sepa-
rated at G with the separation energy of 1.6 eV. Above this,
there are two energy bands at the bottom of VB, which belong
to Sn 5s orbitals and partial contribution of S 3s orbitals. In
large part of the BZ, these bands are nearly degenerate and are
strongly separated at points X and Y. Above this, there are six

FIG. 5. (a) Valence band density of states calculated for the band structures of SnS along the symmetry lines D, S, and L, and
electron density distribution for localized states in the forbidden band on the (010) plane (Ó John Wiley & Sons, Inc. Reprinted
with permission from John Wiley & Sons, Inc.26 Permission to reuse must be obtained from the rightsholder.); (b) VSn and (c)
VS. (Ó John Wiley & Sons, Inc. Reprinted with permission from John Wiley & Sons, Inc.27 Permission to reuse must be obtained
from the rightsholder.)
 6 N. KOTEESWARA REDDY ET AL.

bands related to S 3p states hybridized strongly with Sn 5p

states, which are responsible for the formation of covalent Sn-
S bonds. Noticeably the energy band pairs in most parts of the
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BZ are degenerate in special directions. Between the VB and

the CB there is an indirect gap of 0.3 § 0.1 eV, and a direct
gap of 1.4 § 0.1 eV. Theoretically evaluated density of states
in VB of SnS (Figure 5a) reveals that SnS is probably contain-
ing six distinguishable valance bands.26 Three of them belong
to half-filled states and other three belongs to fully occupied
states. Based on the hierarchy of orbital energies, the evaluated
peaks can be assigned as: first three peaks to S (3pz), Sn-S
(hybridized 5py and 3py), Sn (5px) and other three peaks to S
(pair 3px), Sn (pair 5s), and S (pair 3s). The relative separation
between these peaks is 0.5 (S 3s - Sn 5s), 1.8 (S 3s - S 3px),
3.2 (S 3s - Sn px), 4.5 (S 3s - Sn py), and 6.5 (S 3s - S pz) eV.
In terms of electronic configuration, the SnS contains 40
valence electrons per unit cell since each unit cell consists of
four Sn and four S atoms, as shown in Figure 1 and every Sn
(5S2 5p2) atom shares four valence electrons and S (3s2 3p4) FIG. 6. Schematic representation of wet-chemical method.
atom contributes six valence electrons to the lattice. From the
Green-function analysis of SnS energy spectrum it can be
understood that the cationic vacancy (VSn) contains two local- using appropriate quantities of salts. Stoichiometric
ized levels: one is in the gap between energy spectrum polycrystalline SnS powders have been synthesized by
branches of the main crystal at E D ¡12.6 eV and the other passing hydrogen sulphide (H2S) through an acidic
one is in the fundamental forbidden band at E D C0.31 eV.27 solution of stannous chloride (SnCl2) dissolved in
Usually, the anionic vacancy (VS) creates a deeper energy aqueous solution having the pH »1 (Figure 6).13.
level in the forbidden band at E D C0.37 eV. The localized Although this is a simple and low-cost route for the
states in the fundamental forbidden band are unoccupied for synthesis of SnS crystals, the handling of sulfur precur-
either VSn or VS. This analysis also shows that the defect sor, i.e., H2S, is difficult and also toxic.
potential of VS is slightly higher and deeply localized than that B. Mechanochemical Synthesis (Ball Milling). It is one of
of VSn. However, the electron density distributions for the cat- the simplest ways to prepare crystals of various materials. In
ionic and anionic vacancies are similar (Figures 5b and 5c) this method, hardened steel-balls are kept in a container
due to stronger defect potential of VS. Therefore, the creation (Figure 7a) along with required materials and filled with
of a vacancy in the ideal crystal drastically increases or inert gas. The fine particles are produced by rotating the con-
decreases the density of states as compared to an unideal tainer around its own axis with high speed. Here, the particle
crystal.

4. EXPERIMENTAL PROCEDURE
The growth of SnS materials in single crystal, polycrystal-
line, thin films and other forms has been carried out by various
well known chemical, mechanical and physical methods. A
brief description about the synthetic methods and optimized
growth/deposition conditions of SnS single crystals and thin
films is given in the following sections.

4.1. Powders and Single Crystals

The growth of SnS crystals is mainly carried out by four
methods: wet chemical method, mechanochemical (top-
down), melt growth, and melt-mixing. Among these techni-
ques, melt growth using Bridgman technique and melt-mixing
methods are well established.
A. Wet Chemical Method. Compound semiconductor FIG. 7. Schematic representation of (a) the ball-milling appa-
materials are synthesized by wet chemical method ratus and (b) horizontal Bridgman apparatus.
 REVIEW ON TIN SULFIDE MATERIAL
size of the final product depends on the balls size. If the size
of the balls is large then the outcome of the product contains
smaller grains. Stoichiometric SnS compounds have been
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synthesized in a planetary activator by milling of homo-
geneously mixed individual elements (i.e., Sn and S) in
methanol with the weight ratio of 1:3.7. It was carried out
under argon atmosphere by maintaining thimble axes at a
rotational speed of 70 rpm with 1000 mps2 centrifugal
acceleration.28 Using the same methodology, small SnS
nanoparticles have been produced by continuous mixing of
powders with the combination of 100 steel-balls having
5 mm diameter in the duration of 60 min.
C. Bridgman Method (Melt Growth). The Bridgman tech-
nique, a well-known technique, basically consists of a
two-zone furnace (Figure 7b). Here, one zone will be
maintained at low temperatures in order to allow sufficient
overpressure of chalcogenide(s) within the sealed system.
The other zone of the furnace, contains the polycrystalline
compound materials, will be at slightly higher tempera-
tures, i.e., just above the melting point of the compound.
Upon moving the furnace to higher temperatures, initially
the source compound melts and upon going from hot to
cold side, the melt cools and solidifies. By placing a seed
crystal at the left-hand side of the melt, single crystal of
the compound can be obtained with specific orientation.
Single crystals of SnS have been prepared by vapor con-
densation method. Pure and stoichiometric SnS compound
was taken in a silica boat and kept in evacuated quartz
container at a temperature of 400
C. Then, it was moved
through a high temperature zone of 900
C with slow-rate
of movement (»1 cm h¡1).29
D. High Temperature Melt-Mixing. It consists of a high
temperature furnace (»1200
C) and two ceramic tubes,
as shown in Figure 8. The inner tube is connected to a syn-
chronous DC (direct current) motor and placed horizon-
tally on two supporting legs. The furnace is connected to
high power source through a temperature controller. The
required homogeneous compound can be obtained at
higher temperatures by keeping the vacuum sealed quartz
ampoule charged with appropriate materials at the center
of the inner tube under regular and continuous rotation.
The temperature of the furnace has to be increased at slow
FIG. 8. Schematic diagram of high temperature melt-mixing
method.
7
rates up to higher temperatures slightly above the melting
point of the expecting compound. SnS compounds have
been synthesized by high-temperature melt-mixing
method under the laboratory conditions using high pure
“Sn” and “S”.30 Appropriate amounts of Sn and S were
weighed (»2 g) and transferred into a cleaned quartz
ampoule (70 mm in length and 9 mm diameter). Ampoule
was flame sealed under a high vacuum of 10¡5 Torr and
loaded into a home-built horizontal rotary furnace. It was
heated slowly up to 950
C in steps of 100
C per h and
kept at 950
C for two days under constant and continuous
horizontal rotation. Finally, it was allowed to cool slowly
to RT in the span of 24 h and the SnS compound was
recovered by breaking the ampoule.
4.2. Thin Films
SnS thin films have been prepared by using various chemi-
cal and physical methods. In general, the deposition of thin
films in chemical methods mainly depends on chemical reac-
tion, whereas in physical methods, the deposition takes place
through evaporation or ejection of materials from source. In
this section we briefly describe the growth/deposition methods
adopted for the preparation of SnS films and also highlight the
optimal growth/deposition conditions for the development of
stoichiometric SnS films.
4.2.1. Chemical Methods
This section deals with various wet-chemical methods
used for the growth of SnS thin films. It is well known that
the chemical methods are quite simple and economical.
They require less instrumentation and low-temperature.
Major assets of these methods are possible in-situ doping
and excellent control over the deposition conditions.
Depending on the nature of chemical reaction and process,
the deposition methods are categorized as thermal deposi-
tion and electro deposition. Although these methods are
simple and economic it is very difficult to achieve device
grade films and also, the control over chemical composition
of the deposited films is very poor.
A. Chemical Precipitation or Bath Deposition. It is a sim-
ple method used for the deposition of thin films of various
materials and their compounds. SnS films have been pre-
pared on conducting and non-conducting substrates from a
bath solution containing 0.1–1.0 M tin chloride (SnCl2)
and sulfur dissolved in deionized water (DIW) and pro-
pionic acid (PA), respectively, at a bath temperature
»100
C.31 Here, initiation of nucleation on the surface of
solids through ion-by-ion condensation leads to formation
of compact and adherent film. Smooth, adherent and thick
(»1 mm) films have been obtained within a short time of
30 min. By adding potassium gluconate (PG) or tartaric
acid (TC) the growth rate of SnS films have been con-
trolled well since they serve as Sn2C complexing agents.
 8 N. KOTEESWARA REDDY ET AL.

This process works well with the powder source of Sn, and
very smooth films can be obtained by using anhydrous
sources.
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SnS films with a maximum thickness of »0.12 mm

