Journal of Materials Science: Materials in Electronics

https://doi.org/10.1007/s10854-019-01922-9

An attempt to co‑deposit photovoltaic quality ­CuInSe2 thin films:

effect of surfactant and deposition potential
Ramkumar Chandran1 · Akhya Kumar Behera1 · Archana Mallik1

Received: 15 May 2019 / Accepted: 21 July 2019

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
CuInSe2 (CISe) thin films were prepared by single step electrodeposition technique using citrate-SDS electrolyte. Preliminary
studies revealed that the initial deposition conditions have significant influence over the composition, film quality and the
addition of SDS in the citrate electrolyte enhances adhesion, smoothness and eliminates multinuclear growth. To explore the
capability of the citrate-sodium dodecyl sulfate (SDS) electrolyte, the CISe thin films deposited at various potentials were
annealed at 300 °C in nitrogen atmosphere. The structural, morphological and compositional properties of the annealed CISe
thin films were compared. Finally, CISe thin film deposited at − 0.65 V/SCE exhibiting the p-type electrical conductivity
was confirmed by Mott–Schottky (M–S) and photoelectrochemical (PEC) studies.

1 Introduction
CISe is considered as an attractive absorber material for
thin-film solar cells, due to its high absorption coefficient
of about ­105 cm−1 and band gap of nearly 1.0 eV which
is in well match to the solar spectrum. In addition, CISe
thin film is low-cost, environmentally friendly material,
and has a long-term stability in photovoltaic applications.
Regardless of deposition techniques employed in thin film
CISe fabrication (PVD, ink jet printing, solution processing
and electroplating), the ultimate goal of every route is to
prepare a compositional film exhibiting good crystallinity
leading to a material with good photovoltaic characteris-
tics. For industrial-scale applications, non-vacuum deposi-
tion technique such as electrodeposition and screen print-
ing is considered to be suitable approaches for reducing the
device fabrication cost. Moreover, electrodeposition has
the potential to prepare large area thin films as it requires
cheap raw material sources and synthesis equipment capital
[1–4]. The formation of CISe thin films can be processed
either by direct electrodeposition of Cu-In binary alloy or
ternary CISe and by sequential deposition of Cu/In or Cu-In
bilayer followed by selenization [5]. Comparatively, a direct
* Archana Mallik
archananitrkl@gmail.com
1
Electrometallurgy and Corrosion Laboratory, Department
of Metallurgical and Materials Engineering, National
Institute of Technology, Rourkela, Odisha 769008, India
single step deposition is attractive due to its urge for simplic-
ity and subsequently better adaptability [6]. According to
Nernst equation, the equilibrium reduction potential of Cu,
In and Se ions in the EMF series is +  0.337/SHE, −  0.342/
SHE, and +  0.741/SHE, respectively. As the reduction of
Se(IV) and Cu(II) ion precedes In(III) ions during electro-
deposition, difficultness arises during the co-deposition due
to active standard reduction potential of In ions. Though
increasing the concentrations of In(III) ions can shift the
potential closer to Cu(II), the excessive currents generated
due to high bath concentrations may cause significant pitting
and corrosion of substrates [7] and to the thin film itself.
Further electrodeposition at high cathodic potential con-
ditions affects the In plating efficiency due to the parallel
occurrence of hydrogen evolution, which is considered to be
the origin for film inhomogeneity and pin holes formation.
This makes electrodeposition of stoichiometric and pinhole
free CISe thin films even more challenging. This shortfall
arised as an attempt for the controlled inclusion of In(III)
ions can be taken care by adding complexing agents. In the
recent years several literatures have reported on the electro-
deposition of CISe thin films using complexing agents in
aqueous electrolytes such as citric acid [8], trisodium cit-
rate [9], triethanol amine [10], thiocyanate [11] and in non-
aqueous electrolytes such as alcohol [12], ethylene glycol
[13], reline [14] and DMF [15] etc. Among these possible
complexing agents used, citric acid is advantageous as it
is a non-toxic pH adjuster and can limit the activity of the
­Cu2+ ions by forming metal complexes at acidic conditions

