Article

pubs.acs.org/JPCC

Direct Synthesis of Single-Phase p‑Type SnS by Electrodeposition

from a Dicyanamide Ionic Liquid at High Temperature for Thin Film
Solar Cells
Marc Steichen,*,† Rabie Djemour,† Levent Gütay,† Jérôme Guillot,‡ Susanne Siebentritt,†
and Phillip J. Dale†
†
Laboratory for Photovoltaics, University of Luxembourg, 41 rue du Brill, L-4422 Belvaux, Luxembourg
‡
Département de Science et Analyse des Matériaux, Centre de Recherche Public Gabriel Lippmann, 41 rue du Brill, L-4422 Belvaux,
Luxembourg
*
S Supporting Information

ABSTRACT: Thin film solar cells based on nontoxic and earth-abundant elements are
necessary for future-generation photovoltaic devices. Tin monosulfide is a promising candidate
that can be used as an absorber material in thin film photovoltaics. In this paper, we introduce
the direct synthesis of stoichiometric and single-phase p-type SnS films via the
electrodeposition from the ionic liquid 1-butyl-3-methylimidazolium dicyanamide ([C4mim]-
[DCA]) containing elemental sulfur and SnCl2 at high temperature. The electrochemical
behavior is studied, and a deposition mechanism of tin monosulfide from the elemental sulfur
saturated ionic liquid is proposed. XRD, XPS, and Raman spectroscopy demonstrate the sole
presence of α-SnS without any secondary sulfide phases (e.g., SnS2, Sn2S3). XPS depth
profiling confirmed the phase purity and disproved the presence of organic contamination in
the as-deposited films. Photoelectrochemical measurements affirmed the p-type conductivity
of the SnS films. The as-deposited layers have an indirect optical band gap at 1.17 eV and high
optical absorption (α ≥ 104 cm−1) at photon energy above 1.4 eV. First solar cells with a
standard thin film substrate cell configuration are presented.

1. INTRODUCTION Various formation methods have been used to grow SnS

Cost-effective, sustainable, and environmentally friendly
absorber materials are required for thin film photovoltaic
(PV) technologies to establish as a major energy supplier with
terawatt production scale for a low-carbon future.1 The two
most promising thin film PV materials CdTe and Cu(In,Ga)Se2
could be limited by the scarcity and supply issues of indium and
tellurium, restricting large-scale production and increasing the
production costs.2 New earth-abundant materials could allow
significantly decreasing the costs per kilowatt hour. The
quaternary Cu2ZnSnS4 is such a promising material allowing
the fabrication of efficient solar cells.3 However, recent
investigations showed issues related to its stability along with
the presence of secondary phases detrimental for solar cell
performances.4,5 For these reasons, simpler binary absorber
materials have been targeted as possible candidates for future
thin film PV applications. Tin monosulfide (tin(II) sulfide, α-
SnS), composed solely of nontoxic and earth-abundant
elements, is such a potential material and presents suitable
properties for thin film PV applications: SnS has an indirect
band gap at around 1.1 eV and a high absorption coefficient (α
> 104 cm−1) above the direct band gap at 1.3 eV.6−9 Further, it
shows intrinsic p-type conductivity and appropriate charge
carrier concentrations of 1013−1016 cm−3.10−12 Despite these
properties, SnS-based thin film solar cells have only reached low
power conversion efficiencies with a maximum of 1.3%.7
absorber layers. The first deposition methods are based on
vacuum and thermal techniques, such as electron beam
evaporation,13 thermal evaporation,14,15 RF sputtering,16 spray
pyrolysis,7,17 chemical vapor deposition18,19 (CVD), and atomic
layer deposition12 (ALD). The second deposition route
involves solution-based techniques, such as chemical bath
deposition,20 successive ionic layer adsorption and reaction21
(SILAR), and electrodeposition.9,22−30 Besides the formation of
the orthorhombic SnS phase, the secondary sulfide phases SnS2
and Sn2S3 are often codeposited.14,19,23,31 The incorporation of
these secondary phases is undesired, as they are n-type
semiconductors and are thus detrimental for the p−n
heterojunction formation in the solar cells. High-temperature
nonequilibrium techniques are restricted by the high vapor
pressure of sulfur, which evaporates from the deposits, leaving
behind nonstoichiometric films. Nevertheless, pure SnS films
can be formed at high deposition temperatures depending on
the growth method.12,17,18,32 Electrodeposition is an interesting
low-cost and low-energy growth method for chalcogenide
absorber layers33 as it is compatible with large-scale production
and economical in material usage. The electrochemical
Received: November 23, 2012
Revised: February 11, 2013
Published: February 11, 2013

© 2013 American Chemical Society 4383 dx.doi.org/10.1021/jp311552g | J. Phys. Chem. C 2013, 117, 4383−4393
The Journal of Physical Chemistry C
synthesis of tin monosulfide in aqueous solutions suffers from
the commonly encountered issues in this media; Sn2+ can be
oxidized to Sn4+, leading to the formation of secondary SnS2
and Sn2S3 phases,22,23 and the traces of dissolved oxygen in
nonbuffered electrolytes results in the coformation of stable tin
oxide phases.9,34 Recently, Mathews et al.23 have reported on
the electrochemical synthesis of SnS from an aqueous solution
containing SnCl2 and Na2S2O3 on FTO-coated glass at pH 2.5
and 45 °C. Pulse electrodeposition was used to dissolve any
weakly bonded SnS and Sn formed during the deposition
process. Crystalline orthorhombic SnS was grown in the
presence of secondary tin sulfide phases. Brownson et al.25,35
investigated the galvanostatic electrodeposition of tin mono-
sulfide from an aqueous solution of SnCl2 and Na2S2O3
containing a tartaric acid additive on FTO-coated glass at pH
1.5−2.5 and temperatures of 50−90 °C. The addition of tartaric
acid resulted in the formation of a new polymorph (δ-SnS),
which can be transformed into α-SnS by thermal annealing at T
> 350 °C.
