Applied Surface Science 454 (2018) 334–342

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Applied Surface Science

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

Full Length Article

Improved stability toward photo-electrochemical behavior of multi- T

chalcogenide CdSeS thin films
⁎
Mukul Hazraa, Atanu Janaa, Jayati Dattaa,b,
a
Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur, Howrah 711103, India
b
Department of Chemistry, Renewable Energy Research Centre, Heritage Institute of Technology, Kolkata 700107, India

A R T I C LE I N FO A B S T R A C T

Keywords: The present study deals with the synthesis of polycrystalline n–CdSeS composite films on FTO-coated glass
CdSeS composite film substrate routed through galvanostatic method of deposition at constant temperature from the electrolytic so-
Photo-electrochemical cell lution containing respective precursors, while varying the concentration of elemental sulfur in the bath. Band
EIS gap energies of the nano-structured films were found to lie within the range 2.26–2.48 eV. The structure,
Potentio-dynamic polarization
composition and morphology of the film matrices were revealed through the respective techniques, XRD, UV–vis
Anodic stripping voltammetry
spectroscopy and electron microscopy, while, their photo-electrochemical (PEC) properties were determined
through several electrochemical investigations. The best ternary CdSeS film was identified with 0.15 M S con-
centration in the preparative bath. This particular film shows a photoconversion efficiency of 0.94% which is
higher than the individual binary systems. The optimized film bears high carrier concentration, almost twice
than that of CdSe and thrice than that of CdS films and shows significant photo-response. Furthermore, the
inherent stability of the matrix increases with the incorporation of S and the film developed at 0.15 M S is found
to be ∼100 times more stable than the bare CdSe films.

1. Introduction has to be accepted. This concept has further geared up combinatorial

In recent times, extensive work has been reported on Cd-chalco-
genide compounds (II-VI Group) as promising materials [1–6] in pho-
tocatalysis, biosensing, luminescence, biomedical labelling, and opto-
electric, especially solar cells and optical communication detectors
[7–12] due to their wide range of band gap energies of 1.73 eV (CdSe)
to 2.64 eV (CdS) [13,14] befitting to the visible solar spectrum range.
However, the inherent defects in polycrystalline semiconductor (SC)
materials results into a considerable loss of the photo-generated charge
carriers due to recombination particularly in the space charge region of
the SC matrix [15]. For CdS matrix with comparatively higher band gap
energy, the photo-corrosion is somewhat restricted as manifested by
less photocurrent decay in polysulphide medium, the stable photo-
current output and shift of the flat band potential to more negative
region [16] compared to the low band gap chalcogenides. However, the
photo-generated current output is comparatively low in case of using
such wide band gap materials.
It is understood that one of the major criteria for promoting liquid
junction cells for harvesting solar energy is to impart stability to the
PEC electrode matrices. Thus, to formulate a sustainable PEC anode
material, a compromise between conversion efficiency and durability
approaches in fabricating mixed semiconductor matrices involving
additional chalcogenide or stable metals into the binary SC compounds
leading to composite structures with highly improved functional
properties. Several reports are available on CdTeS [17,18], CdSeTe
[11,19], PbSeTe [20,21], Bi2(S1−xSex)3 [22], BiTeSe [23,24] multi-
chalcogenide systems which target towards exploring the maximum
span of the visible spectrum by possible adjustment and tailoring of
their physical properties so as to overcome the photo-recombination
and grain boundary effects [25]. Sulfur introduction into other chal-
cogenide matrices are reported with various methodologies like AACVD
technique [26], ion-beam-implantation [27], as well as with simple cost
effective wet chemical and electrochemical bath deposition process
[28–30]. Hassanien et al. [31] have reported the effect of Se addition on
the optical and electrical properties of CdSSe films prepared by thermal
evaporation technique. CdSSe deposition on Ag (1 1 1) through elec-
trochemical atomic layer epitaxy (ECALE) was studied by Foresti et al.
[4] where (1:1) sequential deposition of the two binary species, CdS,
and CdSe were involved toward formulating ternary CdS0.2Se0.8 species.
Besides these efforts, the durability studies related to the sulfo-selenide
systems are not extensively studied.
In this context, primarily to arrest photo/anodic degradation of a