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[16, 17]. However, the as-deposited thin films exhibited
poor morphology and suffer surface non-uniformities issues
such as blisters, presence of In-rich CISe nano islands over
the surface [18] and irregular columnar morphology [16,
19, 20]. For CISe deposited using sodium dodecyl sulfate
(SDS) in acidic electrolytes, the as-deposited thin films were
submicron grain sized. Though they have the potential to
inhibit ­CuxSe secondary phase [21, 22], the as-deposited
films were powdery in nature [21]. Till date, rare attempts
have been made to use the combinations of Citric acid and
sodium dodecyl sulfate (SDS) as a suitable electrolyte for
CISe electrodeposition.
In the present study an attempt has been made to co-
deposit Cu, In and Se ion from a novel electrolyte consisting
of citric acid and SDS. The said bath has been experimented
with an aim to synthesize a near stoichiometric photovol-
taic quality thin films without any pinholes. The study also
emphasizes the significance of the initial deposition condi-
tions on film morphology and composition. A detailed study
on the effect of deposition potential has also been carried
out to optimize the deposition condition to synthesize com-
mercial quality CIS photovoltaic thin films.
2 Experiment
The deposition bath electrolyte was prepared by using chlo-
ride salts of copper (3.70 mM), indium (5 mM) and seleni-
ous acid (6 mM). The electrochemical deposition and stud-
ies were performed in a potentiostat (Corrtest, China). In
our experiments, citric acid was used as complexing agent
(0.326 M) and pH adjuster. The SDS concentration was fixed
to be 12 mM. The addition of SDS would improve adhesion,
control the ­Cu2+ content and enhance the Indium inclusion
during deposition. For electroplating, well cleaned FTO
coated glass substrates (active area-1 × 0.5 cm2) were used
as the working electrode and platinum foil as the counter
electrode. The reference electrode used was saturated calo-
mel electrode. The deposition potential is identified from
the cyclic voltammetry (CV) measurements. Before each
experiment the working electrodes were subjected to a pre-
treatment (PT) process using chronoamperometry technique
(CA) where a pulse of − 0.65 V was given for 100 s followed
by cleaning and washing in DI water, then flushed with nitro-
gen gas to remove water molecules and finally dried in IR
lamp. After this, CISe thin films were electrodeposited for
20 min at different potentials. The thin films were annealed
at 300 °C in nitrogen atmosphere for 30 min by using a
conventional tubular furnace (at a ramp rate of 5 °C/min).
The morphology and compositional analysis was carried
out by Electron microscopy (SEM, JEOL JSM 6480 LV
and FEI Novanano SEM 450). The X-ray diffraction study
was performed by using Ultima IV system diffractometer
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Journal of Materials Science: Materials in Electronics
with Cu Kα radiation in the range between 20° and 70° at
a scan rate of 5°/min. MicroRaman spectra were recorded
on WITec Wissenschaftliche Instrumente and Technologie
GmbH Model-XMB3000-3000, a high resolution spectrom-
eter with ­Ar+ polarized laser green line (λ = 532 nm). A laser
beam intensity of 5% was used on the films with the acquisi-
tion time of 400 s to avoid crystallization. The Spectra fitting
was done with software supplied with the apparatus. For
Mott–Schottky (M–S) and photoelectrochemical (PEC) stud-
ies, 0.5 M of ­Na2SO4 was used as the electrolyte junction.
A 100 Watts conventional white light was used as the light
source for the PEC measurements at − 0.4 V/SCE.
3 Results and discussion
Figure 1a shows the cyclic voltammetry behavior of ternary
Cu-In-Se ionic system containing 3.70 mM C ­ uCl2, 5 mM
­InCl3 and 6 mM ­H2SeO3 dissolved in citrate electrolyte
with and without SDS. Four reduction peaks were observed
between the experimented potential of 0 V to − 1 V/SCE.
The steep increase in current density up to − 0.35 V (C1)
can be attributed to the double step reduction of C ­ u2+ ions
0
to ­Cu . The reduction peaks C2 centered on − 0.45 V can
be assigned to the formation of C ­ uxSey binary compounds
and deposition of elemental Se(0). Through surface induced
reaction, indium may start to incorporate at this potential
by reacting with elemental selenium. Between the potential
− 0.50 to − 0.70 V (C3), the excess Se(0) over the C ­ uxSey
phase also undergo a reduction from Se(0) to H ­ 2Se which
facilitates the incorporation of ­In3+ ions in the form of
­In2Se3. The peak C4 at − 0.85 V can be assigned to the direct
reduction of I­ n3+ to I­ n0 [23]. With the addition of SDS, all
the reduction peaks have been shifted to low polarization
potentials and the corresponding reduction current values
have also been reduced. This information definitely indicates
the influence of complexing agents. Furthermore the anodic
shift of prominent crossover and reduction peaks indicates
the onset of the nucleation process taking place with faster
kinetics and increased nucleation density. From the cyclic
voltammetry results, the optimal reduction potential of
− 0.65 V/SCE was chosen for preliminary studies.
Figure 1b shows the chronoamperometry plot for CISe
thin film deposition at − 0.65 V/SCE in citrate, citrate-PT,
citrate-SDS, citrate-SDS-PT bath conditions. For all the
chronoamperometry curves, the rapid decay in the cathodic
current indicates the consumption of the cations at the vicin-
ity of the cathode followed by the formation of nucleation
centers and contributing towards the growth process. The
rapid decay of current density followed by attaining the
steady state indicates the transition of the surface reaction
state to mass-transfer kinetics. Major changes in CA plots
were observed for CISe deposited in citrate electrolyte with
Journal of Materials Science: Materials in Electronics