High deposition temperatures are expected to result in the
growth of chalcogenide films with enhanced crystal quality. We
have recently reported on the direct potentiostatic electro-
deposition of p-type trigonal selenium from the ionic liquid 1-
ethyl-3-methylimidazolium tetrafluoroborate/chloride at tem-
peratures above 100 °C36 and demonstrated that the
crystallinity of the t-Se was improved by increasing the
deposition temperature from 100 to 160 °C. Ionic liquids
(IL) are defined as liquids consisting of molecular cations and
anions that have a melting point below 100 °C.37,38 ILs exhibit
intrinsic high thermal stability and give the opportunity to
deposit at temperatures in excess of those possible in water (T
≥ 100 °C), allowing the direct synthesis of crystalline device-
quality PV chalcogenide absorbers without further thermal
annealing requirements.33
Boros et al. have shown that ionic liquids are good solvents
for elemental chalcogens.39 The authors showed that the
solubility of elemental sulfur strongly dependent on the Lewis
basicity and the nucleophilicity of the anion. Manan et al. have
recently investigated the electrochemistry of elemental sulfur
and polysulfides in several ionic liquids on Au, Pt, and GC
electrodes at room temperature.40 In-situ UV−vis spectroscopy
in elemental sulfur saturated 1-butyl-3-methylimidazolium
dicyanamide allowed to identify S62− and S42− as the main
cathodic species at room temperature.
Only a few reports on the electrodeposition of sulfide
compound semiconductors from ionic liquids are presented to
date. Dale et al.41 have explored the electrodeposition of n-type
CdS and ZnS films from the deep eutectic based ionic liquid
chlorine chloride:urea. Izgorodin et al.42 have studied the
electrodeposition of thin CdS thin films on FTO coated glass
from methyltributylphosphonium tosylate containing Na2S2O3
and CdCl2 at 130−150 °C. The authors proposed the direct
reduction of S2O32− to S2−, which then reacts with Cd2+ to form
CdS. Elemental sulfur could not be directly used as sulfide
precursor as too negative potentials were needed for the
reduction in the phosphonium ionic liquid. Very recently, Chen
et al.43 demonstrated the electrodeposition of CuS from the
ionic liquid 1-ethyl-3-methylimidazolium bis-
(trifluoromethanesulfonyl imide) ([C2mim][Tf2N]) containing
Cu(Tf2N)2 and elemental sulfur on Pt at high temperature (T
≥ 120 °C). Copper(II) sulfide films have been formed at low
overpotential (E = +0.25 V vs Ag) in the regime of Cu0
deposition and positive of the sulfur reduction. So far, no p-
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type sulfide semiconductors have been formed by electro-
deposition from ionic liquids.
In this report, we present the direct electrochemical synthesis
of stoichiometric and single-phase p-type SnS thin films from
the ionic liquid 1-butyl-3-methylimidazolium dicyanamide
([C4mim][DCA]) containing elemental sulfur and SnCl2 on
Mo-coated glass at temperatures between 80 and 120 °C. The
SnS films have been characterized for their elemental
composition, surface morphology, crystal structure, phase
purity, and optoelectronic properties. First, SnS thin film
solar cells have shown that the direct electrochemical synthesis
route of tin monosulfide absorbers from ionic liquids at high
temperature have potential for future low-cost PV applications.
2. EXPERIMENTAL SECTION
2.1. Reagents and Materials. Anhydrous SnCl2 (Alfa
Aesar, 99.995%) and elemental sulfur (Alfa Aesar, 99.999%)
were used as received. The ionic liquid 1-butyl-3-methylimida-
zolium dicyanamide, [C4mim][DCA], was purchased from Io-
li-tec (Germany) in the highest available purity (>99%). The
solvent was further purified prior to usage under vacuum (10−3
bar) together with P2O5 (Sigma-Aldrich) desiccant for 48 h to
reduce water levels below 100 ppm, determined by coulometric
Karl Fischer titration. All chemicals have been handled in a
nitrogen-filled glovebox (MBraun Unilab) with water and
oxygen levels below 1 ppm.
The S8-saturated deposition baths were prepared by
dissolving elemental sulfur together with SnCl2 at 100 °C.
The mixture was then stirred for 2 h at 100 °C and left
overnight at room temperature. Some of the S8 remained
undissolved and was kept in the electrochemical cell to ensure
the saturation of the deposition bath. The solution was yellow-
orange, and the saturation concentration of elemental sulfur in
[C4mim][DCA] was estimated to be 10 mM by successive
addition experiments in agreement with reported values.40
2.2. Electrochemical Deposition and Characterization
of SnS Thin Films. The electrochemical experiments were
performed in the glovebox in a thermally controlled three-
electrode cell (±2 °C), connected to an Ecochemie μAutolab
type III potentiostat. The counter electrode was a large surface
platinum foil, and the reference electrode was a silver wire
directly immersed in the ionic liquid. The working electrode
consisted of a Mo layer sputtered on soda lime glass with a
geometrical surface area of 2 × 2 cm2. The cathodic
electrochemical synthesis of the SnS films was performed
under potentiostatic control at temperatures between 80 and
120 °C. Prior to use, the substrates were etched in an aqueous
30% ammonia solution for 5 min, ultrasonically cleaned in
water and ethanol, and dried under a nitrogen flow. After the
deposition, the films were allowed to naturally cool to room
temperature and were sequentially washed with ultrapure water
and ethanol to remove the remaining ionic liquid and dried
under nitrogen.
X-ray diffraction (XRD) measurements were collected on a
Bruker Discover D8 diffractometer with a Cu Kα1/2 source (λα1
= 1.54056 Å) and a scintillation detector in grazing incidence
configuration (3°). Scanning electron microscopy (SEM) was
performed on a Hitachi SU-70 equipped with an Oxford
Instruments INCA X-MAX analyzer for energy-dispersive X-ray
(EDX) and wavelength-dispersive X-ray (WDX) spectroscopy
to distinguish the overlapping S Kα and Mo Lα peaks. Raman
spectroscopy was performed on a confocal home-built setup
equipped with a piezo-element for scanning measurements. All
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Raman measurements were line scans of 10 μm performed with

an excitation wavelength of 514 nm at 2 mW. The excitation
diameter of the laser area is 1 μm. The Raman analysis depth is
estimated to be 100 nm, based on the calculated absorption
coefficient (section 3.6.2.).