have been prepared at RT using chemical precipitation
method.32 The films deposited on glass substrates from the
bath solution consists of 5 ml (0.1 M) thioacetamide, 5 ml
(0.1 M) Sn-precursor prepared by dissolving SnCl2 in gla-
cial acetic acid, 15 ml of (7.4 M) tri-ethanolamine (TEA)
and 8 ml of (14 M) ammonia. The growth rate of SnS
films has been accelerated by maintaining the bath temper-
atures at around 75
.33 Further, SnS films have been
deposited on glass substrates at the bath temperature of
30
C by using a mixed solution, which contains 30 ml of
0.15 M SnCl2 2H2O, 30 ml of 0.7 M NH4F, 5 ml of 2 M
Na2S2O3 5H2O, and 6 ml of 0.25% NH4OH in a reaction
time of 24 h.34
B. Immersion or Dipping. This is another simple and eco-
nomic technique35 applied for the growth of various
thin films. A major process involved in this technique is
sequential dipping of substrates in cold and hot solu-
tions in regular intervals. SnS thin films have been pre-
pared by immersion or dipping of substrate(s) in a cold
solution of 25 mM sodium sulfide or ammonium sulfide
[Na2 S or ðNH4 Þ2 S] and then in a hot (80–90
C) 25 mM
solution of SnCl2. In this method, upon immersion of
substrate in the hot solution a chemical reaction takes
place on its surface and final precipitation form as a SnS
thin film. The films adhesion to the substrate is very poor
and can be rubbed easily when the pH of the solution is
less than 3. By maintaining pH of the solution between 3
and 7 we can obtain adhesive and uniform SnS films
even on glass substrates. Further increase of pH upto 12,
except 7, enhances the growth rate and crystalline quality
of the SnS films.
Alternatively, SnS films have also been obtained by
dipping the substrates in a mixed solution prepared
with stannous chloride dihydrate (2.22 M) and thiourea
(1.31 M) [SnCl2 2H2O and SC(NH2)2] at the pH of 3,
followed by backing at 300
C in a furnace for the
duration of 5 min.36 In this technique, the thickness of
the films can be easily controlled by varying the num-
ber of dips. Further, the SnS films have been obtained
even at RT by successive ionic layer adsorption and
reaction (SILAR) method. In this approach the sub-
strates has been immersed in 0.1 M SnSO4 solution
dissolved in dilute H2SO4 (pH D 1.8) for 25 s and 10 s
in 0.1 M Na2S (pH D 12.5) solution followed by rins-
ing with deionized water at each steps for 15 s.37
4.2.2. Electrochemical Deposition (ECD)
Electrochemical deposition is a method used for the depo-
sition of metals as well as compound materials. In this
FIG. 9. Schematic diagram of three-electrode electrochemical
cell.
technique the deposition of substance occurs only upon pass-
ing the electric current through the conducting medium even
at low temperatures. In general, the deposition is carried out
in an electrochemical cell (ECC). ECC usually have three
electrodes namely working electrode (WE), where the depo-
sition takes place, counter electrode (CE) electrode for clos-
ing the circuit and reference electrode (RE), for referring the
voltage between electrolyte and WE. A schematic diagram is
shown in Figure 9. Based on nature of process the ECD
method can be broadly categorized into two types: anodic
ECD (AECD) and cathodic CED (CECD). Apart from these
methods, brush plating method also belongs to ECD method-
ology. All of these methods are simple, low-temperature,
scalable, and low-cost techniques. Also, these methods have
good control over the deposition rates as well as chemical
composition of the compound material since the deposition
occurs under electrically driven reactions. However, as com-
pared to CECD method, AECD method has major drawback
as its self-limiting growth rate makes it difficult to achieve
thicker films.
A. Cathodic Electrochemical Deposition (CECD) (Poten-
tiostatic). Stoichiometric SnS thin films have been
obtained at RT using the CECD method from the 0.01 M
aqueous solution consisting of tin chloride (SnCl2) and thi-
osulphate (Na2S2O3 (TS)) at the pH of 1.5.38 The deposi-
tion has been carried out onto titanium or ITO-coated
glass substrates by applying ¡0.7 V constant potential
with respect to RE. Further, the SnS thin films have also
been obtained by just replacing SnCl2 with 7 mM stan-
nous sulfate (SnSO4) solution at a potential of ¡1V.39 The
thickness of SnS films has been controlled by varying
either Sn2C concentration or WE potential. By adding eth-
ylene-diamine-tetra-acetic acid (EDTA) to the aqueous
solution of SnCl2 and thiosulphate, excellent improvement
 REVIEW ON TIN SULFIDE MATERIAL
in the adhesion of films with substrate has been achieved
along with the improvements in their thickness, uniformity
and photoactivity.10 Here, EDTA additive play a great role
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as a chelating agent and minimizes the direct reaction of
Sn2C and S, and thereby improves the longevity of the
deposition.
B. Constant-Current ECD (CCECD) (Galvanostatic).
Implementation point view, it is a simpler technique than
the potentiostatic modes since CCECD method does not
require any reference electrode and also the thickness of
the deposited films is simply related to the deposition cur-
rent density. This technique works only with two electro-
des: WE and CE under a constant current. Stoichiometric
SnS thin films were obtained on ITO substrates by
CCECD method using the a bath solution consisting of
20 mM of SnSO4 and 100 mM of Na2S2O3 at pH of 2.7
and Sn2C/S2 O23 ¡ ratio of 0.2 under a current density of
3.0 mA cm¡2 with a reaction time of 1.5 h.40
C. Pulsed Electrochemical Deposition (PECD). Pulsed
ECD is a unique technique, which effectively improves
the morphology as well as optical properties of as-depos-
ited films.41 By applying potential with shorter pulses in
shorter intervals as: “On” potential at ¡1V for 1 s and
“Off” potential at 0 V for 1 s to WE nearly stoichiometric
SnS films have been obtained even at RT.
D. Brush Plating Method. Brush plating is a cold electro-
lytic method usually applied to deposit a thin layer of
material(s) on a conductive surface without dipping the
object in a bath of electrolyte. This method provides good
adhesion and is used in the manufacturing industry for var-
ious applications. This is a simplest, cost-effective, and
scalable method. The brush plating equipment includes
power packs, solution(s), plating tools, anode covers, and
auxiliary equipments. The schematic diagram of brush
plating system is shown in Figure 11b. The axial brush is
typically a stainless steel or conducting rod, wrapped with
a cloth material. The brush has to be connected to a posi-
tive terminal of DC voltage and the negative terminal is
connected to substrate. The wrapped cloth holds the plat-
ing solution and also prevents direct contact with sub-
strate. Initially, the brush has to dip in the plating solution
and then by moving the brush continuously on the
FIG. 10. Schematic diagram of (a) PECVD system and (b) APCVD system.
9
substrate with a slow rate of movement the desired film
can be obtained. SnS films were deposited by brush plat-
ting method42 using the mixture solution 5 mM SnCl2 and
2.5 mM Na2S2O3 at the pH of 1.5 by applying constant
current density of 80 mA cm¡1 for 5 min.
4.2.3. Chemical Vapor Deposition (CVD)
Chemical vapor deposition (CVD) is a versatile technique
used for the deposition of thin films as well as nanostructures.
It has relatively simple instrumentation, ease of processing,
possibility of depositing different type of materials and eco-
nomic viability. It is also widely used in the semiconductor
industry. A simple CVD system consists of a reaction cum
growth chamber with temperature controller, precursors cum
carrier gas regulators, and vacuum pump. In a typical CVD
process, one or more volatile precursors purged into the CVD
chamber through regulators react and/or decompose on the
surface of the substrate kept at higher temperatures and form
desired compound as film or nanostructure. The volatile
byproducts produced in these processes are exhausted with the
combination of carrier gas through the vacuum pump. The
flow rate, gas composition cum concentration, growth temper-
ature, partial pressure in the reaction chamber, and chamber
geometry are the typical processing variables for the growth of
desired structures. Depending on the growth environment, the
CVD techniques are broadly classified as metalloorganic CVD
(MOCVD), atomic layer epitaxy (ALE), vapor phase epitaxy
(VPE), plasma enhanced CVD (PECVD), atmospheric pres-
sure CVD (APCVD), rapid thermal CVD (RTCVD), and low
pressure CVD (LPCVD) techniques.
A. Plasma-Enhanced Chemical Vapor Deposition
(PECVD). In recent years there has been an increasing
interest in PECVD technology to meet the demand for
novel and better materials in science and technology. In
this technique, the plasma produced by radio-frequency
(RF), direct-current (DC), or microwave field plays a
major role as a reaction initiator by promoting the chemi-
cal reaction through ionization and dissociation of precur-
sors, and leads the formation of a variety of thin film
materials on temperature sensitive substrates. Since the
plasma produces energetic ions/particles, there is usually
 10 N. KOTEESWARA REDDY ET AL.
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FIG. 11. Schematic diagram of (a) the CSVT system and (b) brush plating system.
good adhesion of the film to the substrate. The schematic
diagram of PECVD setup used for the preparation of SnS
thin films is presented in Figure 10a. Good quality SnS
films have been achieved by PECVD technique at the sub-
strate temperatures higher than 200
C using H2S (2 sccm,
standard cubic centimeter per min) and SnCl4 (2 sccm)
gases as sources of Sn and S and hydrogen gas (15 sccm)
as carrier gas.43 The other deposition conditions including
deposition pressure, total glass flow rate, 13.56 MHz RF-
plasma power density, and inter-electrode distance are
kept as constant at 150 mTorr, »20 sccm, 0.023 Wcm¡2
and 3 cm, respectively. The thickness of the SnS films has
been well controlled by varying RF-power and/or growth
temperature.
B. Atmospheric Pressure CVD (APCVD). APCVD works
at normal pressures and is mainly used in the glass produc-
tion at large scales. The advantage of APCVD is that the
films can be deposited in shorter times. In this technique,
the precursors of materials combine and react at atmo-
spheric pressure and deposit on the substrates kept at high
temperature. Further, it undergoes nucleation followed by
coalition and finally forms thin film of the desired mate-
rial. The growth rate of the films is quite high at about
»2 mm min¡1. A simple APCVD system used for the
development of SnS films is schematically presented in
Figure 10b. Good quality SnS films were obtained using
APCVD technique by purging of SnCl4 (1.5 lmin¡1) and
H2S (0.3 l min¡1) gases mixed with high-pure nitrogen
gas onto heated substrates at »550 § 5
C.44 Alternatively,
the SnS films have also been obtained with the help of tri-
n-butyl-tin trifluoroacetate .Bun3 SnO2 CCF3 / organic pre-
cursor along with H2S gas at slightly low-growth tempera-
tures, »450
C.45 The flow rates of the precursors and
nitrogen carrier gas are maintained at 0.4, 0.6 and
11.6 sccm, respectively. Thick films (»750 nm) were
obtained within the time of 15 min.
Further, Hibbert et al.46 developed a novel and volatile
precursor of (fluoroalkythiolatin) tin (IV) (CF3CH2S)4Sn
for the deposition of tin sulfide thin films. By using this
precursor (boiling point is around »35
C), nearly stoichio-
metric SnS films (Sn:SD1:0.96) have been achieved in
APCVD technique at the substrate temperatures varied
between 525 and 600
C. Similarly, two asymmetric tin
dithiocarbamate precursors namely SnMe3(S2CNMeBu)
and SnBu(S2CNMeBu)3 have been developed by Kana
et al.47 and also applied successfully for the growth of SnS
films in APCVD. Parkin et al.48 also developed a single
source precursor of Sn(SCH2CH2S)2 and obtained single-
phase SnS films using aerosol-assisted CVD (AACVD)
technique at the growth temperatures above 500
C in
absence of H2S. By following the same approach, Bade
et al.49 obtained stoichiometric SnS films at the growth
temperature of 475
C using a new single volatile precur-
sor, tribenzyltin(IV)chloride thiosemicarbazones.
4.2.4. Close-Space Vapor Transport (CSVT)
The close-space vapor transport (CSVT) method is similar
to thermal evaporation method. However, it consists of a verti-
cal reactor made with a quartz tube (Figure 11a) with the
diameter of 2 cm and length of 10–20 cm. As shown in the
figure, the source material and substrate are separated with
quartz spacers of thickness 0.3—a few mm. A solid iodine
slab is placed at the upper part of the reactor and sealed under
vacuum. Finally, the complete system is placed on a SiC heat-
ing element that is operated by a voltage regulator. The ther-
mal gradient between the source and substrate can be adjusted
by using a movable heating-coil, which also allows for pre-
heating of the substrate. SnS films have been deposited using
CSVT technique50 onto glass substrates at a substrate tempera-
ture of 500
C by evaporating pure SnS compound for duration
of 10 min.
4.2.5. Atomic Layer Deposition (ALD)
ALD is a unique technique used for the deposition of vari-
ous thin films and nanostructures by a sequential spraying of
 REVIEW ON TIN SULFIDE MATERIAL 11

precursor materials. Basically, the sprayed precursors react

with the surface of the substrate one at a time in sequential
steps and form continuous thin films. Due to its self-limiting
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and sequential feeding of precursors, the depositions are con-

formal and can also be controlled at atomic scales. Using ALD
method the films can be finely controlled for thickness and
deposited in a large area with excellent reproducibility. Also,
lower deposition temperatures can be used in order to deposit
the films on temperature sensitive substrates. A simple ALD
system consists of three major parts such as control unit of pre-
cursors, deposition chamber and vacuum pump, as shown in
Figure 12a. Stoichiometric SnS films have been deposited on
glass, sapphire and Si substrates by ALD technique through
the sequential purging of 2,4-pentanedionate (Sn-precursor),
nitrogen (carrier gas) and hydrogen sulfide (S-precursor) with
the combination of nitrogen in the intervals of 1-30-1-30 s.
The depositions have been carried out at the chamber base
pressure of 1 Torr and temperature of 175
C.51 Here the nitro-
gen gas flow rate was maintained at 100 sccm and the partial
pressures of Sn- and S- precursors were maintained at 10 and
150 mTorr.

4.2.6. Spray Pyrolysis

The spray pyrolysis technique involves the spraying the
solution, which contains the solvable salts of the constituent
elements of the desired compound, onto a heated substrate.
The sprayed droplet upon reaching the surface of hot-substrate
undergoes pyrolytic decomposition and forms a single crystal-
lite or a cluster of crystallites of the product. The volatile
byproducts and the excess solvents escape in the vapor phase.
Here, the heated substrate provides the thermal energy neces-
sary for the decomposition and subsequent recombination of
the constituent species. This is followed by sintering and re-
crystallization of the clusters of crystallites giving rise to con-
tinuous film. A simple spray system (Figure 12b) consists of a
spray head connected to two channels and substrate heater
cum controller. The purified compressed air/nitrogen and solu-
tion are fed to the spray nozzle from opposite sides and are
then sprayed onto hot-substrates kept at below the spray noz-
zle. The substrate temperature is controlled using a tempera-
ture controller.
SnS films have been obtained using spray pyrolysis tech-
nique by spraying the equimolar solution prepared SnCl2 and
n, n-dimethyl-thiourea ((CH3NH)2CS) in a mixture DIW and
isopropyl alcohol (1:3) with a concentration of 0.1 M.52 Single
crystalline and stoichiometric SnS films have been obtained by
depositing them at a substrate temperature of »380 § 10
C by
keeping other deposition conditions including solution flow
rate (»10 cm3 min¡1), gas flow rates (»10 l min¡1), nozzle to
substrate distance (30 cm), and spraying time (10 min) as con-
stant. Further, Reddy et al. synthesized SnS films by using the
same technique and optimized the deposition conditions
including substrate temperature (300–375
C) and solution
FIG. 12. Schematic diagram of (a) the ALD system and (b)
spray pyrolysis system.
concentration (0.09–0.13 M) for the growth of single crystal-
line and stoichiometric device grade films.53,54 Recently, this
method has been also applied by Sajeesh et al.55 for the
growth of SnS thin films and optimized the growth tempera-
ture for single phase films as 375 § 25
C with the precursor
equimolar concentration of 0.15 M.
4.2.7. Physical Deposition
The deposition of thin films in the physical deposition
methods occurs mainly through evaporation or ejection of
material from the source and thereby condensation onto the
substrates under high vacuum. The films deposited using
these techniques are qualitatively better than those from
chemical methods due to the presence of high-vacuum.
Based on the method applied for material evaporation, there
are a variety of physical vapor deposition techniques. Resis-
tive heating, flash evaporation, electron beam heating, laser
heating, arc evaporation, sputtering, etc. have been devel-
oped and applied for the deposition of various materials.
The methods, which were used for the deposition of SnS
films, are briefly described below.
4.2.7.1. Thermal Evaporation. Thermal evaporation tech-
niques (resistive-, electron beam-, and flash- evaporation are
 12 N. KOTEESWARA REDDY ET AL.

the simplest techniques as compared to all other physical Alternatively, single-phase SnS films have been achieved
vapor deposition (PVD) techniques. This technique basically by co-deposition method at the substrate temperature of
involves on the transformation of source material into vapor, 300
C with a rate of 2 nm s¡1 under a pressure of 10¡5
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transport of this vapor onto the substrate surface and finally Torr.57 The depositions have been done through the evap-
condensation of the vapor on the substrate to form the thin oration of high pure Sn and S from two different boats.
film. Here, the source-to-substrate distance has been maintained
as 15 cm and substrates were placed exactly at center and
A. Resistive Evaporation, A schematic diagram of simple
normal to both the sources as shown in Figure 14a. Fur-
vacuum coating system used for the deposition of SnS
ther, Devika et al.58 developed polycrystalline SnS thin
films is shown in Figure 13. It consists of a stainless-steel/
films on glass substrates by resistive evaporation of high-
glass bell jar mounted on the top flange of the unit. A three
pure SnS compound with the substrate temperatures varied
stage diffusion pump backed by a two stage rotary pump is
between 275–325
C under the vacuum of 10¡6 Torr. Here,
used to create a vacuum of the order of 10¡5 Torr. Here, a
the other deposition conditions such as the source to sub-
liquid nitrogen trap connected between the chamber and
strate distance, film thickness, and the rate of deposition
diffusion pump to avoid the back streaming of oil into the
were maintained constant as 14 cm, 0.5 mm, and 1 nm
chamber. Further, two Pirani gauges and one Penning
s¡1, respectively.
gauge are used to measure the fore-vacuum and high-vac-
B. Electron-Beam (e-Beam) Evaporation, The deposition
uums, respectively, and a radiant heater generally used to
process in e-beam evaporation is similar to resistive
heat the substrates. The thickness of the film is monitored
evaporation except nature of source. Here, the evapora-
using a quartz crystal thickness monitor. High quality stoi-
tion of the material(s) is achieved by high-intensity
chiometric SnS films have been obtained by resistive
e-beam source instead of thermal heating. In e-beam
evaporation of high-pure SnS powder (»4N) onto glass,
evaporation, an electron beam is aimed at the source
ITO, and Al-substrates at the substrate temperature of
material causing local heating and evaporation. A sche-
»300 § 50
C under a vacuum of 10¡6 Torr.56
matic diagram of e-beam evaporation is shown in
Figure 14b. High quality stoichiometric SnS films have
been obtained using e-beam evaporation of SnS powder
on to glass substrates at the substrates temperature of
300
C under a vacuum of 10¡6 Torr.59 Here, the dis-
tance between source and substrate is about 24 cm and
the rate of deposition is maintained at 3 nm s¡1.