Fig. 1  a Cyclic voltammetry of a solution containing 3.7 mM C

­ uCl2, 5 mM I­ nCl3, 6 mM H
­ 2SeO3 with 0 mM and 12 mM SDS, scanned at a rate
of 20 mV/s and b chronoamperometry plot recorded at various conditions and at − 0.65 V polarization (Color figure online)

(red curve) and without PT process (black curve). Upon pre-
treatment, the decay current density was even more lower
which may indicate the high formation rate of the nucleation
sites and low growth rate.
To complement the above analysis, the morphological
characterization was carried out. Figure 2a, b shows the
SEM micrographs of CISe thin films deposited in citrate
bath without and with PT. For CISe deposited without PT
(Fig. 2a), the SEM shows a compact dendrite like struc-
tures with the mean size of ~ 400 nm. With PT (Fig. 2b),
the micrograph exhibited nanocrytsalline aggregates with
multi-nuclear cauliflower shaped protrusions on the growth
deposits. The obtained microstructures in Fig. 2a, b are
trivial when deposited using citrate electrolyte [9, 16, 23].
A simple pinhole analysis (Figure not provided) was per-
formed by illuminating white light optics behind the thin
films revealed that the samples deposited in citrate bath in
both the conditions suffered pinholes. The existence of pin-
holes in the absorb layer may cause severe shunting prob-
lems and thereby can degrade the device performance [24].
For CISe deposited using SDS, the decay current density of
the chronoamperometry plot was lower than the values when
compared to citric acid. The addition of SDS enhances the
formation rate of the nucleation sites (green curve) which

Fig. 2  SEM microstructure of
as-deposited CISe thin films
deposited at − 0.65 V from
baths of a citrate without PT,
b with PT c citrate-SDS bath
without PT and d citrate-SDS
bath with PT

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Table 1  Compositional analysis Electrolyte Cu (at.wt%) In at.wt%) Se (at.wt%) [Cu/In] ratio

of CISe deposited at various
conditions Citrate bath 24.12 20.18 55.07 1.19
Citrate bath—with PT 24.81 25.51 49.68 0.97
Citrate + SDS 25.91 24.29 49.80 1.06
Citrate + SDS—with PT 19.18 23.74 57.09 0.80

Fig. 3  a FE-SEM of CISe

deposited at − 0.40 V for
20 min, and its corresponding
elemental mapping of b Cu, c In
and d Se

was found to be further improved after PT process (Blue Table 2  Composition of CISe thin films deposited at − 0.40 V/SCE
curve) (Fig. 1b). Noticeable changes were observed in the Morphology Cu (at.wt%) In Se [Se/Cu] ratio
microstructure from fine grains to smooth large nodules
with compact morphology (Fig. 2c, d). The pre-treatment Irregular flower shaped 41.59 9.64 48.77 1.17
process resulted in even more smooth films with reduced Base layer spherical 43.75 11.45 44.80 1.024
pinholes and surface non-uniformities. From these prelimi- Overall 41.96 13.10 44.94 1.07
nary results, it is evident that the addition of SDS in the
electrolyte eliminates the multinuclear growth protrusions,
reduces the pinholes and improves the crystallinity of the deposition conditions. Hence all the samples were depos-
as-deposited CISe film. ited in Citrate + SDS bath with prior pretreatment process.
The compositional analysis of the films is provided in To have a better understanding on the correlation
Table 1 and it reveals the fact that addition of SDS has between the deposition potential and its influence on the
indeed improved the In-inclusion in CISe thin films. The composition and morphological changes, the CISe thin
pretreatment process was found to be effective towards films were deposited at various potentials ranging from
reducing the pinholes and multinuclear growth protrusions − 0.40 to − 0.80 V for a time period of 1200 s. Further,
which can cause compositional non-uniformities. On the the morphology and composition studies were performed
basis of the results presented above, it can be initially con- by FE-SEM/EDAX studies and are shown in Fig. 3 and
firmed that the composition and morphological evolutions Table 2. The thin films deposited at − 0.40 V was found
of the as-deposited thin films are highly dependent on the to be Cu–Se rich and patchy silvery bright in appearance.