⁎
Corresponding author.
E-mail addresses: jayati_datta@rediffmail.com, jayati.datta@heritageit.edu (J. Datta).

https://doi.org/10.1016/j.apsusc.2018.05.141
Received 12 February 2018; Received in revised form 26 April 2018; Accepted 18 May 2018
Available online 19 May 2018
0169-4332/ © 2018 Elsevier B.V. All rights reserved.
M. Hazra et al.
selected photosensitive PEC material, the present investigation attempts
to synthesize polycrystalline CdS-CdSe composite thin films on the FTO
glass surface by a galvanostatic technique from a non-aqueous (DMF)
bath under constant temperature with varying sulfur concentration.
The films prepared were characterized for their structural, morpholo-
gical, compositional and spectral properties by respective techniques.
The functional properties of the films for PEC cells have been justified
through a series of electrochemical procedures like electrochemical
impedance spectroscopy (EIS), polarisation studies along with anodic
stripping voltammetry (ASV) and finally the stable yet best performing
composite film was identified through the current-potential measure-
ments under illumination. The entire process was extended toward
characterizing the binary counterparts CdS and CdSe for the sake of
comparison.
2. Experimental
2.1. Materials
Fluorine-doped SnO2 (FTO) coated glass substrate was provided by
Dyesol, Australia. The glass substrate was cut into small pieces (2
cm × 5 cm) initially and cleaned thoroughly by Milli Q grade water
(conductivity, ρ = 18.2 MΩ cm) and dried in air. AR grade reagents (E-
Merck, Germany) CdCl2, KI, elemental selenium (Se) powder, sulfur (S)
powder were used as precursors to prepare the ternary SC films by
electro-deposition method.
2.2. Synthesis of the semiconductor films
The CdSeS composite film semiconductors were electrodeposited
through galvanostatic deposition technique from non-aqueous DMF
bath at 130 °C. Cathodic deposition was carried out using FTO glass as
the substrate and a large area Pt foil as a counter electrode. The pre-
parative bath contained 10 g/L CdCl2 as Cd2+ ion source, elemental S
and Se as the chalcogenide ion sources, while 6 g/L KI as complexing
agent. The current density of 0.4 mA cm−2 was applied from a multi-
meter current source for 30 min duration. In order to obtain S rich film
matrix, S concentration was kept ∼100 times greater than that of Se
concentration (∼1 mM), by varying amount of S such as, 0.05 M,
0.10 M, 0.15 M, 0.20 M and 0.25 M in the bath. All the prepared films
were air-dried prior to experiment.
2.3. Spectral characterizations, surface morphology, and compositional
study
The optical measurements of the as-deposited ternary composite
films were carried out with the help of JASCO V-530, UV–VIS-NIR
Spectrophotometer, Japan, within the spectral window of 400 nm to
800 nm and band gap was calculated from the differential transmit-
tance plot. The photoluminescence (PL) study was carried out for the
films using Photon Technology International (PTI-LPS-220B) spectro-
fluorimeter with an excitonic wavelength of 450 nm.
In order to determine the crystallinity of all the films, XRD data
were recorded in a Rigaku Miniflex-II X-ray diffractometer using CuKα
radiation (λ = 0.154 Å) with an operating tube voltage of 30 kV and
tube current of 15 mA and the scan range within 2θ = 20–80° with
0.02° s−1 scan rate. The surface morphology and composition analysis
(EDX) of different types of the composite films were carried out using a
Hitachi S4800 field emission scanning electron microscope (FESEM).
Dielectric properties of the electrodeposited films were studied by
measuring the capacitance (C) within the frequency (ω) range of
0.5–200 kHz, under a constant bias of 1.0 V by using an Agilent 4284A
Precision LCR Meter. The thickness of the deposited composite films
was determined gravimetrically.
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Applied Surface Science 454 (2018) 334–342
2.4. Electrochemical impedance spectroscopy records
The prepared films were subjected to electrochemical impedance
spectroscopy (EIS) analysis under 50 mW cm−2 illumination at room
temperature with the help of AUTOLAB 12 PG-stat, Eco-Chemie BV
(The Netherlands) combined with frequency response analyzer (FRA)
using a standard three-electrode cell configuration [FTO glass/ syn-
