Arabian Journal of Chemistry (2020) 13, 346–356

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

A study on solution deposited CuSCN thin films:

Structural, electrochemical, optical properties
Blessing N. Ezealigo a, Assumpta C. Nwanya a, Aline Simo b, R. Bucher b,
Rose U. Osuji a,b,c, Malik Maaza b,c, M.V. Reddy d, Fabian I. Ezema a,b,c,*

a
Department of Physics & Astronomy, University of Nigeria, Nsukka, Nigeria
b
Nanoscience African Network (NANOAFET), iThemba LABS-National Research Foundation, Capetown, South Africa
c
UNESCO-UNISA Africa Chair in Nanosciences/Nanotechnology, College of Graduate Studies, University of South Africa,
South Africa
d
Department of Physics and Material Science &Engineering, Faculty of Science &Engineering, National University,
Singapore 117542, Singapore

Received 13 January 2017; accepted 16 April 2017

Available online 27 April 2017

KEYWORDS Abstract A cost-effective successive ionic layer adsorption and reaction (SILAR) method was used
CuSCN; to deposit copper (I) thiocyanate (CuSCN) thin films on glass and steel substrates for this study.
Successive ionic layer The deposited thin films were characterized for their structural, morphological, optical and electro-
adsorption and reaction chemical properties using X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–vis-
(SILAR); ible spectroscopy and VersaSTAT potentiostat. A direct band gap of 3.88 eV and 3.6 eV with film
Band gap; thickness of 0.7 lm and 0.9 lm was obtained at 20 and 30 deposition cycles respectively. The band
Micro strain; gap, microstrain, dislocation density and crystal size were observed to be thickness dependent. The
Photoluminescence; specific capacitance of the CuSCN thin film electrode at 20 mV/s was 760 F g
1 for deposition 20
Electrochemical activities cycles and 729 F g
1 for deposition 30 cycles.
Ó 2017 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is
an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction