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Journal of Materials Science: Materials in Electronics

The morphology and composition of CISe deposited at

− 0.40 V is provided in Fig. 3 and Table 2.
For CISe deposited at − 0.40 V (Fig. 3a), a mixed mor-
phology consisting of uniform spherical grained base layer
and presence of irregular coral like structures on the base
layer have been distributed unevenly on the top of the base
layer. The as-deposited CISe thin films were of patchy sil-
very bright in appearance. From the elemental mapping
(Fig. 3b–d) and composition studies (Table 2), the coral
shaped irregular clusters were found to be Se rich than the
spherical particles. From the [Se/Cu] at.wt% ratio, we specu-
late that the phase of these coral morphology particles may
coexist as CuSe and elemental Se(0), where the excess Se(0)
can react with I­ n3+ ions to from In–Se species. For the base
layer spherical particles, the [Se/Cu] ratio was close to unity
which might be due to the consumption of the excess Se(0)
over the CuSe phase contributing towards In-Se phase for-
mation. Studies by Chassaing et al. also revealed that dur-
ing the initial stages of ­CuInSe2 deposition (− 550 mV to
− 750 mV/MSE ~ − 160 mV to − 350 mV/SCE), the inclu-
sion of indium starts when [Se/Cu] ratio is greater than unity
[25]. Also the presence of excess Se(0) over the CuSe phase
is prerequisite for the Indium inclusion at lower cathodic
potentials.
Figure 4 shows the morphology and composition anal-
ysis of the as-deposited and annealed CISe thin films at
potentials − 0.50 V to − 0.80 V is shown in Fig. 4a–h and
Table 3. All the as-deposited CISe thin films were observed
to be compact, crystalline and free of pinholes. For CISe Fig. 4  FE-SEM of as-deposited and annealed CISe at a and b
− 0.50 V, c and d − 0.60 V, e and f − 0.70 V and g and h − 0.80 V/
thin films deposited at − 0.50 V (Fig. 4a), the cauliflower SCE
shaped morphology are found to have a [Cu/In] ratio of 1.19
indicating the Cu-richness. In addition there are some plate-
lets like protruding structures on the surface of the films. Cu content (− 0.6 to − 0.80 V), the film appearance was pale
The protruding white platelet like structures between the silvery gray indicating the presence of In-rich superficial
interconnected grains indicates the presence of CuSe phase layer. For CISe thin film deposited beyond − 0.80 V, the
[26]. With the increase in the deposition potential, the occur- film was pale silvery black in appearance, powdery in nature
rence of the Cu-Se secondary phase has been reduced. For with pinholes which may be due to the simultaneous solvent
− 0.60 V, the difference in the morphology is clearly visible reduction taking place at high cathodic deposition potential.
in Fig. 4c. The CISe thin films were composed of larger Hence from the compositional studies, the deposition poten-
grains with globular morphology and improved compact- tial window to obtain a near stoichiometric Cu-poor CISe
ness. The [Cu/In] ratio of the deposits was determined to thin films with good crystallinity was found to be within
be 0.91. For deposits at − 0.70 V (Fig. 4e), the [Cu/In] ratio − 0.60 to − 0.70 V/SCE.
decreased to 0.88 indicating decrease of copper content and For annealed CISe thin films, no noticeable changes were
increase in indium content in the films. Furthermore, an observed in the morphology (Fig. 4b, d, f, h). However
interesting observation is that there was no change in the changes in bulk composition such as increase in Cu con-
morphology when compared to CISe deposited at − 0.60 V. tent, In and Se loss were observed (Table 3). The plausible
However, a decrease in the particle size was observed with explanation for the variations in the [Cu/In] ratio may be due
the increase in the In content. Further increase in the deposi- to the volatile nature of selenium and I­ n2Se which escapes in
tion potential (− 0.80 V) resulted in In-rich films of round the gaseous form during annealing [27]. Except CISe depos-
spherical morphology (Fig. 4g). Regarding the appearance, ited at − 0.80 V, all the samples suffered significant Se loss.
all the Cu-rich films exhibited excellent silvery metallic sil- Figure 5a depicts the XRD pattern of electrodeposited
very gray appearance with a highly compact microstructure CISe thin films annealed in nitrogen atmosphere. All the
and exhibited very less pinholes. With the decrease in the diffraction peaks corresponding to CISe were identified and