thesized SC films/S2− – Sx2−, 0.5 M/Pt], including a reference satu-
rated calomel electrode. The capacitance-voltage measurements at a
frequency of 1 kHz for different films derived the Mott-Schottky (M−S)
plots at dark condition, and the functional parameters like carrier
concentration (ND), type of conductivity and the interfacial SC-elec-
trolyte parameters were evaluated using the Mott-Schottky equation
[15,32]
−2
CSC = (V −Vfb−kb Te−1)2(ε0 εs ND e )−1 (1)
where V and Vfb are respectively the electrode potential and flat
band potential, ε0 and εs the permittivity in vacuum and in SC com-
pound respectively, e is electronic charge, T the operating temperature
(298 K), kB the Boltzmann’s constant and CSC the space charge capaci-
tance of the SC film.
2.5. Current – voltage (J-V) and %IPCE measurements
J-V characteristics of the films were recorded in an identical cell
configuration as above, with the help of AUTOLAB 12 PG- stat,
Eco–Chemie BV (The Netherlands) and under illumination of 50 mW
cm−2 light intensity using a 1 kW tungsten filament light source.
Incident photon to current conversion efficiency (IPCE) spectra of the
same cells was recorded under monochromatic light using grating
monochromator (Sciencetech 9055, Canada).
2.6. Potentiodynamic polarization study followed by anodic stripping
voltammetry (ASV)
Inherent stability of the film matrices was studied by conducting
potentiodynamic polarization in aqueous solution containing 0.1 M
NaClO4 as supporting electrolyte within the potential range of −1.0 to
+1.0 V vs. SCE (W) with a slow scan rate of 0.5 mV s−1 with the help of
AUTOLAB 12 PG-stat, Eco-Chemie BV (The Netherlands), using similar
cell assembly as described above. The current – potential relationship at
a polarized electrode-electrolyte interface is given by the well-known
Buttler–Volmer equation:
icorr = i 0(corr ) [e S1 (E − Ecorr )−e S2 (E − Ecorr )] (2)
where icorr is the corrosion current density in A cm−2, i0(corr) is the
exchange current density for the polarization process, S1 the slope of
the anodic branch, S2 the slope of the cathodic branch, E, the applied
potential, and Ecorr is the corrosion potential. The linear sweep vol-
tammetry (LSV) evolved the Tafel plots which were analyzed to eval-
uate the anodic corrosion parameters Ecorr, icorr, and corrosion rate
(rcorr) for each of the films [33,34].
Subsequent to the anodic polarization of the films, the working
solutions were subjected to anodic stripping voltammetry and the
amount of Cd2+ leached out in the electrolyte media was estimated
[35]. Voltammetric – amperometric (VA) measurements were carried
out in an inert XL grade N2 purging atmosphere by using a Metrohm
Ltd. 663 VA Trace Analyzer (Switzerland) combined with an AUTOLAB
30 PG-stat by the standard addition procedure using a hanging mercury
drop (drop size 0.20 mm2) electrode (HMDE) as the working electrode,
Ag/AgCl [3M KCl] as the reference electrode and a large area glassy
carbon counter electrode.
M. Hazra et al.
Scheme 1. Growth mechanism of CdSeS composite films.
3. Results and discussion
3.1. Galvanostatic electrodeposition of the SC thin films
Initially, during application of cathodic current, respective ele-
mental ions present are deposited on the electrode surface according to
2 +/Cd = −0.403 V
their standard reduction potential values such as ECd 0
0
(SHE), ESe/Se 2− = −0.924 V (SHE) and E 0
S/S2 −
= −0.476 V (SHE) [36].
0
Since ES/S 0 0 0
2 − and ECd2 +/Cd are almost at par and ES/S2 − > ESe/Se2 − , S starts
nucleating at a faster rate than Se while Cd nano-particles (NPs) si-
multaneously deposited, undergo surface diffusion to form thermo-
dynamically favorable CdS and CdSe crystallites [respective ΔGformation
(CdX) is −156.5 KJ/mole and −100.4 KJ/mole where X = S, Se],
[36,37] thereby formulating a blended structure of mixed chalcogen-
ides of CdS and CdSe NPs. With increasing S concentration in the bath,
the CdS particles aggregate to form larger entities. In case of such co-
deposition, there is a fair chance of forming the ternary entities like Cd
(S)Se or Cd(Se)S. Since CdSe particles are much smaller in size than the
CdS particles, the overgrowth of CdS surrounding CdSe may lead to a
pseudo core-shell like structure. Scheme 1 represents a model for the