In recent times the unique combination of the optical and electronic

properties of CuSCN has been exploited for optoelectronic devices.
Early descriptions showed that the high optical transparency and suit-
* Corresponding author at: Department of Physics & Astronomy, able energy levels of CuSCN along with its solution process-ability and
University of Nigeria, Nsukka, Nigeria. chemical stability made it another promising choice for use as a hole-
E-mail address: fabian.ezema@unn.edu.ng (F.I. Ezema). transporting layer in organic photovoltaic (OPV) and organic light
emitting diode (OLED) devices. The high optical transparency of this
Peer review under responsibility of King Saud University.
material is indisputable as it is clearly evident from the transmission
spectra (Jaffe et al., 2010; Wu et al., 2005; Pattanasattayavong,
2014). Copper (I) thiocyanate (CuSCN), a p-type semiconductor is
usually used as a window layer in thin film solar cells (Sankapal
Production and hosting by Elsevier
et al., 2004).
http://dx.doi.org/10.1016/j.arabjc.2017.04.013
1878-5352 Ó 2017 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
A study on solution deposited CuSCN thin films
uSCN
Scheme 1 Structure of b-CuSCN.
CuSCN that has been reported to possess a wide band gap
(3.6 eV) (O’Regan and Lenzmann, 2004; Fernando et al., 2002;
Tennakone et al., 1987) exists in two polymorphic forms: a and b,
the b-CuSCN being more stable and readily available (Perera et al.,
2005; Pattanasattayavong et al., 2013). The a-phase has an
orthorhombic crystal lattice, while the b-phase can be a hexagonal
or rhombohedral structure (Jaffe et al., 2010), the b-CuSCN has layers
of SCN ions separating the plains of Cu atoms and a strong CuAS
bond that interconnects three dimensionally as shown in Scheme 1
(Ji et al., 2012).
Its polymer-like structure has made it a distinct semiconductor
material, because CuSCN thin films free of defects and pinholes can
be deposited on large surface areas (Perera et al., 2005; Hehl et al.,
2000; Tennakone et al., 1984). CuSCN has received so much attention
because of its application as a solid electrolyte in dye-sensitized solar
cell (Kumara et al., 2001; O’Regan et al., 2002; Perera et al., 2005).
So far, the p-type copper (I) thiocyanate (CuSCN) has been studied
mainly for use as a hole-transporting layer for photovoltaic applica-
tions (Snaith and Schmidt-Mende, 2007; Yanagida et al., 2009),
quantum-dot-sensitized solar cells (QDSCs) (Ruhle et al., 2010), extre-
mely thin absorber (ETA) solar cells (Briscoe and Dunn, 2011), hole-
transporting thin film transistors (TFTs) (Pattanasattayavong et al.,
2013; Perumal et al., 2014), high efficiency organic bulk hetero-
junction (BHJ) cells (Xu et al., 2015), as an interfacial layer in conven-
tional polymer solar cells (Takahashi et al., 2007; Chappaz-Gillot
et al., 2014).
CuSCN has been prepared and deposited by various techniques
including electrochemical deposition (Chappaz-Gillot et al., 2014;
Tennakone et al., 1995; Wu et al., 2005; Ni et al., 2007; Selk et al.,
2008; Kamiya et al., 2012), successive ionic layer adsorption and reac-
tion (SILAR) (Sankapal et al., 2004; Gao et al., 2008) and chemical
bath deposition (Ahirrao et al., 2011). Previously, the electrodeposition
of CuSCN was carried out in organic solvents (Chappaz-Gillot et al.,
2014; O’Regan et al., 2000) and recently it is now performed in aque-
ous electrolytes containing Cu2+ chelating agents so as to improve its
stability (Tennakone et al., 1995; Wu et al., 2005; Ni et al., 2007;
Kamiya et al., 2012). It is also used as a material for the synthesis of
polymer electrolytes (Sindhu et al., 1993) and used to improve the
long-term durability and stability of nanocrystalline photovoltaic cells.
CuSCN, a molecular metal pseudo-halide (polyatomic groups that
incorporate a pseudo-halogen anion such as thiocyanate) of singly-
ionized copper behaves like halide ions in chemical reactions
(Wijeyasinghe and Anthopoulos, 2015).
In this work, we studied the optical and electrochemical properties
of CuSCN thin films deposited at room temperature on glass and stain-
less steel substrates using SILAR method. Sankapal et al. (2004) and
Gao et al. (2008), have done some work on SILAR deposited CuSCN
thin films; however, they did not study the electrochemical properties.
Extensive work has been done on CuSCN regarding its hole transport-
ing and conducting properties (Jaffe et al., 2010; Ji et al., 2012). Here,
we present an in-depth study of the optical and electrochemical prop-
erties of CuSCN thin films. Electrochemical capacitors also known as
supercapacitors or ultracapacitors are energy storage devices capable
of charging and discharging in a few seconds, with life cycle in the
order of thousands of cycles (Makino et al., 2015). We were able to
347
show for the first time, the properties of CuSCN thin films for electro-
chemical energy storage application. This, to the best of the knowledge
of the authors has not been studied before now.
2. Experimental details
All the chemicals used were of analytical grade and include
copper sulphate pentahydrate (CuSO45H2O), sodium thiosul-