4.2.7.2. Molecular Beam Epitaxy (MBE). Epitaxy or epi-

taxial growth is a method applied for the deposition of thin
layers of single crystalline material(s) over the lattice-
matched substrates through molecular vapor deposition. If

FIG. 13. Schematic diagram of thermal evaporation FIG. 14. Schematic diagram of (a) the co-evaporation appara-
system. tus and (b) e-beam evaporation apparatus.
 REVIEW ON TIN SULFIDE MATERIAL
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FIG. 15. Schematic diagram of (a) the molecular beam epi-
taxy apparatus and (b) rf-sputtering apparatus.
the substrate is made with the same material of deposition
then the process can be treated as homo-epitaxy, or simply,
epitaxy. However, when the deposited film is different
material from substrate, it is called as hetero-epitaxy. MBE
is an ultra-high-vacuum (UHV)-based system used to pro-
duce high-quality epitaxial films of variety of materials
including metals, insulators, and superconductors. In prin-
ciple, the MBE consists of atoms or clusters of atoms pro-
duced by heating up a solid source of material
(Figure 15a). They then travel in an UHV environment and
deposit on a hot substrate surface and form a film. Major
control over the vacuum environment as well as on the
quality of the source materials allows the development of
high quality crystalline films compared to other non-UHV
techniques. Epitaxial grown SnS films have been obtained
by MBE technique on slightly lattice matched magnesium
oxide substrates at substrate temperatures varied from 100–
335
C with a thickness of 135 nm.60
4.2.7.3. Sputtering. Sputtering is a technique belonging
to physical deposition methods. It usually consists of a deposi-
tion chamber, radio-frequency (RF)-source and vacuum pump.
13
The substrates placed in a vacuum chamber and the source
material, i.e. target, placed above the substrates as shown in
Figure 15b. Inert gas, generally argon, is introduced at lower
pressures. Plasma is created using an RF power source, and so
the gas becomes ionized. The ionized-ions are accelerated
toward the surface of the target and release atoms from target
due to their bombardment. The released atoms condense on
the surface of the substrates. Highly crystalline and amorphous
SnS films have been obtained on glass substrates by RF-sput-
tering (RF, 13.65 MHz) method at substrate temperature of
300 § 50
C, under the argon gas pressure of 5 £ 10¡2 Torr.61
Here, the other deposition parameters such as RF power, anode
voltage, cathode voltage, and target to substrate distance have
been maintained at 45 W, 1 kV, 40 mA and 8 cm, respec-
tively. Further, Hartman et al. successfully deposited SnS
films by RF-sputtering on glass substrates by keeping them at
16.5 cm away from target using sulfur-rich SnS target.62 The
depositions were carried under argon plasma (»150 W) with
the base pressure of 10¡7 Torr by varying argon pressure from
5–60 mTorr.
4.2.7.4. Sulfurization. The sulfurization setup (Figure 16)
basically consists of a two-zone furnace, quartz tube (length-
»1 m and diameter » 0.1 m) and a vacuum pump. One end of
the tube is connected to a vacuum system and the other end is
connected to a gas-line, i.e., carrier gas. In general, the high
vapor pressured sulfur is placed at the low temperature zone
and the sample which has to be sulfurized is placed at the
higher temperature zone in the flow-direction of carrier gas.
Single-phase SnS films have been obtained through the sulfuri-
zation of sputtered tin metallic layers on glass substrates at
temperatures varied between 300 and 350
C under a vacuum
of 10¡2 Torr for 20 min.63 Minemura et al.64 developed SnS
thin films by sulfurization of Sn-sheet in two-zone vertical fur-
nace in a reaction time of 76–103 h. Here, the sulfur source
and Sn-sheet were kept at 275
C and 200
C, respectively.
Alternatively, the SnS films were obtained through the sulfuri-
zation of Sn-films on glass as well as Mo-coated glass sub-
strates with the thickness of 600 nm in a vacuum chamber at
200
C for 60 min.
4.2.7.5. Hot-Wall Deposition. Hot-wall deposition
method is frequently used for the deposition of single crystals
and thin films of various materials. It mainly consists of three
parts: a quartz-tube (hot-wall system), a vacuum chamber, and
a vacuum pump. One side enclosed hot-wall tube directs the
vapor from the source to the substrate placed at the open end
of the tube (Figure 17). The quartz-tube is heated by Kanthal
wire wounded closely along its length. The evaporated mole-
cules from the source, placed at the bottom of the tube, deposit
on the substrate by migration through the column of tube. The
whole arrangement is placed in a vacuum chamber and gener-
ally the deposition are carried out at pressures >10¡5 Torr.
SnS films were developed by hot-wall deposition on glass
 14 N. KOTEESWARA REDDY ET AL.
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FIG. 16. Schematic diagram of two-zone sulfurization
apparatus.
substrates kept at 10 cm away from open-end of the tube.65
The wall-temperature was kept at 550
C and the films were
deposited at different growth temperatures varied between 210
and 300
C under a pressure of 10¡6 Torr.
5. RESULTS AND DISCUSSION
The physical properties like crystal structure, chemical
composition, morphology, electrical, and optical properties of
SnS grown in single crystals and thin films are reviewed in the
following sections and discussed.
5.1. Physical Properties of Single Crystals
The Bridgeman technique has been frequently used for the
synthesis of SnS single crystals. The as-synthesized SnS crys-
tals appear like shiny flakes, which can be easily cleaved in a
direction perpendicular to the c- axis similar to tin mono sele-
nides.66 Thin platelets upto the thinness of 1 mm can be
obtained by adhesive tape pulling technique. The SnS crystals
obtained from a high-temperature melt-mixing method have
an excellent chemical stoichiometry with the Sn/S atomic
FIG. 17. Schematic diagram of hot-wall deposition setup.
FIG. 18. FESEM image of SnS compound synthesized by
high-temperature melt-mixing method. (Ó Cambridge Univer-
sity Press. Reprinted with permission from Cambridge Univer-
sity Press.30 Permission to reuse must be obtained from the
rightsholder.)
percent ratio of »1 and uniformly appended slices like surface
morphology (Figure 18).30 These SnS crystals are preferen-
tially oriented along the [010] direction and have orthorhom-
bic structure.
5.1.1. Structural Properties
Single crystals of SnS compound exhibit a phase transition
from a-phase to b-phase at a critical temperature (Tc) of
878 K22 due to the displacements of Sn and S atoms along the
[100] direction (Figure 19). The displacement of Sn and S
atoms positional parameters occurs from the distorted values
of orthorhombic phase to those of ordered values of the high
temperature b-phase. While increasing temperature, the lattice
parameters “a” and “c” vary continuously and approach each
other at Tc, whereas “b” increases continuously, as shown in
Figure 20. At around Tc, the axial ratio (a/c) also abruptly
changes from a/c>1 to a/c <1. On the other hand, while
decreasing temperature from 600 to 100 K, the crystal struc-
ture of SnS crystals remains stable as orthorhombic.30 The
FWHM (full width at half maximum) value of (040) peak
increases with the decrease of temperature (Figure 21) and,
however, the overall changes in FWHM value is found to be
0.029
. As compared to GaAs,67, the impact of temperature
fluctuations on SnS material is low since the volume expan-
sion coefficient of the SnS is 3 £ 10¡6 K¡1 whereas for GaAs
it is about 6 £ 10¡6 K¡1.67
The lattice parameters of orthorhombic (a-phase) as well
as tetragonal (b-phase) SnS crystals are slightly temperature
dependent.19 Both the phases exhibit different thermal
 REVIEW ON TIN SULFIDE MATERIAL 15

expansion coefficients along their crystallographic axes. The

thermal expansion coefficients of orthorhombic phase along
three principal crystallographic axes are d[100] D ¡89.1£10¡6,
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d[010] D 80.1£10¡6 and d[001] D 35.6£10¡6 K¡1 and for tetra-

gonal phase, d[100] D ¡26£10¡6 and d[001] D 51.8£10¡6 K¡1.
Therefore, the expansion or compression in both the phases is
clearly anisotropic.68 On the other hand, while increasing sur-
rounding pressure of SnS, orthorhombic (a-SnS) under goes a
phase transition to monoclinic (g-SnS) at around the pressure
of 17.5 § 1 GPa.24 The linear compressibility of this layered
compound along its crystallographic axes is 0.008, 0.0122,
and 0.0036 GPa¡1, which is attributed to decrease of S–S gap
and thereby increase of repulsive forces. Noticeably, the linear
compressibility parallel to the staking direction of the layers is
1.5 times higher than along “a” direction and 3.4 times higher
than parallel to the “b” direction.68
SnS crystals exhibit excellent structural stability upon dop-
ing of rare-earth (RE) elements. Such stability in the crystal- FIG. 20. Variation of the lattice constants of SnS compound
line structure of SnS has been observed by Nasirov et al. for with temperature. (Ó Elsevier. Reprinted with permission
the first time.19 RE elements (like Nd, Sm, and Gd) doped SnS from Elsevier.22 Permission to reuse must be obtained from
crystals exhibit temperature independent structural properties. the rightsholder.)
For examples, the RE elements doped SnS crystals with differ-
ent concentrations varied between 0.001 and 0.002 wt.%
showed an excellent crystalline stability upto the elevated tem- from Nd, Sm, and Gd doped SnS crystals for two typical con-
peratures of »600
C19 and the observed lattice parameters centrations are given in Table 1.

5.1.2. Electrical Properties

Usually SnS single crystals exhibit p-type conductivity.
At RT, the conductivity of these crystals is of the order of
10¡1–10¡4 V¡1 cm¡1.69,70 These SnS crystals show a
hole-concentration of the order of 1017 cm¡3 at RT and it

FIG. 19. Variation of the positional parameters (x and y) of Sn FIG. 21. Variation of FWHM of SnS compound as a function
and S atoms of SnS as a function of temperature. (Ó Elsevier. of temperature. (Ó Cambridge University Press. Reprinted
Reprinted with permission from Elsevier.22 Permission to with permission from Cambridge University Press.30 Permis-
reuse must be obtained from the rightsholder.) sion to reuse must be obtained from the rightsholder.)
 16 N. KOTEESWARA REDDY ET AL.

TABLE 1 RT, the mobility of holes along the c-axis is approximately

Lattice parameters of orthorhombic (SnS)1-x(LnS)x crystals six times smaller than the mobility perpendicular to the c-
(Ó Springer Science and Business Media. Reproduced with axis,29,72 which is probably attributed to the differences in
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permission from Springer Science and Business Media.19 Per- lattice constants of orthorhombic SnS.73 Besides this, the car-
mission to reuse must be obtained from the rightsholder) rier density of p-type SnS crystals is increased upto 1019
cm¡3 by doping of silver (Ag) and the conductivity of SnS
Ln x a (nm) b (nm) c (nm) changed from p-type to n-type by doping of antimony (Sb).72
Nd 0.001 0.3978 0.4322 1.1193 The Sb doped SnS crystals show low carrier concentration of
0.002 0.3978 0.4339 1.1193 the order of 10¡14 cm¡3.
Sm 0.001 0.3962 0.4527 1.1176 Upon increasing temperature from 140 and 523 K, the
0.002 0.3978 0.4323 1.1193 p-type SnS single crystals exhibit two distinguishable con-
Cd 0.001 0.3984 0.4326 1.1189 duction regions namely extrinsic and intrinsic regions
0.002 0.3969 0.4328 1.1247 (Figure 23).70 These regions are well separated by a broad
region treated as transition region, which occurs in between
60 and 140
C. The variation of electrical conductivity in
the extrinsic region is strongly attributed to the concentra-
is quite temperature independent between 100 and 500 K. tion of ionized acceptors, whereas in the intrinsic region
The Hall-mobility .mH / of holes perpendicular to c-axis of the conductivity is strongly related to the excitation of car-
SnS crystal, increases with increasing temperature from 100– riers from VB to CB. Upon treating the SnS crystals with
175 K (i.e., mH 1T3/2) as shown in Figure 22,29 which is hydrogen at relatively low temperatures (»200
C), their
probably attributed to the ionic impurity scattering. Above conductivity greatly decreases from 10¡4 to 10¡8 V¡1
this temperature (>175 K), the hole-mobility is proportional cm¡1.69 This abrupt decrease in the conductivity of SnS
to T¡5/2, which indicates that at higher temperatures the lat- crystals is due to the drop in excess of sulfur atoms with
tice scattering of carriers dominate the hole-mobility.71 At hydrogen treatment that results in a decrease in the positive
holes concentration and thereby its conductivity gradually
reduces to lower values.

5.1.3. Optical Properties

The optical properties of SnS crystals have been studied by
using various techniques. Before 1970s, the scientists identi-
fied SnS as an indirect band gap material. However, in 1977
Chamberlain et al. observed a direct band gap in SnS crystals

FIG. 22. Hole mobility (mp) perpendicular to the c-axis as FIG. 23. Temperature dependence of the electrical conductiv-
a function of temperature for three different SnS crystals. ity of SnS compound. (Ó Elsevier. Reprinted with permission
(Ó Elsevier. Reprinted with permission from Elsevier.29 from Elsevier.70 Permission to reuse must be obtained from
Permission to reuse must be obtained from the rightsholder.) the rightsholder.)
 REVIEW ON TIN SULFIDE MATERIAL
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FIG. 24. Photoconductivity curves for SnS in the spectral
region below the band edge. (Ó IOP. Reproduced with permis-
sion from IOP.19 Permission to reuse must be obtained from
the rightsholder.)
along with indirect gap.74 As a continuation of this, Lukes
et al. noticed a strong direct interband transition in SnS crys-
tals while studying their electroreflectance measurements.75
Further, Valiukonis et al. also suggested the optical transition
in SnS compound as a direct allowed transition.16
Temperature-dependent infrared photoconductivity meas-
urements on SnS crystals reveal that while decreasing temper-
ature from RT to 35 K the indirect band gap (Eg) of
the crystals increases from 1.13 § 0.02 to 1.22 § 0.02 eV,
whereas their direct band gap remains stable at »1.43§
0.02 eV.74 Below its indirect band, it exhibits three distin-
guishable peaks at 0.55 (E1), 0.66 (E2) and 0.83 (E3) eV (Fig-
ure 24). The peak E1 originates from the transition of carriers
between the doubly-ionized acceptors to the CB, and E2 origi-
nates from transitions between the VB and the acceptor states.
The temperature dependence of SnS indirect optical band gap
can be expressed by a linear equation:76
Eg D 1:21 ¡ 4:8 £ T £ 10. ¡ 4/ .eV ; T in K/;
and their refractive index “n” can also be formulized by the
following equations:77
na ðEÞ D 3:523 C 0:692E2 {Eka
nb ðEÞ D 3:523 C 0:467E2 {Ekb
Under polarized light (E), SnS exhibits a direct transition at
1.3 § 0.02 eV when Ejja. However, these crystals exhibit a
17
FIG. 25. Electroreflectance spectrum of SnS single crystal for
the Ejja and Ejjb polarizations. (Ó Elsevier. Reprinted with
permission from Elsevier.75 Permission to reuse must be
obtained from the rightsholder.)
strong direct transition at around 1.59 eV when Ejjb along
with a weak transition at previous position (Figure 25).75 It
clearly demonstrates the existence of different forbidden gaps
in SnS crystals along its crystallographic axes. Contrary to
this, Valiukonis et al. observed the lowest direct energy gap
(Eb) of 1.3 eV for SnS when Ejjb, i.e., 1L4¡1L4 allowed for
optical transitions and the next direct energy gap (Ea) of
1.6 eV when Ejja, i.e., 1L1¡1L1 is allowed for transitions. At
RT, the SnS single crystals are strong absorbents for the wave-
lengths below 1 mm. These crystals have similar absorption
coefficients along it’s “a” and “c” axes (Figure 26).
Further, the SnS crystals exhibit a refractive index no(λ D 0)
of 3.6 and dielectric constant of 19.5. The effective mass of
holes in SnS crystals along its three principle axes is
ma D mb D 0:2mo ; mc D mo ; where mo is the rest mass of the
electron; and the effective charge on the atoms is e D 0:7eo ,
where eo is the electron charge.29,72 It is also realized that the
values of no and e* are isotropic since the total oscillatory
strength of three mutually perpendicular Sn-S vibrations is
one ({cos2 u1 C cos2 u2 C cos2 u3 D 1, where u is the angle
between Sn-S vibration and direction of light polarization)
that makes the oscillator strength independent of the direction
of polarization. However, the polaron effect at lower frequen-
cies is small in SnS because of its week hole-phonon coupling
constant (»0.2).78
SnS crystals exhibit Raman peaks at 40, 49, 70, 85, 95, 160,
164, 192, 208, 218, and 290 cm¡1 (see Figure 27) and infra-
red peaks at 69, 99, 145, 178, 188, 220, and 222 cm¡1.8 Due
to the structural anisotropy, SnS exhibits a low static dielectric
constant .eo / of 32 when the electrical vector . E ¡ / is parallel
to a-axis .Ejj a / or c-axis .Ejj c / than for the b-axis .Ejj b /,
(eo D 42). On the other hand, a high frequency dielectric
 18 N. KOTEESWARA REDDY ET AL.
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FIG. 26. Absorption spectra of SnS at room temperature for

three different polarizations. (Ó John Wiley & Sons, Inc.
Reprinted with permission from John Wiley & Sons, Inc.16
Permission to reuse must be obtained from the rightsholder.)