X-ray photoelectron spectroscopy (XPS) analyses were
realized on a Kratos Axis-Ultra DLD instrument using a
monochromatic Al Kα X-ray source (hν = 1486.6 eV, 150 W)
at a pass energy of 160 and 20 eV for survey and high-
resolution spectra, respectively. In order to obtain depth
profiles, the samples were etched prior to the analysis using an
Ar beam (3 kV, 0.2 mA) at an incident angle of 45°. The XPS
analysis spot was 110 μm in diameter.
Photoelectrochemical measurements were carried out in a
three-electrode setup in 0.2 M Eu(NO3)3 aqueous solution with
platinum counter and Ag|AgCl (sat.) reference electrodes. The
absorber layers were illuminated with a white light LED source
chopped at constant frequency on a home-built apparatus
during potential sweep and potentiostatic measurements.
The optical absorption properties of the samples were
determined by optical transmission measurements, performed
on a PerkinElmer Lambda 950 UV−vis spectrometer equipped
with an Ulbricht sphere. The recorded optical transmission data
were evaluated by an optical modeling tool kit in the program
Diplot44 as described in detail here.45 The modeling includes
the optical absorption behavior of the absorber material as such
and the geometrical properties and structure of the sample.
After the electrodeposition of the p-type SnS absorber layer,
photovoltaic devices were completed by chemical bath
deposition (CBD) of a ca. 50 nm thick CdS buffer layer,
followed by radio-frequency (RF) sputtering of an intrinsic
ZnO (i-ZnO) layer and a n-type Al2O3-doped ZnO (Al:ZnO)
window layer. Finally, Ni−Al front contacts were formed on
top via e-beam evaporation.
The final device configuration is Mo/SnS/CdS/i-ZnO/ Figure 1. Cyclic voltammetry (CV) of the ionic liquid [C4mim]-
Al:ZnO/Ni−Al. Current−voltage (I−V) characteristics of the [DCA] containing (a) saturated S8, (b) 20 mM SnCl2, and (c)
devices have been measured on a home-built I−V setup, saturated S8−20 mM SnCl2 on a Mo electrode, T = 100 °C, vscan = 20
equipped with a halogen lamp as light source. Under mV s−1. Pt counter electrode, Ag pseudoreference electrodes. The
illumination, the system is calibrated to 100 mW cm−2 at 25 arrows indicate the scan direction.
°C. The devices have been further characterized by measure-
ments as a function of illumination wavelength to generate liquid at room temperature. In-situ UV−vis spectroscopy
external quantum efficiency (EQE) spectra. The EQE spectra showed that S62− is the main reduction product at c1 and
have been recorded on a home-built apparatus and allow the S42− is the main species formed at the cathodic peak c2 on Au
extraction of the bandgap of the SnS. electrode at room temperature. At this temperature, the ionic
liquid prevents the further dissociation reactions of the dianions
3. RESULTS AND DISCUSSION S62− and S42− into lower polysulfides Sx2− (x < 4). The
3.1. Cyclic Voltammetry Studies. To understand the formation of the blue radical S3•− is not observed in
electrochemistry of S8 and SnCl2 in [C4mim][DCA] at high [C4mim][DCA] at room temperature, contrary to reports
temperature, cyclic voltammetry (CV) studies have been from other ionic liquids39 and molecular solvents, such as
performed. Figure 1 shows the CV of the ionic liquid dimethylformamide46 and acetonitrile,47 where the decom-
[C4mim][DCA] containing (a) saturated S8, (b) 20 mM position of S42− into S3•− and other Sx2− (x < 4) is observed.
SnCl2, and (c) saturated S8−20 mM SnCl2 on a Mo electrode The coloration of the S8-saturated ionic liquid [C4mim][DCA]
at 100 °C. The CV in Figure 1a is started at the open circuit is yellow-orange at 100 °C; thus, the formation of large
potential (OCP) at +0.05 V and scanned into the cathodic amounts of the radical S3•− is also excluded at higher
direction until the turning potential at −1.2 V with a scan rate temperatures.
of 20 mV s−1. Two distinct reduction peaks c1 and c2 are clearly Figure 1b presents the CV of [C4mim][DCA] containing 20
observed at −0.33 and −0.54 V, respectively. On the backward mM SnCl2 on a Mo at 100 °C. The potential is scanned in the
scan, two anodic current peaks a2 and a1 are recorded at −0.37 negative direction from the OCP at +0.05 V, and deposition of
and +0.01 V. metallic tin (peak cSn) occurs at −0.63 V, which is more
The anodic peak a1 is related to the cathodic peak c1 (and a2 negative than the reduction waves of elemental sulfur under the
is related to c2) as indicated by experiments realized with same conditions (curve a). On the reverse scan, a typical
different cathodic turning potentials. Recently, Manan et al.40 nucleation loop is observed and is followed by the stripping
studied the electrochemistry of elemental sulfur in this ionic peak at −0.16 V, presenting a shoulder at −0.30 V, which could
4385 dx.doi.org/10.1021/jp311552g | J. Phys. Chem. C 2013, 117, 4383−4393
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be explained by different tin speciation during the stripping
process.48 The further oxidation of Sn2+ to Sn4+ is not observed
on the Mo electrode. Control experiments have been
performed on platinum (Pt) and glassy carbon (GC)
electrodes; as in the case of Mo, no further oxidation of Sn2+
to Sn4+ was recorded on Pt. However, large oxidation currents
were observed on a GC electrode (cf. Supporting Information).
These results agree with previous studies48 realized in a similar
ionic liquid [C2mim][DCA]−50 mM SnCl2 at 40 °C, where
the oxidation of Sn2+ was absent on Pt, but was present on GC
electrodes.