phate (Na2S2O35H2O), sodium thiocyanate (NaSCN), sodium
sulphate (Na2SO4), sodium thiosulphate (Na2S2O3) and
sodium thiocyanate (NaSCN). The substrates: glass (micro-
scopic glass slide with the dimension of 75  25  1 mm) and
steel (of dimension of 2.5  1.4 cm) were washed with deter-
gent, rinsed with distilled water, soaked in acetone for
30 min, rinsed with distilled water and then ultrasonicated
for 20 min and rinsed again, after which the substrates were
dried in a sterilizing oven at 60 °C for 20 min, and then kept
in an air tight box to prevent contamination.
0.1 M of CuSO4, the cationic precursor was dissolved in
distilled water and complexed with 0.1 M of Na2S2O3. The
anionic precursor was prepared by dissolving 0.2 M of NaSCN
in distilled water. The substrates were immersed in beaker A
containing the cationic precursor for 10 s, rinsed in distilled
water in beaker B for 3 s and immersed in the anionic precur-
sor in beaker C for 15 s and rinsed again in distilled water in
beaker D to remove the weakly held ions from the substrates
as shown in Fig. 1(A) & (B). The process of immersing the sub-
strates through all four beakers gives a complete SILAR cycle.
The samples were then dried in the oven for 10 min at 60 °C
before been characterized. For this study 20 and 30 deposition
cycles were employed so as to study the effect of number of
cycles on the properties of the thin films.
The deposited CuSCN films were characterized for their
structural properties using X-ray diffraction (XRD), with a
scanning range angle of 10–100° and radiation of wavelength
(k = 1.5406 Å). The optical properties of CuSCN thin films
were determined using UV-1800 Schimadzu spectrophotome-
ter which gave a measurement of the absorbance of the films
in the range of wavelengths 300–1000 nm, and the photolumi-
nescence (PL) emission and excitation spectra were recorded at
room temperature using a Shimadzu RF-5301-PC spectrofluo-
rometer. Zeiss Scanning Electron Microscope (SEM) was used
at various magnifications to study the morphological proper-
ties of the thin films. Quantitative composition of the deposited
thin films on glass substrate was determined using Energy Dis-
persive X-ray (EDX) spectroscope with counts up to 1000 in
the energy range of (0–20) eV. Finally, the electrochemical
properties were investigated using Princeton Applied Research
VersaSTAT (potentiostat) in a three-electrode configuration
which consists of the working electrode (CuSCN films on
stainless steel substrate), graphite counter electrode and satu-
rated Ag/AgCl reference electrode, using 0.1 M sodium sul-
phate (Na2SO4) solution used as electrolyte.
3. Results and discussion
3.1. XRD analysis
The XRD pattern of the deposited CuSCN thin films at 20 and
30 deposition cycles is shown in Fig. 2 for samples deposited
on glass substrate. The prominent peaks were observed at 2h
348
Figure 1 (A) Schematic diagram of SILAR deposition of CuSCN thin film, (B) schematic formation of the nanorods of CuSCN
deposition on glass and steel substrates.
Figure 2 XRD pattern of CuSCN thin film 20 & 30 deposition
cycles.
angles of 16.16°, 27.22°, 32.64°, 34.57°, 47.07°, 49.87° and
50.10° which correspond to a rhombohedral phase orienta-
tions of (0 0 3), (1 0 1), (0 0 6), (1 0 4), (1 1 0), (0 0 9) and (1 1 3),
respectively. The deposited CuSCN thin films match the refer-
ence b-CuSCN diffraction pattern (JCPDS 29-0581).
The crystallite sizes were obtained using Debye Scherrer’s
formula (Vinila et al., 2014):
kk
D¼
b cos h
B.N. Ezealigo et al.
30 cycles
where D is the crystallite size, b is the full width of the observed
diffraction line at half its intensity maximum, k = 0.9 and
k = 1.5406 Å is the wavelength of X-ray source, h is the
Bragg’s diffraction angle at the peak position. The crystallite
sizes were estimated to be 11.67 ± 0.05 nm and 11.88 ± 0.05
nm at 20 and 30 deposition cycles, obtained at (0 0 6) and
(1 0 1) plane respectively, and this proved that the deposited
CuSCN thin film is nanocrystalline. The result obtained is in
range with values reported by Hatch et al. (2013) and
Tennakone et al. (1987).
Stress resulting from micro strain ðeÞ in the films can nega-
tively affect the structural properties of the films. The micro
strain was calculated using the formula (Moreh et al., 2013):
b cos h
e¼ ð2Þ
4
Dislocation density (d) was obtained using the formula (Henry
et al., 2016):
1
d¼ ð3Þ
D2
The films possessed a micro strain of 0.0296, 0.0292
± 0.0001 at 20 and 30 deposition cycles respectively. It was
observed that the value of the micro strain decreases with an
increase in film thickness which may be related to reduction
in inter-planar spacing between the atoms, thereby reducing
the stacking fault in the films (Henry et al., 2016; Chen
et al., 2005). The dislocation density that is a measure of
imperfection of the crystal associated with misalliance of a part
of the lattice of the crystal with respect to another part was
also seen to decrease with an increase in film thickness. At
20 cycles the thin film has a dislocation density of 0.74 m
2
ð1Þ
and 0.709 ± 0.001 m
2 at 30 cycles.
A study on solution deposited CuSCN thin films 349