FIG. 27. Raman spectra of SnS recorded at room temperature.

constant .e 1 / value of SnS crystals obtained along b-axis (Ó American Physical Society. Reprinted with permission
.Ejj b / or c-axis .Ejj c / is higher (»16) than that the value from American Physical Society.8 Permission to reuse must be
(»14) obtained along a-axis .Ejj a /. Using the Raman and obtained from the rightsholder.)
infrared data of SnS (see Tables 2 and 3) the splitting factor
(D) raised by interlayer coupling is calculated by using the
equation for the split-off modes .v § /.79,80 calculated values of no, D and (no/D)2 are given in Table 2.
Here, the values of intra-layer and interlayer force constants

1/2 (k/q (no/D)2, where k and q are the intralayer and interlayer
v § D v2o § D2 ;
force constants, respectively) are very close and are in between
5 and 7. This implies that SnS is a layered compound. How-
where no is the frequency of the corresponding intra-layer ever, by comparing this value with similar compounds like
mode. The splitting between Raman and infrared peaks, the GeS (k/q D 15) it is concluded that SnS is a weak layer-like
compound than the GeS, which can be considered as an inter-
TABLE 2 mediate compound between layer-like and three-dimensional
Frequencies of the six pairs of Raman and infrared active
phonons together with the corresponding values of no, D and
(no/D)2. The frequencies are given in cm¡1 (Ó IOP. Repro- TABLE 3
duced with permission from IOP.79 Permission to reuse must A comparison of Raman and infrared frequencies which were
be obtained from the rightsholder) split in accordance with the given equation (Ó IOP. Repro-
duced with permission from IOP.79 Permission to reuse must
Splitting nC n¡ no D (no/D)2 be obtained from the rightsholder)
Ag-B1u 111 97 104 37.5 7.7 Ag B1u B2g B3u B3g B2u
Ag-B1u 216 183 199.5 80.7 6.1
Ag-B1u 264 220 242 100.8 5.7 264 220 194 229 160 190
B3g-B2u 160 190 175 70.8 6.1 216 183 170 200
B2g-B3u 170 200 185 76 6 111 97 78
B2g-B3u 194 229 211 84 6.4 50 47 58
 REVIEW ON TIN SULFIDE MATERIAL
crystals. Further, the SnS crystals grown with a hole-concen-
tration of the order of 1017 cm¡3 exhibit a plasma frequency
(vp) of 100 cm¡1, which clearly emphasizes the presence of
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complex plasmon-phonon coupling effect.81
5.2. Physical Properties of SnS Thin Films
The SnxS films grown by chemical bath deposition (CBD)
method exhibited polycrystalline orthorhombic crystal struc-
ture and their elemental composition ratio (Sn/S) varied
between 1.5 and 1.31 While introducing 10% H2O in the aque-
ous solution, the resulting films contained mainly single-phase
SnS and exhibited average indirect optical band gap of 1.15 §
0.15 eV and activation energy of around 0.56§0.05 eV. On
the other hand, the films grown in absence of H2O showed
Sn2S3 phase as predominant and they showed indirect band
gap of 1.7 § 0.2 eV. Further, the films grown in the presence
of PG and TA exhibited SnS2 phase as dominant phase. These
films are thicker than the above films and also have smooth
and uniform surface, which exhibited the optical band gap of
»2.2 eV. The SnS films grown at RT are amorphous in nature
and consist of n-type conductivity. The optical indirect band
gap of these amorphous films is found to be »1.51 eV.32 How-
ever, the SnS films developed at bath temperature of 75
C
exhibited good crystalline properties along with photoconduc-
tivity as compared to the films deposited at RT.33 The SnS
films grown at 30
C by CBD on glass substrates with a thick-
ness (t) of 290 nm exhibited slightly sulfur-rich chemical com-
position and consist of p-type conductivity.34 These films also
have smooth surface morphology (Figure 28a) and orthorhom-
bic polycrystals, which are preferentially oriented along the
(040) planes. The band gap of these films is found to be direct
at around 1.31 eV along with high absorption coefficient.
The SnS films grown by dipping methods exhibited
mainly polycrystalline orthorhombic crystal structures and
their degree of preferred orientation increased with increas-
ing pH of the hot solution.35 The conductivity of these
films is drastically increased with the increase of alkalinity
of SnCl2 solution. These films also showed an acceptor
activation energy of »0.3 eV. The SnS films developed by
dipping followed by baking are smooth, shiny and strongly
adherent to the substrate.36 The thickness of these films
strongly depended on the number of dippings of substrate
in solution. For example, the films grown by 5 dippings in
a mixed solution of 2.22 M SnCl2 2H2O and 1.31 M SC
(NH2)2 at pH of 3 followed by baking at 300
C for 5 min
have a thickness of around 500 nm. These films are nearly
single-crystalline and grown exclusively along the <040>
directions. Further, these SnS films exhibited a photocon-
duction band edge at »1.4 eV. However, the SnS films
grown at RT on glass as well as ITO substrates by SILAR
method with the thickness of 200 nm exhibited a polycrys-
talline orthorhombic crystal structure.37 These as-grown
films are slightly tin-rich in chemical composition and
19
show direct optical band gap of 1.43 eV. The PL analysis
of these films revealed that the as-grown SnS films have
tin-vacancies that are located at deeper levels since these
films exhibit a broad band centered at 625 nm (1.82 eV).
SnS thin films grown by cathodic electrochemical deposi-
tion (CECD) on conducting substrates (ITO and titanium)
using aqueous solutions containing 0.01 M SnCl2 and 0.01 M
thiosulphate ions under the electro-potential of ¡0.7 V are
slightly tin-rich and have smooth and uniform surfaces.38
These tin-rich films exhibited polycrystalline orthorhombic
crystal structure, and contrary to above results, showed p-type
conductivity. These films also showed indirect band gap of
around »1 eV. Similar results have also been observed by
Subramanian et al.82 from the SnS films grown under the
same conditions. However, the SnS films grown in the pres-
ence of EDTA exhibited improved crystallinity and good sur-
face coverage (Figure 28b)10 than the SnS films grown
without EDTA. These SnS films have densely grown rocksalt
like crystal morphologies (Figure 28c), and exhibits slightly
higher indirect band gap (»1.1 eV). These results indicate that
the addition of EDTA to the aqueous solution of Sn and S
probably control the formation of Sn and S ions and thereby
SnS clusters. This could lead to grow a highly-quality SnS
films with a slow-rate of nucleation.
Ichimura et al. obtained stoichiometric SnS films by ECD
techniques using SnSO4 and Na2S2O3 as precursors of Sn and
S.39 The films deposited on In2O3 coated glass substrates at
higher Sn2C concentrations (>5 mM) with a constant electro-
potential of ¡1 V are thicker (2.5 mm) and uniform than the
films grown at lower Sn2C concentrations (<1 mM). However,
upon increasing of Sn2C concentration by keeping other depo-
sition conditions as constant, the elemental ratio of SnS films
remained as nearly constant, whereas this ratio linearly
decreased with the increase of pH as well as electro-potential.
The SnS films grown in the duration of 1 hour are slightly tin-
rich in nature and consists of polycrystalline orthorhombic
crystals. These tin-rich films also exhibited direct and indirect
band gap of around 1.3 and 1.0 eV, respectively. Further,
good-quality SnS films have been obtained on ITO substrates
by cathodic ECD method using an aqueous solution 5 mM
SnSO4 and 25 mM Na2S2O3 at a pH of 2–3 under a constant
deposition potential of ¡0.73 V (vs. SCE) and bath tempera-
ture (Tb) of 40
C.83. The as-deposited films are highly stoi-
chiometric and consist of irregularly aligned nanocubes like
surface morphology (Figure 28d). However, upon increasing
bath temperature from 30–50
C, the tin-rich SnS films gradu-
ally become sulfur-rich in nature, and their direct band gap
gradually decrease from 1.48 to 1.24 eV, but the absorption
coefficient remains stable (>104 cm¡1). Using the same
approach, Kamel et al.84 achieved SnS thin films on stainless
steel substrates using the bath solution made with 25 mM
SnSO4, 250 mM potassium thiocyanate (KSCN), and 250 mM
Na2SO4. The films grown at the lower current densities
(»2.2 mA cm¡2) exhibited orthorhombic crystal structures
 20 N. KOTEESWARA REDDY ET AL.
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FIG. 28. (a) Backscattering SEM image of SnS films grown
on glass substrate (Ó IOP. Reproduced with permission from
IOP.34 Permission to reuse must be obtained from the right-
sholder.), (b) low and (c) high magnification SEM images of
SnS films deposited on titanium substrate by ECD under the
guidance of EDTA (Ó Elsevier. Reprinted with permission
from Elsevier.10 Permission to reuse must be obtained from
the rightsholder.), and (d) SEM image of SnS films grown at a
bath temperature of 40
C. (Ó Elsevier. Reprinted with permis-
sion from Elsevier.83 Permission to reuse must be obtained
from the rightsholder.)
having (040) plane as a preferential orientation. While increas-
ing the current density, the (101) plane becomes more domi-
nant than the (010) plane.
SnS films have been prepared by galvanostatic ECD
method on FTO glass substrates from nitrogen purged warm
(50–90
C) acidic aqueous solution (100 ml) at a pH of 2.5.
The solution is prepared with SnCl2 (50 mM) and Na2S2O3
(150 mM) precursors along with tartaric acid added as an
additive.85 Here, the electro-potential is varied between
¡1and 0.4 V with a rate of 150 mV s¡1 at a current density of
¡3 mA cm¡2. The as-deposited films have a thickness of
around 650 nm, exhibited stoichiometric chemical composi-
tion and orthorhombic crystal structure with (111) as preferred
orientation. These films also showed direct optical band gap
of around 1.05 eV. Thus, these studies reveal that the presence
of organic acids in the precursor solution promotes the unifor-
mity and adherence of the as-deposited films. The SnS thin
films grown by CCECD method on ITO substrates using
a bath solution of 20 mM of SnSO4 and 100 mM of Na2S2O3
under the deposition conditions of pH D 2.7, Sn2C/S2 O23 ¡ D
0.2 and current densityD3.0 mA cm¡2 in the reaction time of
1.5 h are exhibited nearly stoichiometry between its constitu-
ents.40 The SnS films grown at lower pH, Sn2C/S2 O23 ¡ and
current densities are more sulfur-rich in nature, whereas at
higher values, the films have clear Sn-rich chemical composi-
tion. SnS films grown under optimized conditions have rods
like morphology, Figure 29a,b and their adhesiveness to the
substrate is also better. These films also exhibited p-type
conductivity and their direct optical band gap and electrical
resistivity have varied between 1.21 and 1.42 eV, and 7.5 and
20 Vcm, respectively.
SnS films have been grown by pulsed ECD in three-
electrode ECC under ‘On’ potential of ¡1V for 1 s and
“Off” potential of 0 V for 1 s (vs. SCE) using the bath
solution prepared with 30 mM SnSO4 and100 mM
Na2S2O3 at a pH of 2.7. The as-grown SnS films are nearly
sulfur-rich in nature.41 Upon increasing the pulse intervals
from 1 to 10 s, the sulfur content in the films increased.
Besides this, the films grown under pulsed ECD method
with large intervals are more uniform, thicker and have
large direct band gap (1.67 eV) as compared to the films
grown by normal ECD (Figure 29c,d). Further, highly stoi-
chiometric SnS films have been deposited by pulsed ECD
method using the mixed solution consisting of »20 mM of
SnSO4 and »100 mM of Na2S2O3 under constant pH of 2–
3 and “On” potential of ¡0.75 by varying the “off” poten-
tial between ¡0.1 and 0.5 V.86 The SnS films grown under
these conditions have polycrystalline orthorhombic crystal
structure and are grown preferential along the <111>
direction. However, the lattice constants of these SnS films
slightly varied with the increase of “off” potential, as pre-
sented in Table 4. While increasing “off” potential from
¡0.1 to 0.5 V the sulfur-content of SnS films increased
and their grain size also increased along with the surface
roughness (Figure 30). All these films showed p-type con-
ductivity and upon increasing “off” potential their
FIG. 29. (a) Low and (b) high magnification SEM images of
the as-grown SnS films on ITO substrates at Tb D RT, pH D
2.7, Sn2C/S2 O23 ¡ D 1/5, J D 3.0 mA cm¡2 and t D 1.5 h
(Ó Elsevier. Reprinted with permission from Elsevier.40 Per-
mission to reuse must be obtained from the rightsholder.); and
SEM images of SnS films deposited with a thickness of
2.5 mm by (c) normal ECD and (d) pulsed ECD with 10 s
interval condition. (Ó Elsevier. Reprinted with permission
from Elsevier.41 Permission to reuse must be obtained from
the rightsholder.)
 REVIEW ON TIN SULFIDE MATERIAL 21

TABLE 4
The composition, lattice parameters and grain size of the SnS films deposited at different Voff (Ó Elsevier. Reprinted with per-
mission from Elsevier.86 Permission to reuse must be obtained from the rightsholder)
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Voff (V) Sn/S (at.%) a (nm) b (nm) c (nm) a/c Grain size (nm)