Figure 1c shows the CV of the S8-saturated ionic liquid
[C4mim][DCA] containing 20 mM SnCl2 on the Mo electrode
at 100 °C. Starting the cathodic scan from the OCP at +0.10 V,
a first cathodic wave is observed at −0.40 V similar to the
response c1 in the CV of Figure 1a. A second large cathodic
current cSnS is recorded at −0.67 V. On the backward scan, no
stripping peak is recorded, suggesting the formation of a stable
sulfide compound.
3.2. Electrochemical Synthesis and Characterization
of As-Deposited SnS Thin Films. On the basis of the above-
mentioned CV studies, the electrodeposition of SnS films has
been performed under potentiostatic control from S8-saturated
[C4mim][DCA] containing 20 mM SnCl2 on Mo at 100 °C.
Table 1 shows the WDX/EDX analysis of films deposited in the
Table 1. WDX/EDX Analysis of the As-Deposited Thin
Films Deposited on Mo from [C4mim][DCA]−S8 sat.−20
mM SnCl2 at Different Potentials for 30 min at 100 °Ca
Edep (V) WDX/EDX (at. %) Sn/S XRD detected phases
−0.5 2.49 ± 0.09 SnS, Sn
−0.6 1.25 ± 0.08 SnS, Sn
−0.7 0.98 ± 0.05 SnS
−0.8 1.05 ± 0.06 SnS
−0.9 5.1 ± 0.1 Sn, SnS
a higher temperatures are also favorable for crystal growth during
SEM images are provided as Supporting Information.
potential range from −0.5 to −0.9 V. Stoichiometric films are
grown at −0.8 V < E < −0.7 V in the region of the peak cSnS.
On either side of this potential range, Sn0 is incorporated in the
films.
At lower applied deposition potentials (E ≥ −0.6 V) the
polysulfide species formed at the peak c1 do not formed rapidly
enough to participate in the formation of pure SnS films. On
the other side of the stoichiomentric SnS potential range, the
Figure 2. (A) XRD diffractograms of SnS films deposited at (a) E = −0.7 V and (b) E = −0.8 V from [C4mim][DCA]−sat. S8−20 mM SnCl2 on
Mo (∗). The JCPDS pattern 39-0354 (Herzenbergite SnS) is included for comparison. (B) SEM top-view and cross-section images of the two
corresponding SnS films.
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films deposited at E ≤ −0.8 V are also very Sn-rich. Even
though, electroactive sulfides are formed at these potentials;
their formation rate is too low to keep up with the Sn metal
deposition, which is favored compared to the kinetically
hindered SnS compound formation reaction.49
Figure 2 shows (A) the XRD diffractograms and (B) the
corresponding SEM top-view and cross-section images of the
as-deposited SnS films formed at (a) E = −0.7 V and (b) E =
−0.8 V.
The reference pattern (JCPDS card 39-0354) of ortho-
rhombic SnS with the lattice constants a = 0.4329 nm, b =
1.1192 nm, and c = 0.3984 nm is included for comparison. For
both samples, all the diffraction peaks correspond to the
orthorhombic SnS phase. The average coherence lengths D of
the crystals have been estimated from the main (111) Bragg
peak of orthorhombic SnS using the Scherrer formula:
kλ
D=
β cos(θ)
where D is the average coherence length (nm), k = 0.9 is the
shape factor (spherical grain shape), λ = 1.540 56 Å is the
wavelength of the incident radiation, β is the full width at half-
maximum fwhm (rad), and θ is the Bragg angle (rad). The
FWHMs have been determined by fitting Gaussian profile
peaks to the experimental data. As the crystals are not exactly of
spherical symmetry, the values have to be considered as
approximations. Similar average coherence length D = 20.5 ±
0.4 nm have been extracted for both films. These values are
smaller than the average grain sizes observed in the SEM,
showing that the SnS crystallites are subject to crystal defects.
However, the estimated average coherence lengths are
significantly higher than values previously reported for
electrodeposited SnS films from aqueous23 and nonaqueous26
solutions and are close to the average grain size values reported
by thin SnS films grown by ALD at 120 °C,12 showing that
electrodeposition. The SEM top-view image in Figure 2Ba
shows the SnS film deposited at E = −0.7 V. The film presents
a good surface coverage. The film is compact and exposes no
visible pinholes to the Mo back-contact electrode. The film is
formed by larger clusters composed of agglomerated
orthorhombic SnS crystals with grain sizes ranging from 100
to 150 nm. The cross-section image confirms these
observations; uniformly dispersed and well-defined crystals
are visible throughout the 800 nm thick film to form a compact
single-phase SnS layer. The surface roughness of the layer is
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The Journal of Physical Chemistry C
Figure 3. (A) XRD diffractograms of three films deposited at different temperatures from [C4mim][DCA]−sat. S8−20 mM SnCl2 on Mo (∗). (B)
Corresponding high-resolution XRD of the main (111) Bragg peaks. The JCPDS patterns 39-0354 (Herzenbergite SnS) and 04 0673 (Sn) are
included for comparison.
estimated to be ∼100 nm. The films were adherent and brown-
matte black in appearance. The films deposited at E = −0.8 V
present a much rougher surface morphology and were black
and matte in appearance. Needle-like elongated, dendritic SnS
crystallites are randomly grown on the top surface. The cross-
sectional image adds more information to the growth of the
SnS layer. The dendritic morphology of the SnS crystals
observed in the top-view image of the film grown at −0.8 V is
confirmed; however, a compact, dense, and well-crystallized
SnS film of 500−600 nm is revealed on the Mo substrate.
This compact underlayer has been systematically observed
for all SnS films. In a first stage, after the initial nucleation on
the Mo surface, a thin compact SnS layer (cf. Supporting
Information) is quickly formed and covers the Mo electrode
surface completely after 1 min. Depending on the applied
overpotential, the SnS layer either continues to grow thicker
compactly (−0.7 V) or enters a dendritic growth regime (−0.8
V). The presence of the thin compact SnS layer at the early
growth stage can be explained by the fact that α-SnS is a p-type
semiconductor with several orders of magnitude fewer electrons
than a metal. The formation reaction for SnS is caused by a
reduction current, meaning that electrons are flowing from the
electrode to reduce the species in solution. The further
reduction of SnS onto a metallic electrode covered with SnS
nuclei will occur more rapidly on the bare metallic surface of
the electrode due to its disproportionally higher electron
density compared to the p-type SnS. Once the compact p-type
layer formed, the electrodeposition of SnS continues in a slower
second stage on the p-type film due to the lack of available
electrons for electrochemical reduction,50 as evidenced by the
low current densities in ambient light conditions (j ≈ 0.2 mA
cm−2). One way to generate more electrons in a p-type
semiconductor is to illuminate its surface with photons of
energies higher than the band gap. These photogenerated
electrons may then participate in the reduction reaction.