3.2. Morphological studies within wavelength range of 300–840 nm at 30 cycles and

300–480 nm at 20 cycles. The absorption spectrum is similar
The morphology of the deposited CuSCN thin films on glass to that obtained by Iwamoto et al. (2014). It was observed that
substrate showed a well-defined rod-like shaped crystal at 20 an increase in the number of cycles increases the optical
cycles, which is consistent with the report by Chappaz-Gillot absorption capacity of the thin films, and this feature is also
et al. (2013) for CuSCN electrodeposited at room-temperature seen to affect the band gap of the material.
from an aqueous copper sulphate solution stabilized by EDTA. The absorption coefficient a was obtained using Eq. (4)
As the deposition cycles increased to 30 cycles the rods became (Camara et al., 2013):
broader and closely packed. The rod-liked shaped surface mor-


1 1
phology shown in Fig. 3(A-D) is electrochemically favourable, a¼ ln ð4Þ
because it provides high surface area for electrochemical reaction. t T
The Energy Dispersive X-ray (EDX) on glass substrates
confirms the presence of CuSCN with peaks of copper (Cu), where t is the thickness of the film, andT is the transmittance.
sulphur (S), carbon (C), and nitrogen (N) which are the con- The film thickness was estimated using t ¼ qA
M
where t is film
stituent elements of CuSCN. Fig. 3(E & F) confirms the forma- thickness, M is mass of the film material in grams, A is area of
tion of CuSCN with peaks of Copper (Cu) 41.53%, sulphur (S) the film in cm2 and q is the density of the film material
12.97%, carbon (C) 13.85%, and nitrogen (N) 13.75%. The (q = 2.85 g cm
3 for CuSCN).
presence of Si and Ca could be from the glass substrate used The mass, M of the deposited material was estimated using
for deposition. this relation:
3.3. Optical studies M ¼ Mfinal
Minitial
where Minitial Mfinal the mass of the substrate (in grams) before
3.3.1. Absorbance and after deposition respectively.
Fig. 4(A) shows the variation in the absorbance with wave- The measurement was done using Mettler Toledo weighing
length. The CuSCN thin films showed a high absorbance balance B2404-5.