0.5 48.68/51.32 0.4431 1.1128 0.3970 1.116 26.93

0.3 49.26/50.74 0.4426 1.1125 0.3971 1.114 21.54
0.1 50.41/49.59 0.4426 1.1124 0.3973 1.114 23.94
¡0.1 51.5/48.5 0.4429 1.1134 0.3969 1.116 21.54

electrical resistivity and optical band gap are varied
between 17 and 43 Vcm and 1.23 and 1.34 eV, respec-
tively. Stoichiometric SnS films have been realized on ITO
substrates by three-electrode ECD method using the aque-
ous solution made by the procedure described above86 in
the presence of EDTA at Sn2C:EDTA:S2 O23 ¡ D1:1:4 and
different electrode potentials varied between ¡0.95 to
¡1.0 V for the duration of 1.5 h.87 The obtained films are
smooth and also have orthorhombic crystal structure.
SnS films grown by PECVD technique at the growth tem-
peratures above 200
C have purely single SnS phase and
exhibit (111) plane as preferred orientation, whereas the films
grown at below this temperature contain mixed phases.43 The
thickness of SnS films grown by PECVD method increased
with the increase of either the growth temperature or plasma
power. These single phase SnS films have p-type conductivity
and show indirect band gap of 1.16 V along with the phonon
energy of 0.18 eV. The conductivity of these films is found
to be of the order of 10¡6 V¡1 cm¡1 with deep acceptors
activation energy of 0.3 eV.
The SnS films grown by APCVD method at higher temper-
atures (>540
C) are gray in color and show excellent
FIG. 30. SEM images of SnS films grown by pulsed ECD at
different ‘off’ potentials of (a) 0.1, (b) 0.3, (c) 0.5, and (d)
¡0.1 V, respectively. (Ó Elsevier. Reprinted with permission
from Elsevier.86 Permission to reuse must be obtained from
the rightsholder.)
stoichiometry between its constituent elements. The films
grown at below this temperature are yellowish in color and
sulfur-rich in nature probably due to the presence of SnS2 and
Sn2S3 phases.44,88 Structural analysis of these films showed
that at low temperatures (»300
C) Sn-S deposits as SnS2
phase, and upon increasing temperature from 300 to higher
temperatures, this phase gradually undergoes decomposition
and forms Sn2S3 phase as an intermediate phase and at higher
temperatures it forms SnS phase (»550
C). This is in accor-
dance with the observations made by Piacente et al. who
investigated the sublimation properties of tin sulfides.89 These
single phase SnS films showed the Sn 3d5/2 binding energy
peak at 485.7 eV and S 2p3/2 peak at 161 eV and a few Raman
peaks at 96,163, 189, 220, and 288 cm¡1.
Further, good quality SnS films have been deposited at the
substrate temperature of 450
C using Bun3 SnO2 CCF3 and H2S
as precursors in APCVD method. The as-grown SnS films are
chemically stoichiometric and have polycrystalline ortho-
rhombic crystal structure.45 The surface of these films has
cuboids-like crystal morphology and also exhibited optical
band gap of 1.5 eV. SnS films have been grown by APCVD
method using (CF3CH2S)4Sn precursor as single-precursor at
above the growth temperatures of 525
C. These SnS films also
exhibited nearly stoichiometric chemical composition and
orthorhombic crystal structure.46 Noticeably, the films grown
at below 400
C clearly consist of SnS2 phase, whereas the
films grown at medium temperatures (between 400 and
525
C) contain mainly Sn2S3 along with small traces of SnS2
phase. The morphology of these phases also significantly
changed from plates to cubes via wires and rods with the
increase of substrate temperature from 400–600
C, shown in
Figure 31.
The SnS films (Figure 32a) grown by CSVT technique at a
growth temperature of about 500
C for 10 min duration
showed slightly Sn rich in chemical composition along with p-
type conductivity.50 The crystallites of these films have ortho-
rhombic structure that are preferentially oriented along the
<111> direction. The films grown by CSVT showed a low
electrical resistivity and Hall mobility of 14.5 Vcm and
3.73 cm2 V¡1s¡1 along with a higher carrier density of 1017
cm¡3. These films also exhibited direct band gap of 1.32 eV
with a high absorption coefficient (104 cm¡1). SnS films have
 22 N. KOTEESWARA REDDY ET AL.
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FIG. 31. SEM images of the SnS films deposited at different
temperatures of (a) 400, (b) 450, and (c) 550 and (d) 600
C.
(Ó The Royal Society of Chemistry. Reproduced with permis-
sion from The Royal Society of Chemistry.46 Permission to
reuse must be obtained from the rightsholder.)
been grown by ALD technique on glass as well as silicon sub-
strates by sequential feeding of 2, 4-pentanedionate (Sn-pre-
cursor), nitrogen (carrier gas) and hydrogen sulfide (S-
precursor) with nitrogen gas in the intervals of 1-30-1-30 s. at
the growth temperature of 175
C under a base pressure of 1
Torr. The ALD grown SnS films have clear stoichiometry
between the constituents and exhibits a direct optical band gap
of 1.87 eV.51
The SnS films deposited by spray pyrolysis method at the
substrate temperatures between 370–390
C have purely SnS
phase, which is oriented along the (111) plane.52 The films
grown below 370
C contained mixed phases such as SnS and
Sn2S3, whereas the films grown at higher temperatures
(>390
C) showed SnO2 as dominant phase. The crystallinity
of the sprayed SnS films increased with the increase of sub-
strate temperature. The single phase SnS films exhibit p-type
conductivity and their indirect optical band gap and activation
energy are found to be 1.27 and 0.54 eV, respectively. Using
the same method, Thangaraju et al. developed SnS films at the
substrate temperatures between 345 and 355
C on glass sub-
strates.90 Contrary to the above results, these SnS films are
amorphous and exhibit n-type conductivity. Besides this, these
amorphous SnS films show dark and photo-conductivity in the
order of 10¡3 and 10¡2 V¡1 cm¡1, respectively and an indirect
band gap of 1 eV.
FIG. 32. SEM image of SnS films grown by (a) CSVT tech-
nique at a growth temperature of 500
C in the duration of
10 min (Ó Springer Science and Business Media. Reproduced
with permission from Springer Science and Business Media.50
Permission to reuse must be obtained from the rightsholder.)
(b) spray pyrolysis method at a temperature of 350
C
(Ó Elsevier. Reprinted with permission from Elsevier.54 Per-
mission to reuse must be obtained from the rightsholder.), and
(c) XRD profile for SnS films deposited by thermal evaproa-
tion method with a thickness of (top) 18 and (bottom) 135 nm.
(Ó IOP. Reproduced with permission from IOP.91 Permission
to reuse must be obtained from the rightsholder.)
Thin films of tin sulphide (SnxSy) have been deposited on
antimony-doped tin oxide-coated glass (ITO:Sb) and bare
glass substrates by using spray pyrolysis method.53,54 The
depositions have been made using equimolar solutions of
tin chloride and thiourea at different substrate temperatures
from 100–450
C and concentrations between 10–200 mM.
The films deposited in the temperatures between 300
and 375
C and concentrations between 90 and 130 mM
exhibited nearly stoichiometric chemical composition
(Sn/S»1.03), single phase (SnS) and showed a strong (111)
preferred orientation with an average grain size of 370 nm.
The surface of these films also had uniform morphology, as
shown in Figure 32b. These single-phase films exhibited
p-type conductivity with an average electrical resistivity of
30 Vcm and a net carrier concentration of 2£1015 cm¡3.
These layers also showed a direct energy band gap of
»1.32 eV with an absorption coefficient, >105 cm¡2 at
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FIG. 33. (a) XRD profile and (b) SEM image of SnS films
deposited by co-evaporation method at a substrate temperature
of 300
C. (Ó Springer Science and Business Media. Repro-
duced with permission from Springer Science and Business
Media.57 Permission to reuse must be obtained from the
rightsholder.)
above the fundamental absorption edge. The films deposited
at other conditions deviated from chemical stoichiometry
and also exhibited additional phases like SnS2, Sn2S3, and
SnO2 along with SnS phase.
Vacuum-evaporated SnS films at a substrate temperature of
300§50
C exhibit orthorhombic crystalline structures with a
preferential orientation of (040) and higher grain sizes,
>300 nm.56 These films are slightly S-rich in composition and
show high absorption coefficient, >104 cm¡1 with a direct
FIG. 34. (a) XRD profile and (b) SEM image of SnS films
deposited by thermal evaproation method at a substrate tem-
perature of 275
C. (Ó AIP. Reproduced with permission from
AIP.58 Permission to reuse must be obtained from the
rightsholder.)
23
optical band gap of 1.48 eV. These SnS films also exhibit p-
type conductivity with a carrier density, Hall-mobility, and
resistivity of »1015 cm¡3, »400–500 cm2/Vs, and »13–
20 Vcm, respectively. The activation energy of these films is
found to be around, 0.28–0.34 eV due to the presence of deep
acceptor levels. However, the films deposited at below 200
C
exhibited (111) orientation as a dominant plane. As contrary
to this, Johnson et al.91 achieved single-phase SnS films by
vacuum-evaporation of SnS compound even at RT. These SnS
crystallites are oriented along the (111) plane (Figure 32c) and
have a direct band gap of 1.3 eV and photoconductivity of
10¡3 V¡1 cm¡1.
SnS films have been deposited at different substrate temper-
atures (30–300
C) by a thermal co-evaporation technique.57
The films grown at 300
C exhibited single-phase SnS by hav-
ing (040) peak as preferred orientation of orthorhombic crystal
structure (Figure 33a). The surface of these films contains
flakes-like crystalline morphology (inset Figure 33b). These
single-crystalline films showed the electrical resistivity of
6.1 Vcm with the activation energy of 0.26 eV. Further, the
SnS films exhibited an optical band gap of 1.37 eV with a
high optical absorption coefficient, >104 cm¡1. On the other
hand, the SnS films had been developed by resistive evapora-
tion of high-pure SnS compound at different substrate temper-
atures (20–325
C).58 As usual, the films grown at higher
substrate temperatures, >275
C, have nearly good-stoichiom-
etry and polycrystalline nature (Figure 34a). The surface mor-
phology of these films appears like monotonically dispersed
beaks-like crystallites as shown in Figure 34b. These films
also exhibited low electrical resistive and have a direct optical
band gap of 1.35 eV with absorption coefficient, »105 cm¡1.
The SnS films deposited by e-beam evaporation at the sub-
strate temperature of 300
C with a thickness of 810 nm
showed nearly single-crystalline nature with the crystallites
preferentially oriented along the (111) planes of orthorhombic
unit cell.59 These films also showed indirect and direct band
gaps of 1.24 and 1.38 eV and have a high absorption coeffi-
cient, >104 cm¡1.
Single crystalline SnS films deposited by RF-sputtering
method have better chemical stoichiometry between its
constituents. Here, the SnS films were deposited with dif-
ferent Sn and S ratios by simply changing the anode volt-
age.60 While increasing the Sn/S ratio from 0.1 to 1 the
color of the films changed from light-yellowish to heavy
gray. Stoichiometric SnS films exhibited a direct optical
band gap in between 1.43 and 1.46 eV and p-type conduc-
tivity along with low electrical-resistivity of »20 Vcm.
Further, while increasing the argon partial pressure from 5
to 60 mTorr under the power of 150 W, the thickness of
the films deposited in a fixed durations (60 min) decreased
from 1.58 to 0.23 mm and the surface morphology also
changed (Figure 35a–d).62 The SnS films grown at low
pressures have (002) plane as preferential orientation; how-
ever with increasing pressure, (111) plane becomes
 24 N. KOTEESWARA REDDY ET AL.

films have polycrystalline crystals and exhibit a direct optical

band gap of 1.3 eV.
The SnS films grown by hot-wall deposition method at dif-
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ferent substrate temperatures between 210 and 300
C showed

nearly stoichiometry (Sn/S D 1.07) with min sulfur defi-
ciency.65 These films exhibited (040) plane as preferred orien-
tation and had p-type conductivity. While increasing substrate
temperature, the direct band gap of these films decreased from
1.27 to 1.07 eV due to the decrease of film thickness.