Complementary electrodeposition experiments were performed
under constant illumination (W = 100 W m−2) and showed
enhanced deposition current densities by a factor of 2 (j ≈ 0.4
mA cm−2).
3.3. Effect of Deposition Temperature. The influence of
the deposition temperature has been studied from S8-saturated
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[C4mim][DCA] containing 20 mM SnCl2 at constant over-
potentials. At T < 80 °C, no SnS could be grown, solely metallic
Sn0 was deposited. Only at T ≥ 80 °C was α-SnS formation
possible. As shown on the XRD diffractogram in Figure 3,
however, the codeposition of SnS with Sn was observed. At T =
100 °C, pure orthorhombic SnS films are confirmed by the
XRD analysis.
At a deposition temperature of 120 °C, well-crystallized α-
SnS was deposited; nevertheless, we have observed that the
deposition bath was unstable at T ≥ 120 °C. A yellow
amorphous SnSx precipitate formed after 1 h at these
temperatures, depleting the deposition solution of sulfur and
leading to the codeposition of Sn0 together with orthorhombic
SnS. No deposition of single-phase SnS films was possible at T
> 120 °C. The precipitation of colloidal SnS2 has been
previously reported in ethylene glycol of elemental sulfur and
SnCl2 at 70 °C.26 In comparison to this organic solvent,
[C4mim][DCA] appears to stabilize elemental sulfur better up
to 120 °C. At higher temperatures, the imidazolium cation may
undergo reactions with elemental sulfur in the presence of a
base, as reported previously.51
Table 2 summarizes the estimated coherence length D from
the main Bragg peak (111) of the SnS films deposited at 80,
Table 2. Evaluation of the As-Deposited Phases and
Coherence Length D of SnS on Mo from [C4mim][DCA]−
S8 sat.−20 mM SnCl2 at E = −0.7 V for 30 min at Different
Temperaturesa
Tdep (°C) XRD detected phases DSnS (nm)
80 SnS, Sn 15.1 ± 0.6
100 SnS 20.5 ± 0.4
120 SnS, Sn 25.0 ± 0.6
a
The evaluation is realized on the main (111) Bragg peak.
100, and 120 °C. As expected, the crystal quality of the SnS
crystals increases with temperature.
3.4. SnS Phase Purity and Film Contamination. The
unambiguous detection of minor secondary tin sulfide phases is
not straightforward by XRD due to the overlapping of several
Bragg peaks of SnS, SnS2, and Sn2S3.19 Raman spectroscopy has
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The Journal of Physical Chemistry C
been performed in order to assess the phase purity and lateral
uniformity of the as-deposited SnS films. Figure 4 shows the
Figure 4. Raman spectroscopy of a SnS film electrodeposited from
[C4mim][DCA]−sat. S8−20 mM SnCl2 on Mo at −0.7 V, T = 100
°C. The bar plots represent the measured relative peak intensities of
SnS, Sn2S3, and SnS2 single-crystals for comparison. (The intense
mode at 312 cm−1 of the SnS2 single crystal has been reduced by a
factor of 5 for clarity.)
characteristic Raman peaks at 97, 160, 191, 218, and 288 cm−1,
in agreement with single-phase orthorhombic SnS films
prepared by ALD12 and atmospheric pressure chemical vapor
deposition (APCVD).19 Raman line scans on the sample
surface did not show any lateral variations, confirming the
lateral homogeneity of the SnS thin film. Additional Raman
analysis has been performed on tin sulfide single crystals (SnS,
Sn2S3, and SnS2), and the relative peak intensities of these pure
single-crystalline materials are shown in Figure 4 for
comparison. The Raman peaks of the as-deposited SnS film
correspond very well with all the observed Raman modes
measured on the SnS single crystal.
No Raman peaks were observed at 307 and 312 cm−1, which
are the strongest modes for Sn2S3 and SnS2, respectively. For
clarity, the intense mode of SnS2 single crystal is reduced by a
factor of 5 in Figure 4. The relative high intensity of these
modes compared to those of SnS allows to conclude that no
secondary SnS2 and Sn2S3 phases are present and show that the
compact as-deposited SnS thin films prepared on Mo by the
direct electrochemical synthesis from S8-saturated [C4mim]-
[DCA] containing 20 mM SnCl2 at −0.7 V at 100 °C are pure,
single-phase orthorhombic SnS layers. This result shows
significant improvements over previously reports, where
secondary tin sulfide and oxide phases have been present in
the as-deposited films formed by electrodeposition from
aqueous media.23,34
X-ray photoelectron spectroscopy (XPS) analysis has been
performed to study the surface and bulk phase of the as-
deposited films. Figure 5Aa shows the survey spectrum of a
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stoichiometric SnS film from S8-saturated [C4mim][DCA]
containing 20 mM SnCl2 at −0.7 V at 100 °C. The binding
energies measured in the XPS analysis are standardized using
the C 1s signal as reference peak at 284.9 eV. The Sn 3d peaks
measured at 486.6 and 495.0 eV correspond to the binding
energy of Sn 3d5/2 and Sn 3d3/2, and the peak at a binding
energy of 161.1 eV corresponds to S 2p3/2 of tin monosulfide
(high-resolution spectrum in Figure 5Ab). These results are in
good agreement with reported values for pure SnS layers.12,23,29
No other XPS peaks at higher binding energies of tin oxide or
other tin sulfide phases were detected. The low binding energy
shoulders at 485.4 and 493.8 eV are attributed to metallic
Sn023,29 and are due to the partial loss of volatile sulfur under
ultrahigh vacuum in the XPS chamber. SnS(s) is in a pressure-
dependent equilibrium with Sn(s) and S2(g);5 sulfur evaporates
from the SnS surface in UHV, leaving metallic Sn0 on the film
surface.