deposition sequences involved in the growth of CdS-CdSe composite
films, henceforth designated as CdSeS in the rest of the article.
3.2. X-ray diffraction study
Fig. 1(i) represents the XRD patterns showing polycrystalline nature
of the films deposited under the different preparative bath. The dif-
fraction pattern of pure binary CdSe shows mainly the presence of
hexagonal and cubic crystalline planes (hkl) at 2θ: 23.54° (1 0 0); 41.33°
(1 1 0); 42.47° (2 2 0) and 45.26° (1 0 3) [JCPDS # 77-2307; 08-0459;
19-0191], while the binary CdS film is constituted with hexagonal and
cubic lattice for the 2θ values at 24.98° (1 0 0); 26.53° (1 1 1); 28.3°
(1 0 1); 36.83° (1 0 2); 43.91° [(1 1 0) (2 2 0)] and 48.11° (1 0 3) planes
[JCPDS # 75-1546; 80-0019; 80-0006]. The composite films with
mixed chalcogenides indicate the presence of both CdSe and CdS
compound SC NPS in the matrices. Some of the weak peaks at 2θ:
32.85° (1 1 1) and 54.58° (2 2 0) suggest the formation of cubical in-
termixed oxide of cadmium (CdO) [JCPDS # 78-0653] in the compo-
site. It is noticeable that the peak at 24.56° (1 0 0) and 27.36° (1 0 1)
suffer a high angle shift toward binary CdS; 0.417° and 0.647° respec-
tively with increment of S in the preparative bath [Fig. 1(ii)]. Similar
kind of shifting was identified for the peak at 43.91° [(1 1 0) (2 2 0)]
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Applied Surface Science 454 (2018) 334–342
and 48.11° (1 0 3). The distinguishable shifts in Bragg’s angle can only
be attributed to the formation of the composite film. The composite
matrix formulation may, therefore, be regarded as intermix of binary
CdS, CdSe as well as ternary CdSeS NPs. Fig. 1(iii) represents the 2θ
shift of the most intense peak. It is critical to note that at a particular
preparative condition (0.15 M S) the tendency toward ternary com-
pound formation increases and this particular film shows a peak at
2θ = 28.01° (1 0 1) which closely matches with the hexagonal ternary
cadmium-selenide-sulfide compound [JCPDS # 40-0837]. With a gra-
dual increase of sulfur concentration from 0.05 M to 0.20 M for the
composite film, the indexed intense peaks tend to shift toward the pure
CdS hexagonal phase. The average crystallite size in the CdS matrix was
found to be 13 nm while CdSe is characterized with 10 nm crystallite
size, as derived from the most intense peak at 2θ = 28.3° (1 0 1) and
41.33° (1 1 0) respectively, using Debye-Scherrer equation [38]. Most
interestingly, increase of sulfur along the concentration 0.05, 0.10, 0.15
and 0.20 M, in the preparative bath, corresponds to increase of the
crystallite sizes 5 → 8 → 10 → 12 nm in the respective film matrices.
This effect corroborates with the peak shift in the ternary films as well
as the morphology revealed in the SEM images. It may be understood
that intimate atom-atom interaction always exists in the closed packed
composite matrix, as indicated by 2θ shifts in the XRD patterns, es-
sentially considered as an inhomogeneous mixture of the two different
Cd chalcogenides. Since S concentration remains almost 2.5–7 times
greater than Se, it may be predicted that the growth of CdS is in excess
leading to a pseudo core-shell like structure (CdSe)CdS distributed in
the matrix.
3.3. UV spectroscopic measurements
Fig. 2(i) shows the typical transmittance (%T) spectrum of the SC
films. From the differential transmittance records, binary CdSe matrix
shows absorption edges around 712 nm corresponding to band gap
1.74 eV while CdS shows absorption edge at 670 nm corresponding to
the band gap 2.64 eV. It is observed that with increase of sulfur con-
centration from 0.05 M to 0.25 M in the deposition bath, the band gap
energy of the composite films gradually gets blue-shifted in the range
2.26–2.48 eV, as represented by Fig. 2(ii) and this shifting is in agree-
ment with the formation of S-rich CdSeS composite matrix. The similar
phenomenon was also reported by other groups [31,39]. The increment
in the S/Se atomic % ratio (as revealed from EDX study, discussed in the
next section) is shown in Fig. 2(ii) and confirms the gradual enrichment
of S in the film matrices. The thickness of the films gradually increases
M. Hazra et al. Applied Surface Science 454 (2018) 334–342