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 Journal of Materials Science: Materials in Electronics

Table 3  Composition of Deposition [Cu] (at.wt%) [In] [Se] As deposited Annealed

as-deposited and annealed potential (V/ [Cu/In] ratio [Cu/In] ratio
CISe thin films (*as-deposited, SCE) (V) *As Dep. **Ann. As Dep. Ann. As Dep. Ann.
**annealed)
− 0.50 23.23 32.29 19.52 22.09 57.27 45.62 1.19 1.46
− 0.60 20.11 28.29 21.97 26.66 57.92 45.04 0.91 1.06
− 0.70 20.53 26.61 23.09 27.05 56.36 46.34 0.88 0.98
− 0.80 14.79 20.05 26.21 28.82 59 51.13 0.57 0.70

Fig. 5  a XRD of annealed CISe thin films deposited at various potentials (− 0.40 to − 0.80 V/SCE), b Focus on (204) plane

matched by using the JCPDS # 40-1487. The sharp diffrac-
tion peak at 26.70° corresponding to (112) plane indicates
the characteristics of the crystalline chalcopyrite phase. In
addition, the weak double peaks corresponding to (204)/
(220) at 44° and (116)/(312) planes at 52.5° confirm the
crystal structure of CISe thin films.
The diffraction intensity of the Cu–Se rich C ­ u7Se4 sec-
ondary phase around 45° [JCPDS # 26-0557] was found
to be decreasing with increasing deposition potential. For
samples deposited at − 0.80 V, additionally a weak shoulder
peak at 25.50° suggests the presence of some In-rich phase
­(In6Se7) [JCPDS # 25-0385] in these thin films [26].
A small insignificant peak around 30.60° can be assigned
to the ­In2O3 phase [JCPDS # 06-0416] might have probably
caused due to the oxidation of In-rich phase during anneal-
ing. The reduction of Cu content and increase of In content
with the increase of deposition potential may lead to a struc-
tural transformation from tetragonal chalcopyrite structure to
cubic sphalerite structure due to the random distribution of
Cu and In atoms in the metal atoms [28]. With the increase
in deposition potential, the structural transformation of CISe
from chalcopyrite to sphalerite is evident from the shifting
of the reflection peaks (204/220) plane towards higher dif-
fraction angles (Fig. 5b) [29].
To confirm the degree of disorderness of Cu and In atoms
in the cationic sub-lattice, micro-Raman spectroscopy stud-
ies were performed. Figure 6 shows the Raman spectrum
for the CISe thin films exhibiting varying [Cu/In] ratio. The
prominent peak detected at 175 cm−1 can be identified as the
chalcopyrite A1 mode for CISe. The observed peak broad-
ening of A1 mode with the increase in deposition potential
indicates the decrease in the crystallinity due to the reduced
Cu-content as in agreement with the XRD and composi-
tional results. The additional peaks positioned at 213 and
230 cm−1, the B2(E) lattice modes were observed beyond
the deposition potential of − 0.40 V. The presence of detri-
mental ­Cu2Se secondary phase is identified by the peak posi-
tioned at 240 cm−1 [30] and was found to be decreasing with
increasing deposition potential. The spectra also character-
ized the peaks corresponding to ordered vacancy compounds
(OVC) phase between 150 and 160 cm−1. Reports suggest
that the appearance of weak intensity peak at 187 cm−1 can
be assigned to the In-Se binary phase [31]. Despite of the
Cu-poor composition, the weak signatures corresponding to
­Cu2Se phase was observed for CISe deposited at − 0.70 and
− 0.80 V. This discrepancy may be due to the phase segrega-
tion of C
­ u2Se phase because of inadequate post processing
temperature employed.