5.2.1. Temperature Effect

Reddy et al. studied the structural and optical properties of
microcrystalline SnS films at different temperatures under a vac-
uum of 10¡6 Torr.92 Here, the SnS films were deposited by resis-
tive thermal evaporation method on glass substrates at a
substrate temperature of 300
C. At RT, the SnS films showed
orthorhombic crystal structure with lattice parameters of a D
0.424, b D 1.107, and c D 0.397 nm. These films also showed
(measured under vacuum) an optical band gap of 1.47 eV with a
high absorption coefficient, 105 cm¡1. X-ray diffraction studies
at different temperatures (100–598 K) showed that the structure
of SnS films remains stable and their unit cell volume increased
with the increase of temperature. On the other hand, the band
FIG. 35. SEM images of SnS films grown on glass substrate gap of SnS films slightly decreased (Figure 37) with the increase
by RF-sputtering method at different argon partial pressure of of temperature from 4–300 K. The overall change is about
(a) 5, (b) 10, (c) 30, and (d) 60 mTorr; and (e) XRD profiles of 0.03 eV. As compared to similar compound GaAs, the change in
SnS films grown on glass substrate by RF-sputtering method optical band gap of SnS films is much less since the change is
at different argon partial pressure of (a) 5, (b) 10, (c) 30, and 0.1 eV for GaAs. Thus the change in optical band gap of SnS
(d) 60 mTorr. (Ó Elsevier. Reprinted with permission from films with the chance of temperature is marginal.
Elsevier.62 Permission to reuse must be obtained from the
rightsholder.)
5.2.2. Thickness Effect
It is well known that the physical properties of thin film mate-
dominant (Figure 35e) and Sn/S ratio also increases. The
rials depend on deposition parameters as well as on the film
resistivity of the films increased from 1.1 to 33 kV cm
with pressure and their indirect band gap decreased from
1.07 to 1.02 eV.
Single-phase SnS films grown by two-step process or sulfu-
rization method consist of 200 nm thickness and orthorhombic
crystal structure. The as-grown crystallites are preferentially
oriented along the [111] plane.63 These sulfurized films have
slightly tin-rich chemical composition, and regular shaped
nanoparticle morphology with narrow porosity, as shown in
Figure 36. These films also exhibited p-type conductivity and
have an electrical resistivity of 102 Vcm with the activation
energy of 0.65 eV. Moreover, these films show a high absorp-
tion coefficient (>104 cm¡1) along with a direct optical band
gap of 1.35 eV. Alternatively, SnS films have been grown by
sulfurization of Sn-sheet in two-zone furnace for 76–103 h as
well as 600 nm thick Sn-film coated glass substrates in vac-
uum chamber for 60 min at a temperature of 200
C.64 The as- FIG. 36. SEM image of SnS films grown by sulfurization
grown films in both the routes showed SnS phase along with a method. (Ó Elsevier. Reprinted with permission from Elsev-
few other phases like S and Sn. The final thickness of SnS ier.63 Permission to reuse must be obtained from the
films grown in vacuum chamber is found to be 4.5 mm. These rightsholder.)
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FIG. 37. Variation of energy band gap of SnS films as a func-
tion of temperature. (Ó AIP. Reprinted with permission from
AIP.92 Permission to reuse must be obtained from the
rightsholder.)
thickness.93–95 Thus, the understanding of film thickness on the
physical properties of SnS films is important. There have been a
few reports on this issue, which are described below.
Tanusevski et al. deposited SnS films by e-beam evapo-
ration method with different thicknesses from 410–810 nm
by keeping other deposition parameters as constant.59 With
increasing film thickness, their surface roughness increased
from 22 to 51 nm (Figure 38) and all the films showed p-
type conductivity. The SnS films were grown at RT by
chemical bath deposition using the aqueous solution pre-
pared with 0.8 g of NH4F, 1.125 g of SnCl2. 2H2O, 6 ml
of 0.25% NH4OH, and 5 ml of 2M Na2S2O3 in 100 ml of
distilled water at a pH of 7.96 By increasing the deposition
FIG. 38. AFM images of SnS films deposited by e-beam evaporation with a thickness of (a) 410 and (b) 810 nm. (Ó Elsevier.
Reprinted with permission from Elsevier.59 Permission to reuse must be obtained from the rightsholder.)
25
time from 4 to 18 h the SnS films were deposited with
ifferent thicknesses (Figure 39). The thickness of SnS films
increases in the beginning and then gets saturated, probably
due to the ionic product of the solution becoming equal to
solubility product.
Devika et al. investigated the impact of film thickness
on the physical properties of SnS films.97 Here, the SnS
films were deposited on glass substrates by thermal resis-
tive evaporation at a substrate temperature of 300
C with
different thicknesses between 0.1 and 1.5 mm. While
increasing the film thickness, the SnS films becomes more
stoichiometric and their average crystallite size gradually
increased from 30 to 120 nm. However, the SnS films
deposited at 0.5 mm thickness showed (111) orientation
as dominant, whereas, at higher thickness (040) peak
becomes more dominant (Figure 40a). These SnS crystalli-
tes exhibited different electrical and optical properties
depending on their preferential orientations. For example,
SnS films deposited with 0.75 mm have an optical band
gap of about 1.5 eV, whereas films deposited with 0.5 mm
thickness showed the band gap of 1.35 eV. Further, the
SnS films exclusively oriented along the <111> direction
exhibited a low electrical resistivity and activation energy
(39 Vcm and 0.28 eV) than the films oriented along the
<040> directions (65 Vcm and 0.3 eV) (Figure 40b).
5.2.3. Substrates Surface Effect
It is well known that the decrease of lattice mismatch with
substrate reduces the defect state density, and electrical resis-
tivity of the thin films with considerable improvement in their
grain sizes. This could significantly enhance the efficiency of
optoelectronic devices. In particular, the films to be adopted in
the fabrication of optoelectronic devices should possess two
basic requirements: (1) high absorbance (or transmittance) and
 26 N. KOTEESWARA REDDY ET AL.
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FIG. 39. The dependence of thickness of SnS films on the
deposition time in the bath solution. (Ó IOP. Reproduced with
permission from IOP.96 Permission to reuse must be obtained
from the rightsholder.)
(2) low electrical resistivity. There have been several methods
developed to obtain low-resistive metal-chalcogenide films
including by reducing the lattice-mismatch between film and
substrate, and creation of excess metal atoms in the host
films.98,99 In this view, a few groups have been tried to obtain
low-resistive SnS films by selecting nearly lattice-matched
substrates, annealing and doping of foreign elements. In gen-
eral, thin films have very little strength and cannot be made
self-supporting. They must be manufactured onto suitable sup-
porting substrates. Here, the selection of substrate is a critical
issue since it must be compatible with the film material in
every way; chemically, structurally, with respect to tempera-
ture and stress stability. In particular, how different substrates
affect the physical properties of SnS films is briefly described
below.
Nozaki et al. prepared the epitaxial SnS films by deposit-
ing them on MgO(001) substrates using molecular beam
epitaxy.60 The as-grown SnS films on at a substrate temper-
ature of 335
C have smooth surface morphology (Figure 41)
and orthorhombic crystal structures. The epitaxial relations
between SnS film and substrate are found to be: (010)SnSjj
(001)MgO and [100]SnSjj[100]MgO or [001]SnSjj[100]
MgO. These films showed slightly low unit cell volume
(0.193 nm3) than that of its bulk counterpart (0.194 nm3).
Upon increasing the substrate temperature from RT to
600
C or decreasing “a/c” ratio, the lattice parameters “b”
and “c” of epitaxial SnS films increased, whereas the lattice
parameter “a” decreased. From these investigations the
authors realized that the interfacial interaction between the
SnS film and substrate has strong impact on the lattice
dimensions of the films, particularly along the weak bond
FIG. 40. (a) XRD patterns of SnS films deposited at two dif-
ferent thickness of 500 and 750 nm and (b) electrical resistiv-
ity as a function of film thickness (inset shows magnified
view of the curved portion between 500 and 1000 nm).
(Ó The Electrochemical Society. Reprinted with permission
from The Electrochemical Society.97 Permission to reuse must
be obtained from the rightsholder.)
direction, not only near the substrate surface, but over the
whole thickness of the film. While decreasing the a/c ratio
the indirect energy band gap of the SnS films has increased.
However, the indirect band band-gap measured along direc-
tions perpendicular to the b-axis is larger than that along
the b-axis.
The substrate surface effect on the physical properties of
SnS thin films has been investigated by Devika et al.100 Here,
the SnS films were deposited on glass, ITO-coated glass, Si
(100) single crystal wafer and Ag-coated glass substrates using
the resistive thermal evaporation method. All the as-deposited
films exhibited nearly stoichiometric chemical composition
(Sn/S atomic% ratio of »1.05) and different surface morphol-
ogies (Figure 42). These films have orthorhombic structured
crystallites and all of them, except the films grown on Si sub-
strates, showed (111) as a dominant peak. The films deposited
on Si substrates exhibited (0 4 0) as a dominant peak. As com-
pared to other structures, the SnS films deposited on ITO
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FIG. 41. SEM image of SnS film grown on MgO substrate at a
substrate temperature of 335
C. (Ó Elsevier. Reprinted with
permission from Elsevier.60 Permission to reuse must be
obtained from the rightsholder.)
substrates have high rms surface roughness (»14.9 nm) and
average grain size (»225 nm). These films also showed very
low electrical resistivity of 8.9 £ 10¡3 Vcm. The physical
properties of the SnS films deposited on different substrates
are presented Table 5.
Moreover, this group has developed SnS films on nearly
lattice matched substrates and investigated their physical
properties.101 A single crystalline aluminum (Al(100))
sheet has been chosen as lattice matched substrate due to
lower mismatch between Al and SnS (7.14 and 1.41%
along a and c lattice parameters, respectively). The SnS
films grown on these substrates are highly crystalline and
epitaxially oriented along the <101> direction. For com-
parative understanding, the XRD spectra of SnS films
grown on amorphous and lattice-matched substrates are
shown in Figure 43. The rms surface roughness of these
films is found to be »2.5 nm. Raman spectroscopic analy-
sis shows that these epitaxial SnS films have a good crystal
quality and phase purity. The PL analysis reveals that these
films are probably consisting of three types of localized
defect-states namely interstitial Sn, and vacancies of Sn
and S atoms.
5.2.4. Annealing Effect
In general, the resistivity of the films strongly depends on
preparation conditions and techniques. As stated above,
creation of excessive metal atoms in the SnS films leads
their resistivity to lower values, which would be achieved
through various heat treatments. A thermal treatment of as-
grown films also improves their structural quality as well as
stability.102–104 Also, it relieves accumulated strain energy,
27
diminishes defects, and enlarges their grain size since the dis-
locations and other structural defects will move towards grain
boundaries and adsorb/decompose with the surface.
The SnS films grown by dipping method under optimized
conditions have been annealed in vacuum at 285
C for 4
and 24 h and open air at 300–400
C for 30 min.35 Upon
annealing the SnS films in open air for a short time, the con-
ductivity type of the films changed from p- to n-type, and
the electrical conductivity increased by one order of magni-
tude. The films annealed in vacuum for a long time showed
a drastic change in their chemical composition and also
exhibited a new SnS2 phase by partial release of tin. In case
of open air annealing for a long time, SnS films get oxidized
and formed SnO2 phase. As per these observations, the
release of tin atoms with annealing of SnS films probably
leads their conductivity to n-type and have a donor activa-
tion energy of »0.2 eV. Upon annealing the chemically
deposited SnS films at above 300
C in air, a phase conver-
sion from SnS to SnO2 through an intermediate phase of
SnO2-x has been observed by Nair et al.105 While increasing
annealing time from 0 to 10 min at higher temperatures
(400
C), the electrical resistance of SnS films decreased
from 1010 to 104 Vcm¡2 and further prolongation of anneal-
ing time, it drastically increased due to the formation of
SnO2 from SnO2-x phase. These investigations also reveal
that low-resistivity SnS films can be obtained by annealing
them at below 350
C in air.
Johnson et al. studies the impact of annealing on the
physical properties of stoichiometric SnS films deposited by
FIG. 42. SEM images of SnS films grown on different sub-
strates. (a) glass, (b) ITO/glass, (c) Si, and (d) Ag/glass.
(Ó IOP. Reproduced with permission from IOP.100 Permission
to reuse must be obtained from the rightsholder.)
 28 N. KOTEESWARA REDDY ET AL.

TABLE 5
The physical properties of SnS films deposited on different substrates by thermal resistive evaporation method (Ó IOP. Repro-
duced with permission from IOP.100 Permission to reuse must be obtained from the rightsholder)
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Lattice parameters (nm) L (nm)

Preferred
Sub. a b c orientation (PO) Avg. Along PO DPO rms roughness (nm) r (Vcm) Eg(eV)
Glass 0.433 1.121 0.399 (111) 168.3 154 16.5 7.83 38.8 1.35
ITO 0.468 1.133 0.373 (111) 220.1 405 4.76 14.93 8.9£10¡3 1.62
Si 0.428 1.114 0.404 (040) 180.0 80.0 — 8.36 4.67 1.55
Ag 0.433 1.121 0.398 (111) 171.6 164 3.48 10.83 0.26 1.86

vacuum evaporation method. Here, the annealing tempera-
ture was varied from RT to 300
C and executed under air
and argon (Ar) atmosphere for 5 min.91 The films annealed
in air showed good improvement in their conductivity with
the increase of annealing temperature upto 50
C, and above
this temperature, it decreased. In case of Ar atmosphere,
the conductivity increased upto 100
C and above this, it
gradually decreased with annealing temperatures. After
annealing, the SnS films grown by brush plating method
exhibited an average thickness of about 1.5 mm.42 These
annealed films showed slightly tin-rich chemical composi-
tion and polycrystalline orthorhombic crystal structure.
These films have an average grain size of about 320 nm
and exhibit p-type conductivity. The electrical resistivity of
annealed films varied between 10 and 15 V cm. These films
have a high absorption coefficient of »104 cm¡1 and an
FIG. 43. XRD spectra of SnS films grown on glass and Al
substrates. (Ó John Wiley & Sons, Inc. Reprinted with permis-
sion from John Wiley & Sons, Inc.101 Permission to reuse
must be obtained from the rightsholder.)
indirect band gap of 1.1 eV. The SnS films, grown by
cathodic electrodeposition on ITO substrate at a bath tem-
perature of 50 § 20
C under the conditions reported else-
where,101 were annealed under vacuum at 250
C for the
duration of 30 min.83 Upon annealing, the SnS films
showed an excellent improvement in their crystallinity and
surface-smoothness. Further, the average grain size of the
films is also increased from 580 to 760 nm. These films
exhibited p-type conductivity and high transmittance. How-
ever, the as-deposited as well as annealed SnS films showed
an indirect optical band gap of 1.15 eV and electrical resis-
tivity of 20 Vcm with deep-acceptor activation energy
between 0.34 and 0.45 eV.
The SnS films deposited by thermal evaporation method at
RT are amorphous in nature.106 Upon annealing the SnS films
between 150 and 300
C for 1 h under the vacuum of 10¡6
Torr, the films become polycrystalline and their crystallites
are preferentially oriented along the <111> direction. How-
ever, the films annealed at 200
C exhibit better quality than of
the films annealed at other temperatures. At all wavelengths,
the annealed SnS films exhibit lower refractive index and
absorption coefficient as compared to the as-grown films. Fur-
ther, the amorphous SnS films show a higher indirect (lower
direct) band gap of 1.4 eV (2.18 eV) than that of crystalline
films 1.38 eV (2.33 eV). The SnS films grown by chemical
bath technique exhibited stable structural properties upto the
annealing temperature of 250
C in argon environment for 1
and 8 h.96 However, the films annealed at 300
C for 1 h
showed slight improvement in the intensity of preferential ori-
entation, i.e., (111). The transmittance of these films increased
with the increase of annealing temperature as well as time.
While increasing annealing temperature and time, the direct
band gap of the films remained constant at 1.38 eV, whereas
the indirect band gap increased between 0.96 and 1.14 eV.
Further, the SnS films annealed at 250
C even at longer tim-
ings showed lower photoconductivity as compared to as-
grown films, and it is high for the films annealed at 300
C for
1 h, which attributed to the crystallinity of the films.
Devika et al. studied the impact of normal annealing on
the physical properties of SnS films.107 The films were
deposited on glass substrates and annealed at various
 REVIEW ON TIN SULFIDE MATERIAL 29

temperatures from 100–400
C in a vacuum of 10¡5 Torr

for 1 h. Here, the films annealed at 400
C remained on
glass substrate as patches due to partial re-evaporation of
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SnS. While increasing the annealing temperature, the SnS

films become tin-rich in nature and at higher temperatures,
the Sn/S ratio of the films was found to be 1.1. The crystal
structure of annealed SnS films, however, remained stable
as orthorhombic and the change in their lattice parameters
was also marginal. The grain size and rms surface rough-
ness of the films decreased with the increase of annealing
temperature (Figure 44). While increasing annealing tem-
perature, the resistivity of SnS films decreased from 37 to
9 Vcm. However, the films annealed at 100
C exhibited
slightly lower optical band gap (1.35 eV) and activation
energy (0.24 eV) than the other films. Yue et al. studied
the impact of annealing on the physical properties of SnS
films, which were grown by three-electrode ECD
method.108 The growth was carried out onto ITO coated
glass substrates using a bath solution of 30 mM SnCl2 and
100 mM Na2S2O3 with a pH of 1.8 at a growth tempera-
ture of 30
C in the reaction time of 30 min. Then, the
films were annealed at different temperatures between 100
and 250
C in air for 1hr. Upon annealing, the films exhib-
ited drastic change in their surface morphology (Figure 45)
and chemical composition. The crystallinity as well as
grain size of the films increased with increasing annealing
temperature upto 150
C and above this temperature, the
SnS films got oxidized and formed SnO2 phase. Further,
the SnS films exhibited increase in absorption while
increasing annealing temperature (upto 150
C) and their
optical band gap also increased from 1.31 to 1.39 eV.
Devika et al. observed a few interesting physical properties
from the annealed SnS films by rapid thermal annealing
(RTA) process.109 Here, also, the SnS films were deposited by
thermal evaporation technique on glass substrates and treated
by RTA for a short time of 1 min at different temperatures FIG. 44. SEM images of (a) as deposited and annealed SnS
from 300–550
C under N2 atmosphere. As usual, the Sn/S films at (b) 100 and (c) 400
C. (Ó IOP. Reproduced with per-
ratio and crystallinity of the films increased with the increase mission from IOP.107 Permission to reuse must be obtained
of annealing temperature. The resistivity of the annealed films from the rightsholder.)
decreased upto the annealing temperature of 400
C and above
this it slightly increased (Figure 46). The SnS films annealed et al.72 investigated the doping effect of antimony (Sb) and sil-
at 400
C exhibited a low electrical resistivity of 5 Vcm ver (Ag) on SnS single crystals and observed n-type conduc-
(as compared to normal annealing films) with considerably tivity with a carrier concentration of 10£19 cm¡3 in Sb-doped
high Hall mobility and carrier density of 99 cm2 V¡1 s¡1 and SnS crystals and p-type conductivity with a concentration
1.3 £ 1016 cm¡3, respectively. Another noticeable point here 10£18 cm¡3 in Ag-doped SnS crystals.
is that the SnS films survived significantly upto 500
C anneal- Doping of antimony (Sb) into sputtered SnS films fol-
ing temperature upto and as usual, the films exhibited sublima- lowed by annealing between 350 and 450
C in hydrogen
tion at higher temperatures (»550
C). atmosphere also changed the conductivity of SnS films from
p-type to n-type and their resistivity fell down to 2 Vcm.60
The impact of Ag doping on the physical properties of SnS
5.2.5. Doping Effect films has been investigated by Devika et al.110 Here, the Ag
Alternative to annealing, the low-resistive SnS films can be doping was achieved by an instant evaporation of SnS and
obtained by the creation of excess of metal atoms through Ag from a single boat and deposited on glass substrates
incorporation of suitable dopants. In this direction, Albers with a thickness of 0.5 mm at a substrate temperature of
 30 N. KOTEESWARA REDDY ET AL.