Fig. 1. (i) XRD patterns of as-deposited CdSe, CdS and composite CdSeS films, (ii) magnified view of peak shift in composite films and (iii) 2θ shift for the intense
peak and the indexed ternary peak (2θ = 28.01°).

up to a moderate concentration of S (0.15 M) in the bath; however,
with further high S concentration (> 0.15 M S), film thickness reduces
as the matrix becomes porous by larger coverage of the low-density CdS
particles. The digital images of all the electrodeposited SC films are
shown in inset Fig. 2(ii) which indicates that the orange-brown color of
CdSe film gradually fades with increasing sulfur content in the mixed
chalcogenide matrix.
3.4. Surface characterizations by scanning electron microscopy (SEM)
The typical SEM images of the SC film regime [Fig. 3(a)–(d)] show
homogeneous and porous microcrystalline structures, composed of
mixed cubical and hexagonal phases as revealed in the respective insets
of Fig. 3(a) and (b). The average particle size of binary CdSe and CdS
are found to be ∼10 nm, and ∼20 nm respectively whereas that of the
CdSeS (0.15 M S) composite is ∼15 nm. Distinct coalescing of the
particles is also observed in the composite films with higher sulfur
concentrations. The typical pattern is shown in Fig. 3(e) and the

Fig. 2. (i) Transmittance spectrum (ii) Thickness, bandgap, S/Se at% variation profiles and digital images for the synthesized films (inset).

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M. Hazra et al. Applied Surface Science 454 (2018) 334–342

Fig. 3. Typical SEM images of (a) CdSeS (0.05 M S) (b) CdSeS (0.15 M S) (c) CdSe (d) CdS films and (e) Typical EDX pattern of a CdSeS film.