XPS analysis has been performed on the as-deposited SnS
films in order to check that no organic contamination
originating from the ionic liquid has occurred. Figure 5Ba
shows representative XPS depth-profiling survey spectra of a
stoichiometric SnS thin film deposited on Mo from [C4mim]-
[DCA]−sat. S8−20 mM SnCl2 at E = −0.7 V and T = 100 °C.
The corresponding high-resolution scans of the C 1s and O 1s
signals are also represented in Figure 5Bb. O 1s and C 1s peaks
have only been detected at the surface of the SnS films due to
exposure to ambient air. After 800 s of Ar sputtering, no further
impurities were found in the bulk of the SnS layer (detection
limit of 0.5 at. %). The same trend was observed for nitrogen
contaminations. No additional signals originating from Cl, Ag
or Pt have been detected.
3.5. Electrochemical Growth Mechanism of SnS Thin
Films. In light of the above-mentioned studies, a mechanism
for the electrochemical formation of the SnS absorbers from
[C4mim][DCA]−S8 sat.−SnCl2 is proposed.
The polysulfide S42− is formed cathodically at E ≤ −0.6 V,
and the dissociation reactions by disproportionation are slow in
[C4mim][DCA] at room temperature.40 The disproportiona-
tion of elemental sulfur are thermally activated reactions52 (T >
80 °C). Thermal dissociation of sulfur by hemolytic scission
occurs at high temperatures.53 These findings are coherent with
our observations in the ionic liquid [C4mim][DCA] at elevated
temperatures. On the basis of our experiments, we propose that
the formation of the electroactive S2−, required for SnS
deposition, occurs via the electrochemical formation of S42−
followed by the thermally activated disproportionation by the
following mechanism:
2S4 2 − ⇔ S6 2 − + S2 2 −
3S2 2 − ⇔ 2S2 − + S4 2 −
The growth and the composition of the film are ultimately
controlled by the relative rates of the S2− formation and the
reduction of Sn2+ at the electrochemical interface. As presented
in section 3.3, the formation of S2− by the coupled
electrochemical reduction−dissociation reactions is only fast
enough at T ≥ 100 °C. At this temperature, stoichiometric
single-phase SnS films are grown without the codeposition of
metallic Sn. At lower temperatures, the reduction rate of Sn2+ to
Sn0 is too high compared to the S2− formation rate and mixed
SnS/Sn films are deposited. By increasing the temperature
above 120 °C, the dissociation rate of polysulfide in the ionic
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The Journal of Physical Chemistry C
Figure 5. (A) (a) XPS survey spectrum of a SnS film electrodeposited from [C4mim][DCA]−sat. S8−20 mM SnCl2 on Mo at −0.7 V and T = 100
°C. (A) (b) Corresponding high-resolution spectra of the Sn 3d peak and S 2p peak regions. (B) (a) XPS depth-profile spectra of the same SnS film
as a function of Ar sputtering. (B) (b) Corresponding high-resolution XPS spectra of the C 1s and O 1s peak regions.
liquid is very high and results in the formation of amorphous
SnSx precipitates, depleting the ionic liquid in sulfur.
The reduction potential of Sn2+ cations and the potential of
2−
S formation lie close together. Thus, the formation of tin
monosulfide could occur alternatively via two different
mechanisms: (1) The chalcogen can react with the first
deposited layer of metallic Sn0 and convert into SnS on the
surface. (2) The generated chalcogen reacts with Sn2+ cations at
the electrochemical interface to form SnS on the electrode
surface.
To better understand and discriminate between the two
mechanisms, we have investigated the growth of SnS on Sn
electrodes in a S8-saturated [C4mim][DCA] at 100 °C. The Sn
electrode was immersed in the liquid at OCP, and no reaction
with elemental sulfur was observed after 30 min. The same
observations have been made after applying a potential of −0.7
V to the tin electrode for 30 min; negligible amounts of SnS
have been formed in the S8-saturated [C4mim][DCA] at 100
°C. In contrast, when the same experiments were realized on a
Cu electrode instead of Sn, instantaneous formation of black
CuxS deposits have been observed at OCP in the S8-saturated
[C4mim][DCA] at 100 °C, confirming the results of Chen et
al.,43 who have very recently studied the electrodeposition of
CuS in the ionic liquid 1-ethyl-3-methylimidazolium bis-
(trifluoromethanesulfonyl imide) containing Cu(Tf2N)2 and
elemental sulfur on Pt electrodes at high temperature (T ≥ 120
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°C). Copper(II) sulfide was formed by the chemical reaction of
the first deposited Cu0 and the molecular sulfur dissolved in the
ionic liquid. These differences are in agreement with previous
reports on the sulfurization reaction of metals, which showed
that copper sulfide formation is 104 times faster than the
reaction of tin with sulfur.49 Accordingly, we have demon-
strated that the formation of SnS is not possible via this
reaction mechanism. Izgorodin et al.42 have concluded on a
similar reaction scheme for the electrodeposition of CdS thin
films on FTO-coated glass from the ionic liquid methyltribu-
tylphosphonium tosylate containing sodium thiosulfate as sulfur
precursor and CdCl2 at 130−150 °C. Analogically to our case,
the reduction potentials of Cd2+/Cd0 and S2O32−/S2− are close
together, and the formation reaction of CdS proceeded via the
reaction between S2− and Cd2+ at the electrode interface.
In summary, we can discard the SnS formation via path 1 and
conclude that the overall formation reaction of orthorhombic,
single-phase SnS in the S8-saturated [C4mim][DCA] ionic
liquid containing SnCl2 at high temperature is controlled by the
electrochemical reduction of S8 to S42− followed by the
thermally activated dissociation producing S2− anions, which
subsequently react with Sn2+ cations at the electrochemical
interface (int):
Sn int 2 + + Sint 2 − → SnSsurf
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The Journal of Physical Chemistry C
As evidenced in Figure 1, the oxidation of Sn2+ to Sn4+ is not
observed on Mo electrodes in [C4mim][DCA], in contrast to
GC electrodes (cf. Supporting Information). Tin is stable in the
(2+) oxidation state in this ionic liquid, contrary to aqueous
electrolytes54,55 where Sn2+ can be readily oxidized to Sn4+.