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Journal of Materials Science: Materials in Electronics

From the structural investigations, it can be inferred

that the CISe deposited between the potentials − 0.40 to
− 0.60 V/SCE exhibits chalcopyrite structure and between
− 0.70 and − 0.80 V/SCE was identified to be exhibiting
sphalerite structure. The shifting of the (204/220) plane in
the XRD and appearance of broad spectra between 180 and
190 cm−1 in the Micro-Raman studies are evident for the
structural transformations with increase in deposition poten-
tial. In between the potential range of − 0.60 to − 0.70 V, the
compositional transition of Cu-rich to near stoichiometric
was found to be observed in the above mentioned results.
Hence an optimal deposition potential of − 0.65 V/SCE was
chosen to deposit the CISe thin films and analyze their PEC.
The EDAX and compositional analysis of the CISe thin film
deposited at − 0.65 V/SCE is provided in Fig. 7.
Finally, the electrochemical studies were performed for
annealed CISe deposited at − 0.65 V using 0.5 M N ­ a2SO4
as the electrolyte. Figure 8a shows the M–S plot for CISe
thin films measured at 5 and 10 Hz respectively. Both posi-
tive and negative slope features observed in the differen-
tial capacitance curves affirms the n-p type semiconductor
behaviour of the as-deposited CISe thin films. The flat band
potential of CISe thin films measured at 5 and 10 Hz were
determined to be 430 mV and 470 mV respectively. The car-
rier concentration ­(NA) of 1.77 × 1016 and 2.62 × 1016 ­cm−3
were calculated from the M–S plot for a frequency of 5 and
10 Hz respectively by using the relation 2 (eɛɛo × slope)−1
[32]. The obtained values are in good agreement with the
carrier concentration of the p- type absorbers used to fab-
Fig. 6  Raman analysis of annealed CISe thin films deposited at vari-
ricate high efficiency devices [33, 34]. To check the pho-
ous potentials
tocurrent response stability of the thin films, the PEC was

Fig. 7  EDAX analysis of a CISe thin film deposited at − 0.65 V (inset-composition and elemental mapping distribution of CISe thin film)

13

Fig. 8  a Mott–Schottky and b PEC studies (hold at − 0.40 V vs. SCE) of CISe thin film deposited at − 0.65 V/SCE
measured under intermittent illuminated conditions for a
time period of 3000 s (Fig. 8b). The growing cathodic cur-
rent confirms the p-type conductivity of the CISe thin films.
During illumination, a sharp increase in the cathodic cur-
rent followed by steady state is due to reduction of ­H+ ions
by the photogenerated carriers at the electrode/electrolyte
interface [35]. In dark conditions, the photocurrent steeply
decreases and reaches the steady state dark current which
can be a significant indication of high carrier life time of the
photogenerated charge carriers.
For an applied bias of − 0.40 V/SCE, the measured photo-
current density ­(Jlight − Jdark) was calculated to be 1.23 × 10−5
A/cm2. The unaffected current density values measured for
the prolonged illumination time indicates the high stability
and quality of the absorber material.
4 Conclusion
In this work, CISe thin films have been synthesized by sin-
gle step electrodeposition technique using citrate-SDS elec-
trolyte. The addition of SDS along with pre-treatment has
been found to eliminate the binary multinuclear outward
growth and help in obtaining smooth and crystalline CISe
thin films. The effects of deposition potential on the struc-
ture, composition and morphology properties of the CISe
films were investigated. The XRD patterns and the Raman
spectra showed that the CISe film crystal structure changed
from chalcopyrite to sphalerite phase with increase of the
deposition potential. The FE-SEM image showed the signifi-
cant changes in morphology with the deposition potential.
With the increase in the deposition potential, the obtained
morphology of the thin films was smooth and crystalline
with minimized C ­ u2Se phase. The M–S studies revealed
the p-type semiconducting property of the thin films,
13
Journal of Materials Science: Materials in Electronics
a behaviour confirmed by the negative slope in the M–S
plot. The obtained carrier concentration was in the range
of 1.77 × 1016 and 2.62 × 1016 ­cm−3 which matches with
the carrier concentration reported for the high performance
devices. The increasing cathodic current during illumination
is the nature of the p-type semiconductor which comple-
ments the M–S results. Finally, a stable photocurrent density
of 1.23 × 10−5 A/cm2 was obtained at a potential of − 0.40 V
versus SCE electrode was achieved for the CISe film.
Acknowledgements  The Authors would like to thank NIT-Rourkela,
India for providing the infrastructure and experimental facilities.
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