10¡5 Torr at 100
C for 30 min. Although the crystal structure

of SnS films remained unaltered with the increase of Sn-dop-
ing concentration, they exhibited a new Sn2S3 binary phase at
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higher concentration. Upon increasing the doping concentra-

tion of Sn, the resistivity of the SnS films decreased upto 6 mg
of Sn-diffusion and above this, the resistivity slightly
increased. The direct band gap of the Sn doped SnS films also
remained as constant at 1.33 eV.

5.2.6. Metallization of SnS

Despite the progress on SnS and its devices, there are sev-
eral technological challenges in the development of high-qual-
ity SnS films and fabrication of efficient devices. Among
them, selection and development of compatible, low-resistive,
and thermally stable Ohmic contacts to SnS films is one of the
crucial and challenging tasks. To identify such contacts, it is
desirable to use elements which should easily form inter-
FIG. 45. The FESEM images of (a) as-grown and annealed metallic compounds with high melting points after formation
SnS films at (b) 100, (c) 150 and (d) 250
C. (Ó Elsevier. of Ohmic contact. The selected Ohmic contact should also
Reprinted with permission from Elsevier.108 Permission to have good adhesion, smooth surface, and low sheet resistance.
reuse must be obtained from the rightsholder.) The existing reports about the metallization of SnS structures
are described below.
The contact behavior or metallization of highly sulfur-rich
275
C. All the films exhibited crystal structure as ortho- SnS films grown on ITO substrate by pulsed ECD method has
rhombic and (111) plane as preferred orientation. The grain been studied with different metals including Al, Ag, Au, and
size and crystallinity of the films were considerably In.113 Here, prior to the deposition of metal contacts, the films
improved with increasing Ag concentration. However, the had been annealed at 200
C under nitrogen atmosphere. All
electrical resistivity (Figure 47a) and activation energy of these contacts gave excellent Ohmic electrical contacts with
the doped SnS films decreased upto 15 at.% and above this SnS films between ¡1 and C1 V. However, as compared to
concentration, they increased. The optical band gap of the Al contacts, the other contacts have excellent Ohmic behavior
films also decreased with increasing concentration (Fig-
ure 47b). Here, the formation of new Sn-S–Ag ternary phase
is identified as a probable reason for the deviation in electri-
cal and optical properties of Ag doped SnS films.
In-doped SnS films with a thickness of 400 nm have been
obtained on glass substrate using CBD technique at a growth
temperature of 45
C.111 The in-situ doping of In at different
concentrations was obtained by the addition of various
amounts of InCl3 4H2O to the bath solution consisting of 1 g
SnCl2 2H2O dissolved in 5 ml of acetone, 10 ml 50% trietha-
nolamine, 4 ml 1M thioacetamide, 5 ml 25% NH3 H2O, and
distilled water. At all doping concentrations, the SnS films
exhibited orthorhombic crystal structure. While increasing the
In-doping concentration from 0 to 5 wt. % the grain size
and surface roughness of SnS films gradually decreased
(Figure 48) and above this, the Sn content of the films
decreased with increasing In-concentration. However, the SnS
films showed slight decrease in optical direct band gap
(1.39 eV) and electrical resistivity (in M Vcm) up to the dop- FIG. 46. Variation of resistivity and mobility of SnS films as a
ing of 1.5 wt. %, and above this, both the parameters function of RTA temperature. (Ó Springer Science and Busi-
increased. Recently, Sn-doped SnS films have been obtained ness Media. Reproduced with permission from Springer Sci-
by ex-situ diffusion of Sn by the annealing of thermally evapo- ence and Business Media.109 Permission to reuse must be
rated Sn layer on sprayed SnS films55,112 under a vacuum of obtained from the rightsholder.)
 REVIEW ON TIN SULFIDE MATERIAL
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FIG. 47. Variation of (a) resistivity and (b) energy band gap
of SnS films as a function of Ag-concentration. (Ó The Elec-
trochemical Society. Reprinted with permission from The
Electrochemical Society.110 Permission to reuse must be
obtained from the rightsholder.)
and also allow high current in the order of mA. Upon anneal-
ing (100–300
C), the resistivity of the films decreased and the
activation energy of SnS films with all contacts is found to be
»0.05 eV. Metallization of SnS thin films grown on glass sub-
strates with different metals (M D Ag, Al, In, and Sn) has
been studied by Devika et al.114 Further, the stability of the
M/SnS structures was examined by RTA annealing at different
temperatures, 300–500
C. The as-deposited SnS films have
slightly tin-rich chemical composition (Sn/S»1.1) and prefer-
entially oriented orthorhombic crystals along the <010>
direction. All M/SnS structures, except Ag/SnS, have excellent
Ohmic contact behavior between §10 V, which indicates that
these M/SnS structures follow field emission (FE) or tunneling
transport mechanism. However, the Ag/SnS contacts exhibited
Ohmic behavior only between §6 V (Figure 49a) and beyond
these voltages, it showed nonlinear trend due to the presence
of bias-dependent interface charges or states present between
Ag and SnS film, which probably control the barrier height
and thereby the current flow across the junction. Therefore,
Ag/SnS structures follow two types of transport mechanisms
depending on applied bias-voltage. At lower voltages (<6 V),
31
the structures follow FE mechanism, whereas at higher vol-
tages, follow thermionic emission (TE) mechanism, i.e.,
Schottky or rectifying behavior. The resistivity and activation
energy of M/SnS structures are given in Table 6. Here, the In/
SnS structures have shown lower electrical resistivity than
other M/SnS structures.
On the other hand, the M/SnS structures annealed at
various temperatures showed considerably better Ohmic
behavior. However, while increasing annealing temperature
(AT), In/SnS and Sn/SnS structures exhibited degradation
in their electrical properties due to re-evaporation of metal
layers. The Ag/SnS structures showed an excellent
improvement in their Ohmic trend with the increase of AT
(Figure 49b), which is probably due to the diffusion of Ag
atoms into SnS crystal lattice. Thus, the RTA treated Ag
metal contacts at higher temperatures could be also useful
for SnS based devices since they exhibited better and sta-
ble properties as compared to other M/SnS structures.
More recently, Mathews has studied the electrical proper-
ties of SnS films using Al contacts.115 Here, the SnS films
were deposited on florin doped tin oxide substrate by
pulsed ECD method with a thickness of 410 nm. The as-
deposited SnS films exhibited two types of carrier transport
mechanisms such as diffusion and recombination with Al
contacts and also had two-shallow traps activation energies
of 0.14 and 0.27 eV.
6. DEVICE APPLICATIONS OF SnS
SnS semiconductor is a potentially useful material for a
variety of applications including photovoltaics, optoelectron-
ics, chemical sensors, soli-state batteries, holographic, etc.,
due to its unique properties like direct band gap, high absorb-
ability, tunable electrical properties, thermal and chemical sta-
bility, and layered structure. Even though the basic concepts
of SnS are well understood at this time, some practical con-
straint including a lack of proper methodology to produce
highly conductive structures have hampered its potentials and
advantages. In this section, we review photovoltaic and other
applications.
FIG. 48. SEM images of (a) undoped and (b) 0.015 g doped
SnS films. (Ó Shanghai University. Reprinted with permission
from Shanghai University.111 Permission to reuse must be
obtained from the rightsholder.)
 32 N. KOTEESWARA REDDY ET AL.

TABLE 6
The evaluated electrical resistivity and activation energy of M/
SnS structures (Ó AIP. Reprinted with permission from
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AIP.114 Permission to reuse must be obtained from the

rightsholder)
Metal Resistivity (Vcm) Activation energy (eV)

Ag 25.71 0.31
Al 16.78 0.17
In 4.81 0.22
Sn 8.5 0.16

6.1. Photovoltaic Applications

SnS came into limelight as a candidate mainly for the
development of solar cell devices due to its narrow band gap
and high absorption. In this direction, variety photovoltaic
devices have been realized by using p-SnS films as absorber
layer and other n-type materials as window layers, which are
discussed below.
Noguchi et al. prepared SnS films-based photovoltaic (PV)
devices with the configuration of n-CdS/p-SnS on indium
doped tin oxide (ITO) substrate with Ag as Ohmic contacts.
All the layers were developed using thermal evaporation
method, and the schematic diagram of the device is shown in
Figure 50a.56 Under dark, the as-deposited devices exhibit a
high diode quality factor of 3.5 and saturation current density
of 2.83 £ 10¡4 A cm¡2. These devices showed good photovol-
taic performance (Figure 50b) under the illumination of
100 mW cm¡2 light and exhibited a short-circuit current (Isc)
of 7 mA cm¡2, open-circuit voltage (Voc) of 0.12 V with a fill
factor of 0.35. The observed photoconversion efficiency is of
about 0.29%. Ristov et al. realized SnS based solar cells by
using two different materials as window layers and Schottky
contact namely cadmium oxide (CdO), cadmium tin oxide
(Cd2SnO4), and SnO2:F with the configuration of CdO/SnS/
Ag, Cd2SnO4/SnS/Ag, and SnO2:F/SnS/Ag. The device photo-
voltaic characteristics were studied under the illumination of
day light, 50 and 100 mW cm¡2 as shown in Figure 51a–b.116
The open circuit voltage of the devices developed with CdO
and Cd2SnO4 window layers is higher than the other devices,
probably due to the possible formation of very thin interlayer
of cadmium sulfide (CdS). As compared to other devices, the
devices developed with SnO2:F electrodes showed good pho-
toresponse in ultraviolet region, and exhibited a maximum
sensitivity at 520 nm (Eg D 2.4eV).
Sanchez-Juarez et al. have fabricated SnS2/SnS solar cell
devices and estimated their photovoltaic conversion efficiency
under the illumination of 70 mW cm¡2 light.116 Here, thin
films of SnS2 and SnS have been deposited onto the transpar-
ent conductive oxide (TCO) substrate by plasma enhanced
chemical vapor deposition (PECVD) method with a thickness
of 0.15 and 0.35 mm and then, the aluminum contacts were
FIG. 49. Current vs. voltage plots of M/SnS (M D Ag, Al, In,
Sn) (a) as-grown structures measured at room temperature,
and (b) Ag/SnS structures measured at different temperatures.
(Ó AIP. Reprinted with permission from AIP.114 Permission
to reuse must be obtained from the rightsholder.)
deposited by thermal evaporation with diameter and thickness
of 0.2 cm and 0.8 mm. The final configuration of the device is
glass/TCO/n-type SnS2/p-type SnS/Al, shown in Figure 52a.
Under dark, these devices exhibited good rectification behav-
ior and the ratio between forward and reverse bias currents
within the range of applied voltages of §1.0 V is found to be
>300. These devices also showed a reverse saturation current
of about 3.7 £ 10¡7 A and diode factor of 2.7. Under illumina-
tion, a typical device exhibited photovoltaic effect (Fig-
ure 52b) with Voc D 0.35 V and Isc D 1.5 mA cm¡2.
Miyawaki et al. developed ZnS/SnS solar cell devices by
depositing ZnS films on 0.6 mm thick p-type SnS thin films
using photochemical and electrochemical deposition methods,
respectively.117 The as-deposited device showed (Figure 52c)
good rectifying behavior and under 100 mW cm¡2 light these
structures exhibited Isc and Voc as 0.95 mA cm¡2 and
135 mV, respectively. The same group have also developed
SnS based solar cell devices by using CdS and Cd1-xZnxS films
as window layers and studied their PV performance under the
illumination of 100 mW cm¡2 light.118 The PV conversion
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FIG. 50. (a) Schematic diagram of SnS based solar cell and
(b) current-voltage characteristics of SnS/CdS device under
illumination. (Ó Elsevier. Reprinted with permission from
Elsevier.56 Permission to reuse must be obtained from the
rightsholder.)
efficiency of CdS/SnS cells grown under optimized conditions
showed as 0.22%, whereas the cells developed with a configu-
ration of Cd0.87Zn0.13S/SnS exhibited 0.71%, which can be
seen from Figure 53.
SnS-based solar cell devices have been developed by
Avellaneda et al. using CdS as window layer and also pre-
pared cells by using CuS and Cu2SnS3 as buffer layers.119
The performance of these devices has been measured under
the illumination of 85 mW cm¡2 light, and the obtained
results are shown in Figure 54. Here, the SnS, CdS, CuS,
and Cu2SnS3 films were deposited with a thickness of
400–500, 100, 50–100, and 100 nm, respectively by
FIG. 51. Current-voltage characteristics of (a) CdO/SnS, and (b) Cd2SnO4/SnS PV cells under different illuminations. (Ó Elsev-
ier. Reprinted with permission from Elsevier.116 Permission to reuse must be obtained from the rightsholder.)
33
chemical bath deposition method. The configurations of all
the cells and their photovoltaic responses are given in
Figure 54. From the simplest CdS/SnS device they
observed Voc as 380 mV and Jsc as 0.05 mA cm¡2. The
cells developed with an additional absorber layers i.e. CuS,
which was heated at 473 K in air for 10 min in order to
reduce the CuS thin film resistance, showed a Voc D
310 mV and Jsc D 1 mA cm¡2. Finally, Cu2SnS3 layer
grown CdS/SnS device, which was developed by annealing
the 100 nm CuS layer coated CdS/SnS structures in a
nitrogen atmosphere at 315
C for 1 h, showed photovoltaic
characteristics of VocD 340 mV and Jsc D 6 mA cm¡2.
Here, the performance of CdS/SnS/ Cu2SnS3 device is
comparatively better than that of other cells. Ghosh et al.
developed solar cell devices by evaporating CdS and SnS
materials onto ITO substrate with the thickness of 0.3 and
1 mm, respectively.120 Here, the device properties were
investigated with post chemical treatment of the window
material by CdCl2 and their I–V characteristics were mea-
sured under dark and illumination of 100 mW cm¡2 light,
which are shown in Figure 55a–c. The efficiency of these
devices with and without window layer chemical treatment
is found to be 0.08% and 0.05%, respectively. Further, as
compared to untreated layers, the devices treated with
CdCl2 exhibited a high absorptivity particularly in visible
wavelength range, 400–700 nm. This group also developed
SnS/ZnO cells using thermal evaporation and electrodepo-
sition methods, respectively, and observed good photovol-
taic conversion efficiency of 1.29%.121
Nanocrystalline tin sulfide (SnS) based solar cell device has
been developed by Wang et al. using TiO2 as window layer,
and their photovoltaic behavior were studied.122. The devices
showed an open-circuit voltage (Voc) of 471 mV, a short-cir-
cuit current density (Jsc) of 0.3 mA cm¡2 and the conversion
efficiency (h) of 0.1% under 1 sun illumination, as shown in
Figure 55d. Stavrinadis et al. developed solar cell devices by
using 140 nm thick SnS and lead sulfide (PbS) NP films with
the configuration of ITO/SnS/PbS/Al (Au).123 A device made
with Au contacts shows an open circuit voltage Voc D 0.2 V
and short circuit current Isc D 4.2 mA cm¡2 with an overall
 34 N. KOTEESWARA REDDY ET AL.
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FIG. 52. (a) Schematic diagram of SnS2/SnS solar cell, (b) current vs. voltage plot of the device under dark (inset shows its I vs.
V characteristics under illumination) (Ó Elsevier. Reprinted with permission from Elsevier.117 Permission to reuse must be
obtained from the rightsholder.), and (c) current vs. voltage characteristics of ZnS/SnS heterojunction cell. (Ó Elsevier.
Reprinted with permission from Elsevier.118 Permission to reuse must be obtained from the rightsholder.)