Thus, the deposition of pure, single-phase tin monosulfide is
possible, avoiding the formation of the secondary phases SnS2
and Sn2S3.
Potentiostatic depositions with lower [SnCl2] = 10 mM in
S8-saturated [C4mim][DCA] have revealed that the deposition
current is independent of the metal cation concentration,
confirming the proposed formation mechanism. As long as Sn2+
cations are present at high enough concentration ([Sn2+]int ≥
[S2−]int) at the electrochemical interface, the generation of
reactive S2− species is the rate-determining step of the overall
SnS formation reaction.
As shown, stoichiometric SnS is only formed in a narrow
voltage range between −0.7 and −0.8 V under potentiostatic
control. The rate of S2− formation is directly proportional to
the current density at constant temperature. For large-scale
production, galvanostatic electrodeposition on highly conduct-
ing substrates would allow the fine-tuning of the SnS growth by
controlling the rate of S2− generation. Current control and
careful deposition cell design would allow establishing a robust
deposition system for uniform, stoichiometric SnS thin films
from ionic liquids at high temperature on large area substrates.
3.6. Optoelectronic Characterization. 3.6.1. Photocon-
ductivity. Biased photoelectrochemical measurements under
chopped white light illumination of the as-deposited SnS layers
have been performed. In contact with an appropriate redox
electrolyte, a semiconductor film is expected to show a
rectifying diode behavior in the polarization region of the
minority charge carrier current flow. In the case of a p-type
semiconductor (minority electron charge carriers), this
behavior is expected at potentials negative of its flatband
potential. The direction of the photocurrent (anodic or
cathodic) allows the determination of the conductivity type.
For a p-type semiconductor under illumination, the photo-
generated electrons manifest as a cathodic photocurrent.
Figure 6 shows the photoelectrochemical behavior of an as-
deposited SnS thin film on Mo from [C4mim][DCA]−sat. S8−
20 mM SnCl2, E = −0.7 V and T = 100 °C. The sweep
voltammetry of the Mo/SnS electrode was performed in
contact with a 0.2 M Eu(NO3)3 aqueous electrolyte, scanning
from OCP = −0.07 V into the negative direction. The chopping
period was asymmetric (longer illumination period). The dark
current at OCP is low and increases gradually toward more
negative potentials, which can be related to the direct contact of
uncovered Mo with the redox electrolyte and the onset of the
hydrogen evolution reaction in the Eu(NO3)3 aqueous
electrolyte. During the illumination periods, negative photo-
currents are clearly seen in the cathodic direction, demonstrat-
ing the p-type photoconductivity of the as-deposited SnS layers.
The photocurrent increases with the cathodic polarization,
which is due to the increased band bending at the
semiconductor−electrolyte junction and the filling up of
surface traps, both of which allow the minority carriers to be
extracted more easily. The onset of the photocurrent response
is located at E ≈ −0.2 V. The inset of Figure 6 presents the
chopped photoelectrochemical behavior of the as-deposited
SnS film at a constant negative polarization of −0.6 V vs Ag|
AgCl sat. The measurement confirms the p-type photoresponse
of the as-deposited SnS thin films at negative polarization and
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Figure 6. Photoelectrochemical sweep voltammetry of a representative
SnS film in contact with a 0.2 M Eu3+ aqueous electrolyte under
chopped white illumination, vscan = 10 mV s−1, T = 25 °C. Inset shows
the corresponding photocurrent response at E = −0.6 V (vs Ag|AgCl
sat.).
shows that a constant photocurrent is measured over several
illumination periods. Sharp current−time transients during the
dark-light switching are observed and are characteristic for good
diode behaviors.
3.6.2. Optical Absorption Properties. The absorption
behavior of the as-deposited SnS films was determined by
optical transmission measurements and modeling of the
experimental data in Diplot.44 In Figure 7A, the optical
transmission spectrum of a ca. 300 nm thick SnS film is shown.
The black curve is the experimental data, and the red curve
shows the modeling results. The measured spectrum presents a
Fabry−Perot oscillation with its maximum at 0.83 eV. This
oscillation is best fitted with a refractive index of 2.35 and a film
thickness of 305 nm, which matches well the estimation of the
growth rate of the electrodeposition process in [C4mim]-
[DCA]−sat. S8−20 mM SnCl2 at −0.7 V and T = 100 °C after
15 min. The fitted curve shows the result of a model including
an indirect band gap Eg = 1.17 eV and Urbach energy of 50
meV. The experimental data of the as-deposited SnS film were
best fitted to this indirect transition model; i.e., the minimum of
the conduction band is not at the Γ point.
The extracted absorption coefficient is plotted as a function
of the photon energy in Figure 7B. Efficient absorption
coefficients α ≥ 104 cm−1 are observed at E ≥ 1.4 eV. These
values are consistent with the theoretical calculations performed
by Vidal et al.,8 who concluded that tin monosulfide has a 1.07
eV indirect band gap with an effective absorption onset located
0.4 eV higher. From the plot of the absorption coefficient in
Figure 7B, we can confirm very similar behavior of the as-
deposited SnS films from [C4mim][DCA]−sat. S8−20 mM
SnCl2. Effective absorption is achieved at E ≥ 1.5 eV, with
absorption coefficients of α ≥ 2 × 104 cm−1, which is sufficient
for complete light absorption in a typical 1 μm thick absorber
layer for thin film solar cells. Makinistian et al.6 have previously
used ab initio DFT calculations to compute the electronic band
structure and also determined an indirect band gap of 1.16 eV
with anisotropic behavior along the three main crystallographic
axes.