Table 1 densities with increasing sulfur concentration corroborates with the

EDX parameter and density of SC films. increase in S/Se at% ratio in the matrix and attributes to the excess CdS
SC films (S concentration atomic % of the composed elements ρ (g/cc)
formation as discussed earlier.
variation)
S Se Cd
3.5. Photoluminescence study
CdSeS (0.05M) 34.10 14.40 51.50 5.10
CdSeS (0.10M) 37.66 10.55 51.79 5.02
PL spectra (excited at 450 nm) of different composite films and their
CdSeS (0.15M) 42.67 7.89 49.45 4.95
CdSeS (0.20M) 43.02 7.22 49.76 4.94 binary counterparts are shown in Fig. 4. The PL emission intensity was
CdSeS (0.25M) 44.85 6.68 49.47 4.93 dramatically weakened with the gradual increase of S content in the
ternary matrix compared to the binary CdSe and the recombination
process is, therefore, distinctively reduced following the same order, as
compositional analysis data are listed in Table 1. The atomic% ratios the ternary matrix becomes S rich. The distinct blue shifting from
(S/Se) from EDX, have already been shown in Fig. 2(ii). The densities of 488 nm for CdSe to 481 nm for CdSeS composite films corresponds to S-
the as-deposited composite films were calculated using equation rich matrix (CdSeS) formulations. During surface diffusion, and for-
ρ = (Xρx + Yρy )/(X + Y ) where X and Y are the molecular composition mation of ternary clusters of the CdS and CdSe NPs, the surface states
of CdS and CdSe respectively in the composite matrices (EDX analysis), are gradually passivated so that the PL intensities of the matrices were
ρ x (4.82 g cm−3) and ρ y (5.82 g cm−3) are the individual densities of decreased and the band-edge emission due to the quantum size effect
CdS and CdSe respectively. The density variation with film composi- was improved [40] as has been discussed later for the polarization
tions are shown in Table 1. It is seen that the gradual fall in the overall studies.

338
M. Hazra et al.
Fig. 4. Photoluminescence spectra of CdSe, CdS and the composite CdSeS films.
3.6. Electrochemical characterizations through EIS technique
Fig. 5(i) shows the Mott-Schottky plots with positive slopes in-
dicating n-type nature of the SC matrix. The x-intercept and the slope of
the linear region are used to calculate the flat band potential (Vfb) and
the carrier concentration (ND) values, respectively. From the x-intercept
of the plots, the most negative flat band potential is observed for the
composite film deposited under bath concentration of 0.15 M S which
translates to the reduced activation potential required for the redox
reaction by the creation of favorable reaction sites at the electrode-
electrolyte interface in the composite matrix [5,33]. The dielectric
constant (εs) values for the films are obtained from dielectric loss
measurements (Capacitance vs Frequency plot in supplemental file, Fig.
S1) at 1 kHz frequency and were used to determine the ND values,
summarized in Table S1 (supplemental file). Analyzing the composite
films, maximum population density (ND) of carrier species is observed
for CdSeS (0.15 M S) as displayed in Fig. 5(ii). The variation of ND
follows the order, CdSeS (0.15 M S) > CdSeS (0.20 M S) ≫ CdSe >
CdSeS (0.25 M S) > CdS > CdSeS (0.10 M S) > CdSeS (0.05 M S).
Moreover, CdSe in its discrete form has got a high dielectric constant
(εs) values due to its smaller particle size and greater numbers of or-
iented dipoles, while pure CdS with a larger particle size (XRD ana-
lysis), bears the least εs value. With increasing sulfur content in the
composite films, the εs values gradually decline and a moderate value is
obtained for the CdSeS (0.15 M S) films. It may be summarized that this
particular film is characterized with comparatively high carrier con-
centration which enhances the conductivity and facilitates passage of
Fig. 5. (i) M−S plots for the cell (FTO) SC films/Sx2− – S2−/Pt and (ii) Carrier densities and dielectric constant profiles for the films.
339
Applied Surface Science 454 (2018) 334–342
charged species at the electrode-electrolyte interface and at the same
time contributes to building up of optimized space-charge properties.
These are further reflected in the higher electrical performance and less
recombination effect in the CdSeS (0.15 M S) film as discussed later.
The Nyquist plots for the CdSeS films obtained from the EIS records
are shown in Fig. 6(i). A simplified equivalent circuit (EC) was used to
fit the Nyquist plots of the corresponding SC films and displayed in the
inset Fig. 6(i). The EC components include Rs, the solution resistance,
Rct, the charge transfer resistance and CPE, a constant phase element
representing the interfacial capacitance. All these values are listed in
Table S1 (supplemental file). The Rct variation of the SC films are shown
in Fig. 6(ii). The much lower charge transfer resistance (3.04 kΩ) for
the CdSeS (0.15 M S) film compared to the CdS film (7.86 kΩ) is in tune
with all other favorable charge transfer properties of this film as
manifested in the higher photocurrent densities obtained during the J-V
studies which is presented in Fig. 6(ii).
3.7. J-V plots and %IPCE measurement
The performance of the SC films was recorded in terms of photo-
conversion efficiency (PCE) with the help of current-voltage (J–V)
measurements [Fig. 7(i)] under 50 mW cm−2 light intensity. The power
output characteristics of typical PEC cells constituted with the de-
posited films under simultaneous record of the open circuit potentials
(Voc) and short-circuit current densities (Jsc) are presented in inset of
Fig. 7(i). The PCEs (%η) and fill factors (%FF) are plotted in Fig. 7(ii)
(data summarized in supplemental file, Table S1). Amongst all the
ternary films, the CdSeS film 0.15 M S shows the maximum PCE
(0.94%) and best fill-factor (18.22%) and the values are even higher
than pure CdSe films. With further high S concentration the efficiency
decreases again. The present investigation on the mixed chalcogenide
(CdX) films, reveals that stability is imparted to the films with the major
content of X = S while partial existence of X = Se is beneficial for in-
creasing the PEC functional properties. In fact, CdSeS prepared under
0.15 M S concentration formulate a CdSe embedded CdS matrix which
simulates a pseudo core-shell like structure along with mixed CdSe and
CdS SC compounds in the film. This particular film (0.15 M S), attains
maximum thickness (∼2 μm) while beyond 0.15M the film thickness
gradually drops as the matrix becomes porous. In effect, increased cell
efficiency, short circuit current density (JSC) and also higher carrier
density (ND), as calculated from the M−S plot are achieved for this film
with substantial S content and comparatively low Se content. Similar
behavior is also reflected in the IPCE measurements shown in Fig. 8,
where the film (0.15 M S) is found to achieve best photon to current
conversion efficiency in the near-UV to UV range compared to its binary
counter parts (CdSe and CdS). Although CdSe has a broader coverage of
solar spectrum unlike CdS, the composite CdSeS (0.15 M S) film exhibit
%IPCE even higher than the CdS films at around 300–500 nm solar
M. Hazra et al. Applied Surface Science 454 (2018) 334–342