power conversion efficiency of 0.27%. However, the devices
fabricated with Al contacts showed considerably a high Voc of
0.44 V and low Isc of 1.2 mA cm¡2 with a conversion effi-
ciency of 0.17%.
6.2. Other Applications
Apart from the photovoltaic applications, SnS has also
received good attention in different fields including photoelec-
trochemical cells, lithium-ion batteries, infra-red detectors,
etc. Based on its recent advancements a few of them are briefly
described below.
6.2.1. Photoelectrochemical Cells
Polycrystalline tin monosulphide samples were prepared by
passing H2S through an acidic solution of stannous chloride
FIG. 53. Current density vs. voltage characteristics under AM
1.5 for the Cd0.87Zn0.13S/SnS cell (inset shows the schematic
representation of the fabricated solar cell structure). (Ó Elsev-
ier. Reprinted with permission from Elsevier.119 Permission to
reuse must be obtained from the rightsholder.)
and their photoelectrochemical behavior were studied in Fe3C/
Fe2C, Ce4C/Ce3C, and I2/I¡ redox couples.13 As compared to
other electrolytes (Table 7), the SnS samples showed a high
photocurrent with Ce4C/Ce3C electrolyte, probably due to the
formation of a maximum band bending with this redox system.
From the cyclic voltammetric studies it is revealed that the
SnS remains stable against photocorrosion in the Ce4C/Ce3C
redox couple over a period of 60 h. Further, photoelectro-
chemical (PEC) device was fabricated with the configuration
of SnS/Ce4C, Ce3C/Pt and studied under the light intensity of
12 mW cm¡2. I–V characteristic plot of the device is shown in
Figure 56a and its photoconversion efficiency is found to be
0.63%.
Subramanian et al. also fabricated PEC solar cell devi-
ces using cathodic electrodeposited SnS films with the con-
figuration of p-SnSjFe3C, Fe2CjPt and found a short-circuit
current density of 0.65 mA cm¡2 and open-circuit voltage
of 320 mV under 100 mW cm¡2 illumination.82 The over-
all light conversion efficiency for this device is found to
be 0.54%. The same group has examined the performance
of PEC by fabricating the cells with as-grown SnS films
by brush plating method and vacuum annealed films.11 The
photocurrent versus photovoltage curves of the cells under
illumination of 100 mW cm¡2 light are shown in Fig-
ure 56b. The conversion efficiency of the PEC cell fabri-
cated with as-deposited SnS film is very low, 0.21%,
which is probably due to the high series resistance (Rs) of
200 V and low shunt resistance (Rsh). Upon using annealed
SnS films, the PEC conversion efficiency of the device is
increased to 0.51%. This improved efficiency is attributed
to the decrease in Rs and substantial increase in Rsh value.
Further, a considerable improvement in the conversion effi-
ciency (»0.63%) of the device has been obtained by
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FIG. 54. Current vs. voltage characteristics of three different
photovoltaic structures of (a) CdS/SnS, (b) CdS/SnS/CuS, and
(c) CdS/SnS/Cu2SnS2. (Ó Elsevier. Reprinted with permission
from Elsevier.120 Permission to reuse must be obtained from
the rightsholder.)
photo-etching of vacuum annealed p-SnS films in 0.1 M
FeCl3–FeCl2, 0.05M H2SO4 solution for 30 s. This increase
is attributed mainly to the removal of unwanted material
over the film surface as well as in the grain boundaries by
the etching process.
6.2.2. Solid-State Batteries
Recently, solid-state batteries with a solid electrolyte have
received great concern due to their high reliability and safety.
TABLE 7
Photocurrent observed with different electrolytes for n-SnS (Ó Elsevier. Reprinted with permission from Elsevier.13 Permission
to reuse must be obtained from the rightsholder)
Electrolyte Photocurrent (mA cm¡2)
Ce4C/Ce3C(0.1 M in 0.5 M H2SO4)
Fe3C/Fe2C(0.1 M in 0.5 M H2SO4)
I2/I¡(0.1 M aqueous)
*NHE-Normal hydrogen electrode.
35
For example, In/LiCoO2 solid-state cells with Li2S–P2S5 solid
electrolyte exhibited excellent rechargeable performance with
high capacity and excellent cyclability at RT.124 In this regard,
novel tin-sulfide based compounds have considered as an
appropriate negative electrode with a suitable sulfide solid
electrolytes. Among other tin-sulfide compounds, SnS
becomes more prominent due to its excessive electron
exchangeability. As result, there have been a few reports on
the development of SnS-based solid-state lithium batteries,
which are briefly reviewed below.
Hayashi et al. developed SnS-based amorphous electro-
des by mixing 80 mole% of SnS and 20 mole% of P2S5
by mechanical milling technique.125 Then, the solid-state
cells with SnS, SnS-P2S5 have been fabricated by using
80Li2S.20P2S5 as electrolyte. Here, P2S5 sulfide used as a
continuous network former between both the materials.
The charge-discharge curves of Li-In/80SnS¢20P2S5 cells
have higher potential than those of Li-In/SnS based cells,
see Figure 57a. The charge and discharge capacities for
first cell are about 1070 and 590 mA h g¡1, whereas for
second cell these are about 720 and 310 mA h g¡1. On
the other hand, the discharge capacity of 80SnS¢20P2S5
based cells is 1.5 times higher than that of conventional
graphite anode materials used in commercialized lithium
ion secondary batteries. Thus, the addition of P2S5 to SnS
strongly enhances the reversible capacity of the cells. The
cycling performance of measured discharge capacity for
two typical cells is shown in Figure 57b. The discharge
capacity of both the cells gradually decreased with increas-
ing of cycling number. However, even after 50 cycles
these cells showed considerably high capacity of about
400 and 270 mA h g¡1. The same group also fabricated
Li-In/67SnS¢33P2S5 and studied its performance by using
80Li2S.20P2S5 as electrolyte.126 The charge capacity of
the cell with the 67SnS.33P2S5 glass is found to be
1070 mA h g¡1. The better performance of the
67SnS¢33P2S5-based cell is probably attributed to the
establishment of continuous LiC conduction paths by the
self-formed high LiC ion conductive Li2S–P2S5 matrix
around Sn nanoparticles.
Aso et al. developed SnS nanostructures-based solid-
state cells with the configuration of Li-In/80Li2S3.20P2S5/
SnS (different nanostructures) and their charge-discharge
Eredox (V vs. NHE*)
312 C1.42
143.8 C0.71
60.7 C0.31
 36 N. KOTEESWARA REDDY ET AL.
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FIG. 55. Current vs. voltage characteristics of SnS/CdS junction (a) before and (b) after CdCl2 treatment and (c) spectral
response of the treated heterojunction (Ó Elsevier. Reprinted with permission from Elsevier.121 Permission to reuse must be
obtained from the rightsholder.); (d) Current density-voltage (J–V) plot of the SnS/TiO2 cell in the dark and under 100 mW
cm¡2 illumination (the inset by SEM shows that cross-sectional image of the structure based on SnS on TiO2). (Ó Elsevier.
Reprinted with permission from Elsevier.123 Permission to reuse must be obtained from the rightsholder.)

curves under the current density of 0.13 mA cm¡2 at 25
C
are shown in Figure 58.127 Here, all the cells were
discharged and then charged in the voltage range from
FIG. 56. (a) Output power curve of the n-SnS electrode under
the incident light intensity of 12 mW (Ó Elsevier. Reprinted
with permission from Elsevier.13 Permission to reuse must be
obtained from the rightsholder.) and (b) plots of power output
characteristics for a typical p-SnS/Fe3C, Fe2C/Pt PEC solar
cell. (Ó Elsevier. Reprinted with permission from Elsevier.11
Permission to reuse must be obtained from the rightsholder.)
0–2.0 V (vs. Li). The cells using SnS particles with short
needle, plate, and long needle, respectively, showed the
initial discharge capacities of 1090, 880, and 1000 mA h
g¡1, these are slightly low compared to theoretical capacity
is ca. 1140 mA h g¡1. All the cells exhibited the higher
initial discharge capacity than the cell with mechanically
milled SnS particles with micrometer-size, 720 mA h g¡1.
The increase of the initial discharge capacity with the all-
solid-state cells using prepared SnS particles is attributable
to decreasing the particle size. The initial discharge capac-
ity of the all-solid-state cell using needlelike SnS particles
as an active material was larger than that of the cell with
plate like SnS particles. In addition, the cell using SnS par-
ticles with short needle retained the discharge capacity of
620 mA h g¡1 after 15 cycles under the current density of
0.13 mA cm¡2 at 25
C. This result suggests that the use of
needlelike particles as an active material improves the
solid-solid interface in composite electrodes and forms a
continuous lithium ion conducting paths in composite elec-
trodes. Thus, the one-dimensional structure of needlelike
particles as an active material is probably favorable in all-
solid-state cells.
 REVIEW ON TIN SULFIDE MATERIAL
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FIG. 57. (a) Charge–discharge curves of all-solid-state cells
Li–In/80SnS¢20P2S5 and Li–In/SnS at the 1st cycle with
80Li2S¢20P2S5 glass-ceramic solid electrolyte and (b) cycling
performance on discharge capacity for the all-solid-state cells
using the 80SnS¢20P2S5 and SnS electrodes. (Ó Elsevier.
Reprinted with permission from Elsevier.126 Permission to
reuse must be obtained from the rightsholder.)
7. SUMMARY WITH FUTURE ISSUES
In this article, we have reported a brief review on the
synthesis of SnS material in the form of bulk, thin films,
and nanostructures using different synthetic techniques
(chemical and physical vapor deposition methods) and their
physical properties. A brief description about all these syn-
thetic methods and optimized deposition conditions for the
growth of stiochiometric and single phase SnS structures is
presented. The variation of physical properties of SnS struc-
tures including structure, composition, electrical and optical
properties with the change of growth or deposition parame-
ters are also reported. Finally, we have also highlighted the
37
FIG. 58. Initial charge-discharge curves of the all-solid-state
cells Li-In/80Li2S.20P2S5/SnS with different morphologies.
(Ó American Chemical Society. Reprinted with permission
from American Chemical Society.128 Permission to reuse must
be obtained from the rightsholder.)
recent achievements in SnS structures based device applica-
tions including photovoltaics, photoelectrochemical cells,
and solid-state lithium batteries.
The basic properties of SnS compound reveal that the
crystal structure of SnS is considerably stable over a large
temperature range (4–873 K) as a low symmetric disor-
dered orthorhombic structure. However, with the increase
of surrounding temperature, its structure gradually changes
towards high symmetric-ordered tetragonal structure. The
SnS structures possess both indirect and direct band gaps
but the band gaps of disordered structures are slightly
higher than the ordered ones. These properties strongly
emphasize that SnS structures have become one of the
alternative candidates in the field of science and technol-
ogy as active component for various device applications.
The above discussions show that SnS can be synthesized in
any form including single crystals and thin films (amorphous or
polycrystalline) by using all most all well-established techniques
starting from low-cost and low temperature methods to higher
cost capital intensive techniques. The quality of SnS structures
can also be easily tuned by changing the growth or deposition
conditions of the associated technique. Moreover, without dis-
turbing the crystal structure, the optical and electrical properties
of SnS can be tailored through various external post-treatments
including thermal, chemical and plasma ions routes.
Even though there have been good progress in the synthesis
and characterization SnS structures, several key challenges are
still remain as crucial issues that have to be overcome for the
 38 N. KOTEESWARA REDDY ET AL.
realization of its potential applications in devices. A few
important key challenges about SnS thin films and devices are
given below.
Downloaded by [Humboldt-Universit&auml;t zu Berlin Universit&auml;tsbibliothek], [Koteeswara Reddy Nandanapalli] at 00:25 27 August 2015
A. The as-deposited SnS films exhibited stable structural
properties along with good chemically stoichiometry and
optical properties. Surprisingly the SnS films developed
by various methods suffer a lot with high resistance, which
is in the order of kilo to mega Ohms. Thus, it is very cru-
cial to realize good quality and low-resistive films for the
development of efficient devices.
B. Although there have been a few reports on the develop-
ment of low-resistive SnS films exclusively with thermal
treatment, still the realized lowest resistance for SnS films
is in the order of kilo Ohms. Therefore, systematic investi-
gations on the realization of low-resistive films have been
taken up by post treatment of SnS films either with heat,
chemical, or plasma treatment.
C. It is well known that by using appropriate substrate and/or
suitable layer deposited substrate, high-quality SnS films
can be developed. Thus, it could be more appropriate to
grow or deposit SnS films on an appropriate buffer layer
coated substrate.
D. An alternative to these methods, low-resistive SnS films
can also be realized by doping of suitable p-type dopants.
E. SnS films crystallized predominantly in two orientations
such as (111) and (010) depending on growth conditions
and have been exhibited different surface morphologies.
Thus, it has to be addressed since the physical properties
of SnS films strongly depend on morphology and crystal
structure, all of which require significant further research.
F. Regards to photovoltaic applications, though it received
considerable attention, still the device performance is very
poor. Thus, further studies are required to improve the cur-
rent density and efficiency. This could be achieved by
adopting good quality and highly conductive SnS films.
FUNDING
Dr. N. K. Reddy wishes to acknowledge CSIR for the sanc-
tion of Senior Research Associateship under the scheme of
Scientist’s pool (No. 13(8525-A) 2011-Pool). Dr. M. Devika
wishes to acknowledge UGC for the sanction of Dr. D.S.
Kothari Postdoctoral fellowship (No. F.4-2/2006(BSR)/13-
703/2012(BSR)). Prof. Gopal wishes to thank Indian National
Science Academy (INSA) for honorary scientific position.
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