Experimentally, the indirect band gap of SnS has been
observed by several groups.13,16,26,56 Hartman et al.16 have
recently deposited SnS thin films by RF sputtering under
dx.doi.org/10.1021/jp311552g | J. Phys. Chem. C 2013, 117, 4383−4393
The Journal of Physical Chemistry C
Figure 7. (A) Optical transmission measurements (black) and
modeling (red) of a 300 nm thick, compact, single-phase SnS absorber
layer. (B) Absorption coefficient extracted from the model including
the indirect transition of the SnS layer.
various growth conditions. All the films showed indirect band
gaps in the range of 1.08−1.18 eV and α ≥ 2 × 104 cm−1 at E >
1.5 eV. Nonetheless, a large discrepancy still exists in the
literature on the interpretation of the electronic band structure
and the nature of the band gap in SnS absorbers, as several
reports used direct transition models to fit the absorption
coefficient. Band gap values ranging from 1.3 to 1.8 eV are
reported.
The optical absorption properties of the as-deposited SnS
absorber films from [C4mim][DCA]−sat. S8−SnCl2 seem
satisfactory with high absorption coefficients above 1.5 eV,
compatible for the application of the SnS films as absorbers in
PV devices.
3.7. SnS Thin Film Solar Cells. Complete solar cell devices
were realized in order to demonstrate the potential of the as-
deposited SnS films formed by the direct synthesis from the
ionic liquid [C4mim][DCA]−sat. S8−20 mM SnCl2 at high
temperature.
Figure 8A shows the external quantum efficiency (EQE)
spectrum of the best performing SnS solar cell. The spectrum
shows a maximum EQE of 30% at 520 nm and presents the
typical CdS absorption in the wavelength region below 500 nm.
The current decrease at long wavelengths above 550 nm is
characteristic of moderate absorption and transport properties
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Figure 8. (A) EQE spectrum of the best Mo/SnS/CdS/i-ZnO/
Al:ZnO/Ni−Al solar cell. (B) J−V characteristic curve of the
corresponding SnS device in the dark and under illumination. SnS
films electrodeposited from [C4mim][DCA]−sat. S8−20 mM SnCl2 at
−0.7 V and T = 100 °C.
of the absorber layer. The EQE measurements confirm the
optical absorption measurements.
Figure 8B shows the current density−voltage (J−V)
characteristics curve in the dark and under illumination of the
corresponding SnS device. The cell achieved a 0.17 ± 0.02%
total area power conversion efficiency with VOC = 155 ± 0.10
mV, JSC = 3.42 ± 0.80 mA cm−2, and FF = 31.8 ± 0.3% on a
total area of 0.20 ± 0.02 cm2. The errors are evaluated based on
the three best cells. Nevertheless a low shunt resistance Rp =
97.8 Ω cm2 around JSC is observed, lowering the power by
allowing alternative current paths between the cell’s front and
back. These losses can be due to absorber defects or/and metal
impurities present in the absorber layer. The series resistance of
the cell is RS = 1.44 Ω cm2.
Even though the performances are still low, the achieved
power conversion efficiencies are comparable with previously
reported values of 0.20% and 0.17% for SnS devices formed by
electrodeposition30 and sputtering,31 respectively. So far,
absorber films synthesized by spray pyrolysis7 gave the highest
reported efficiency for SnS based solar cells of 1.3%, with VOC =
260 mV, JSC = 9.6 mA cm−2, and FF = 53%.
dx.doi.org/10.1021/jp311552g | J. Phys. Chem. C 2013, 117, 4383−4393
The Journal of Physical Chemistry C
4. CONCLUSIONS
In summary, we have introduced a new low-cost methodology
for the direct synthesis of single-phase orthorhombic, p-type
SnS thin films from S8-saturated [C4mim][DCA] containing
SnCl2 at high temperature. The electrochemical behavior was
studied, and a mechanism of the growth of tin monosulfide was
proposed. The stoichiometry, composition, and morphology of
the thin films are controlled by the applied potential and the
deposition temperature. We conclude that the SnS formation
proceeds via the interfacial reaction between S2− and Sn2+. Tin
is stable under its (2+) oxidation state in [C4mim][DCA] and
allows the synthesis of single-phase tin monosulfide at high
temperature on Mo electrodes. XRD, XPS, and Raman
spectroscopy clearly demonstrated the sole presence of the
orthorhombic SnS without any secondary phases in the as-
deposited layers. XPS depth profiling confirmed that no carbon
and nitrogen impurities were incorporated in the deposits. The
as-deposited SnS films showed an indirect band gap at 1.17 eV
and efficient absorption above 104 cm−1 at photon energy
higher than 1.4 eV, in agreement with theoretical calculation of
SnS band structure.8 Although the photovoltaic device studies
are still preliminary, we have successfully demonstrated that the
as-deposited p-type tin monosulfide absorbers can be
successfully finalized into working solar cells with performances
comparable to other deposition methods.
Ongoing research focuses on the further development of the
direct electrochemical synthesis of SnS thin films from various
ionic liquids allowing the growth at temperatures above 200 °C
for photovoltaic applications.
■
ASSOCIATED CONTENT
* Supporting Information
S Sol. Energy Mater. Sol. Cells 2003, 80 (3), 297−303.
(1) SEM top-view images of films deposited at different
potentials; (2) SEM cross-section image of the initial compact
p-type SnS underlayer; (3) CVs of Mo, Pt, and GC electrodes
in [C4mim][DCA]−20 mM SnCl2 at 100 °C. This material is
available free of charge via the Internet at http://pubs.acs.org.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: marc.steichen@uni.lu.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The present work was realized under the financial support of
the Fonds National de la Recherche (F.N.R.) Luxembourg
within the framework of the CORE Junior Track Project C11/
MS/1211521. The authors also thank the CRP Gabriel
Lippmann for use of SEM/EDX and XRD. Joffrey Didierjean
is gratefully acknowledged for XPS measurements. Dr. Masato
Kurihara (TDK Corporation Japan) is acknowledged for solar
cell finishing. Dr. Sebastian Fiechter (Helmholtz Zentrum
Berlin) is gratefully acknowledged for providing tin sulfide
single-crystal materials.
■
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