Fig. 6. (i) Circuit fitted Nyquist plots for the films with applied equivalent circuit diagram in the inset and (ii) RCT and JSC variation of the developed films.

wavelength region.

3.8. Potentio-dynamic polarization and ASV studies

Typical Tafel plots were derived from potentio-dynamic polariza-

tion studies of the film regime carried out in aqueous medium within
the potential window –1.25 to 1.00 V, and shown in Fig. 9(i). The
evaluated electrochemical corrosion parameters are summarized in
supplemental file, Table S2 and displayed in Fig. 9(ii). For the mixed
chalcogenide films the corrosion rates (rcorr) were considerably reduced
by ∼100 folds compared to the single SC CdSe film, thereby sub-
stantiating the ability of the composite films to resist anodic corrosion.
It implies that ample existence of the CdS NPs protects the CdSeS films
from degradation. Furthermore, smaller the particle size, higher the
number of grain boundaries. Hence the local surface states, defects and
recombination centers are expected to be high in case of CdSe, which in
turn initiate larger electron-hole trapping centers in the semiconductor
itself. Likewise, Fig. 9(i) demonstrates a considerably broader passive Fig. 8. % IPCE variation of CdSe, CdS and CdSeS (0.15 M S) films.
region for the CdSeS composite films deposited under 0.10 M and 0.15
M S concentrations. On the other hand under exposure to illumination, transfer toward the preferable redox reaction and thus acting as a sui-
the chalcogenide films are prone to photo corrosion (CdSe > CdS) table co-catalyst. In the CdSeS films, corrosion inhibition can also be
since the photogenerated holes may not preferably oxidize the redox justified with increase of crystallite sizes and reducing grain boundaries
electrolyte, but the semiconductor itself (CdX + 2 h+ → Cd2+ + X, as observed with increased S concentrations (0.05–0.25 M). This phe-
where X = Se/S here in our case); however, presence of excess sulfur nomenon of acquisition of stability by the composite CdSeS film with
may arrest the dissolution of Cd2+ from CdSe by the recombination optimized S content can further be justified quantitatively through
reaction Cd2+ + S2− → CdS. Thus S plays a key role in protecting the anodic stripping voltammetry (ASV) studied after polarisation of the
mixed chalcogenide matrix from photo-degradation [16]. In fact, films. The typical current-voltage and corresponding current-con-
blending of sulfur with seleno-semiconductor compounds can alleviate centration plots are shown in Fig. 9(iii) for CdSeS (0.15 M S). The Cd2+
the photo-corrosion to a substantial extent by orienting the charge