Figure 3 (A) SEM micrograph of CuSCN at 20 cycles at a magnification of 10 KX, (B) SEM micrograph of CuSCN at 20 cycles at a
magnification of 50 KX, (C) SEM micrograph of CuSCN at 30 cycles at a magnification of 10 KX, (D) SEM micrograph of CuSCN at 30
cycles at a magnification of 50 KX, (E) Energy dispersive X-ray (EDX) at 20 cycles and (F) EDX at 30 cycles deposited on glass substrates.
350
3.3.2. Band gap
2
The variation of (ahm) vs hm which gave a straight line and a
direct band gap of 3.88 and 3.60 eV at 20 and 30 deposition
cycles respectively is shown in Fig. 4(B). The shift in band
gap may be related to the deposition condition of this study
such as molar concentration, number of cycles and dipping
time which are basic parameters that affect the thickness of
the films and important parameter for the estimation of the
band gap of a material (Malliga et al., 2014; Shaban et al.,
2015; Gao et al., 2008). The thickness of the films obtained
was 0.7 and 0.9 ± 0.05 lm for 20 and 30 cycles respectively.
This difference in the thickness implies that the deposition
technique used to enable the control of film thickness for a
desired value. The values obtained for the band gap are in
range with those reported by Gao et al. (2008) and Ahirrao
et al. (2011).
In Fig. 4(C), the plot of (ahm)1/2 versus photon energy (hv)
for indirect band gap gave an estimated value of 2.85 and
2.6 ± 0.02 eV at 20 and 30 deposition cycles respectively,
and these values are in range with the report of
Pattanasattayavong et al. (2013).
3.3.3. Extinction coefficient
The graph of extinction coefficient (k) against wavelength is
presented in Fig. 5(A). The extinction coefficient that is a mea-
sure of absorption of light in a medium, showed a maximum at
a wavelength of 300 nm for both 20 and 30 deposition cycles
followed by a sharp decrease as the wavelength increases,
which indicates light loss due to scattering. The positive value
shows that the deposited film absorbs a good amount of the
optical energy. The drop in k values could be as a result of
absorption of light at the grain boundaries at high wavelength
region and also suggests that surface of the thin films is smooth
(Bhaskar et al., 2001).
3.3.4. Refractive index
The values of the refractive index shown in Fig. 5(B) were
obtained using Eq. (5) for semiconductors, where the extinc-
tion coefficient (k) and refractive index (n) are related by the
given equation (Guneri et al., 2015):
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ð1 þ RÞ 4R
n¼ þ
k2 ð5Þ
ð1
RÞ ð1
RÞ2
where R is the reflectance.
In the visible range of the electromagnetic spectrum, the
refractive index (n) at 20 cycles was 2.65 and 2.68 ± 0.04 at
30 cycles at photon energy of 2.5 eV and 1.75 eV respectively.
These values are in range with the report by
Pattanasattayavong et al. (2013). The magnitude of the refrac-
tive index decreases as it approaches the higher energy region
for both samples. The sharp decrease could be said as a result
of surface imperfections as well as internal reflections or pho-
ton energy trapped within the grain boundary (Ong et al.,
2000). According to Ravindra et al. (2007), the refractive index
originates from narrow bands of absorption; this proves the
similarity between the absorbance and refractive index curve.
3.3.5. Dielectric constant
The real and imaginary dielectric constants were calculated
using the formulas respectively (Wiktorezyk, 2002):
B.N. Ezealigo et al.
er ¼ n2
k2 ð6Þ
ei ¼ 2nk ð7Þ
The real part of the dielectric constant ðer Þ in Fig. 5(C) shows
the dispersion that takes place when a beam of light falls on the
film, while the imaginary part of the dielectric constant ðei Þ
shown in Fig. 5(D) is a measure of the dissipative rate of the
wave medium. The dielectric properties of the films vary with
refractive index. The imaginary dielectric constant represents
the energy absorption from the dipole motion of an electric
field (Taskin and Podder, 2014; Kamruzzaman et al., 2014).
The film at 30 cycles showed a distinctive hump which can
be attributed to deceleration of the light beam as it passes
through the material.
3.3.6. Optical conductivity
The photoconductivity increased with photon energy as a
result of the generation and transport of holes and electrons,
as a result of electrons excited by photon energy. The values
of the optical conductivity obtained were
8.31  1013 ± 0.05 S/cm and 10.5  1013 ± 0.05 S/cm at 20
and 30 deposition cycles respectively. In Fig. 5(E) at higher
energy level, the samples have a high conduction rate, which
is significant at 30 cycles compared to the 20 cycle sample. This
may be as a result of large number of carriers donors present as
the concentration increases and the energy level shifts towards
the conduction band (Henry et al., 2016).
3.3.7. Photoluminescence
The photoluminescence (PL) property showed an emission
peak at 400 nm for both 20 and 30 deposition cycles, excited
at 350 nm. The 30 cycle film showed a higher emission peak
which indicates that the PL response is affected by the thick-
ness of the film and it is consistent with the report by Verma
and Joshi (2009). The PL spectra in Fig. 5(F) showed a peak
in blue region about 407 nm and a broad peak in the blue
region. The peak at 407 nm is as a result of the recombination
of free excitons through an exciton – exciton collision process
(Parganiha et al., 2015) while a broad blue region with slight
emission peak was observed at 510 nm.
3.4. Electrochemical studies
3.4.1. Cyclic voltammetry (CV)
The cyclic voltammetry (CV) measurements of CuSCN thin
films were performed at a scan rate of 5, 20, 30, 40, 50, 75
and 100 mV s
1 and the potential window was between
1.0
and +1.0 V Ag/AgCl.
The specific capacitance, Cs obtained by CV measurement
was calculated by using the relation:
R
IðVÞdV
Cs ¼ ð8Þ
m  v  DV
where I is the response current, m is the mass of the active
CuSCN material of the electrode, v is the scan rate in V s
1
and DV is the range of the potential window.
The specific capacitance of the CuSCN electrode obtained
at 20 mV/s was 760 F g
1 for 20 cycles and 729 F g
1 for 30
cycles. Fig. 6(A & B) shows the plot of current density against
potential at various scan rates for 20 and 30 deposition cycles
A study on solution deposited CuSCN thin films 351

Figure 4 (A) The variation in the absorbance with respect to wavelength at 20 and 30 cycles; (B) variation of (ahm)2 vs hm of CuSCN for
direct band gap at 20 and 30 cycles; (C) variation of (ahm)1/2 vs hm of CuSCN for indirect band gap at 20 and 30 cycles.