Fig. 7. (i) J-V curves; inset: Power output plots and (ii) %η, %FF profiles for respective films.

340
M. Hazra et al.
100n
(iii) 80.0n
60.0n
I/A
40.0n
20.0n
-1e-005
0
-20.0u 0 20.0u
c / (g/L)
Fig. 9. (i) Tafel plots of the CdSe, CdS and composite CdSeS films, (ii) variation of corrosion parameters (rcorr and Ecorr) from Tafel analysis (iii) typical anodic
stripping voltammogram for Cd2+ dissolution for CdSeS 0.15 M S film and corresponding current-concentration plot (inset) and (iv) dissolved Cd2+ concentration for
the SC films during polarization.
stripped off in solution are estimated by using
ip = 2.69 × 105 × A × D1/2 × C 0 × n3/2 × ν1/2 , where ip is the peak cur-
rent, A is the surface area of the Hg drop (mm2), D is the diffusion
coefficient (cm2 s−1), C0 the bulk concentration of the analyte (mol
L−1), n is the number of electron transfer of the charge transfer process
and ν is the scan rate (V s−1) [41]. The estimated Cd2+ concentration is
summarized in supplemental file, Table S2 and plotted in Fig. 9(iv).
Gradual decrease of Cd2+ dissolution is observed with increasing S
concentration in the ternary matrix (from 0.05 M S to 0.25 M S). It is
also observed that the dissolution rate for CdS itself, in terms of rcorr is
almost comparable with the values obtained for composite CdSeS ma-
trices. The ASV data are, therefore, well in agreement with the rcorr
values obtained for the individual films. Overall it appears that the
increased CdS formation in the ternary matrix imparts improved sta-
bility to the composite CdSeS films developed under 0.10 M to 0.25 M S
towards anodic dissolution in the aqueous medium compared to both
the individual CdSe and CdS films.
4. Conclusion
Nanostructured mixed n-type chalcogenide semiconductor films
(CdSeS) with improved functional properties can be developed suc-
cessfully by simple and cost effective galvanostatic technique from a
non-aqueous bath containing respective precursor salts. The synthe-
sized films with varying sulfur contents in the matrix are within the
moderate band gap regime (2.26–2.48 eV) and therefore can be at-
tractive candidate materials for solar energy conversion. The electro-
chemical characterizations and J–V measurements collectively suggest
that the CdSeS (0.15 M S) film achieve significant photo-response and
Applied Surface Science 454 (2018) 334–342
(i) (ii)
(iv)
40.0u 60.0u 80.0u 100u
low charge transfer resistance and therefore can be recommended for
application as photoanode in liquid junction solar cells. On the other
hand, pure CdS can firmly resist disintegration, 100 times less than that
of CdSe, but alone is not a suitable PEC candidate, in view of its feeble
conversion efficiency of 0.23%. Therefore by applying simple galva-
nostatic technique for developing composite CdSeS, the authors could
achieve 0.94% photo convertion efficiency.
Acknowledgement
The authors gratefully acknowledge DST-Nano Mission, New Delhi
for financial support and MHRD, New Delhi, Govt. of India for instru-
mental facility provided to the Institute.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.apsusc.2018.05.141.
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