respectively. The difference in the specific capacitance value at
20 and 30 deposition cycles could be attributed to the charge
on the electrode. The specific capacitance (Cs) decreases at
higher scan rate because of the incapability of active sites to
withstand the redox reactions (Nwanya et al., 2014, 2015) as
shown in Fig. 6(C).
3.4.2. Galvanostatic charge discharge (GCD)
The GCD curves for CuSCN thin films at 20 and 30 deposition
cycles respectively at current densities of 5 mA, 5.5 mA, 6 mA
and 6.5 mA are shown in Fig. 6(C-D). The specific capacitance
decreases with increase in current density, a maximum value of
Cs to be 17 F g
1 at a current density of 5 mA/cm2. Though IR
drop is inevitable in a charge-discharge test it should not be
large, because huge IR drop results in less charge across the
electrodes of the cell than the applied voltage thereby reducing
the performance of the device (Balakrishnan and
Subramanian, 2014). Increase in IR drop reduces the capaci-
tance of a supercapacitor. Therefore, the capacitance value
of the CuSCN material, accompanied with a high IR drop as
a result of large energy loss due to resistance, makes the
CuSCN thin film electrode not so good for supercapacitor
application. The capacity retention of the CuSCN film for
long-term stability was investigated at a current density of
5 mA obtained was 94% after 1000 cycles as shown in Fig. 6
(F). The ragone plot in Fig. 6(G) compared the power density
and energy density of the CuSCN thin film electrode for energy
storage device application. The energy density was found to
decrease with increasing current density while the power den-
sity increases with increasing current density which suggested
that the discharge capacity is proportional to the charging
capacity (Nwanya et al., 2016).
The specific capacitance is calculated from the formula
(Gund et al., 2013):
ID  TD
Cs ¼ ðF g
1 Þ ð9Þ
mv
TD
Columbic efficiency; g ¼  100% ð10Þ
Tc
where V is the potential window, ID is the discharge current,
TD and Tc is the discharge and charge time respectively and
m is the active mass. The electrodes possess a columbic effi-
ciency of about 98%.
352 B.N. Ezealigo et al.

Figure 5 (A) Plot of extinction coefficient versus wavelength, (B) plot of refractive index of CuSCN thin films versus photon energy, (C)
plot of real part of dielectric constant versus photon energy, (D) plot of imaginary part of dielectric constant versus photon energy, (E)
plot of optical conductivity versus photon energy deposited on glass substrates, (F) photoluminescence plot.

3.4.3. Electrochemical impedance spectroscopy
The EIS technique helps to understand the various
mechanisms and kinetics of electrochemical reactions at the
electrodes, electrode/electrolyte interface and within the
electrolyte. Many impedance parameters of the device such
as electrolyte resistance (Rs), the charge transfer resistance
(Rct) over the interface between the electrode and the
electrolyte, the constant phase element (CPE or Q) and
Warburg (W) element can be determined from EIS analysis.
The constant phase element is due to inhomogeneity at the
electrode/electrolyte surface and dynamic disorder associated
with diffusion. The Warburg (W) element gives an indication
of the ion diffusion into the electrode materials and is seen
in the intermediate frequency and is the 45 line to the imagi-
nary impedance (Z00 ) axis.
Fig. 7(A) shows the Nyquist plot of the CuSCN thin film
electrode in the frequency range of 100 kHz to 10 mHz, with
an amplitude of 10 mV and at a bias voltage of 0.7 V. The
A study on solution deposited CuSCN thin films 353

Figure 6 (A) CV curves for CuSCN thin film electrodes at 20 cycles at various scan rates, (B) CV curves for CuSCN thin film electrodes
at 30 cycles at various scan rates, (C) galvanostatic charge discharge curve of the CuSCN thin electrode at various current densities at 20
cycles, (D) galvanostatic charge discharge curve of the CuSCN thin electrode at various current densities at 30 cycles, (E) variation of
specific capacitance with scan rate, (F) variation of capacitance retention of the electrode films with cycle number for both 20 and 30
cycles, (G) ragone plot of CuSCN film electrode deposited on steel substrates.
354 B.N. Ezealigo et al.

(A)

Figure 7 (A) Nyquist plot for CuSCN thin films at 20 & 30 deposition cycles on steel substrates; (B-C) bode plot of CuSCN thin film
electrode at 20 and 30 cycles respectively.

1
Table 1 Values of the fitted electrochemical circuit parameters ZCPE ¼ ð11Þ
QðjwÞn
from EIS analysis of the electrodes.
Circuit element 20 cycles 30 cycles where Q is the frequency-independent constant relating to the
Rs (X) 5.96 6.05 surface electroactive properties, and w represents the radial fre-
CPE (F) 6.41  10
3 6.50  10
4 quency. For n = 0, the CPE is a pure resistor; n = 1, CPE is a
n 0.8 0.8 pure capacitor, n =
1, CPE is an inductor, while n = 0.5 it is
Rct (kX) 1.08 1;36 Warburg impedance (Zw). The value for n obtained is greater
than 0.5 but less than the ideal value of unity for pure electric
double layer capacitors (EDLC). This confirms that the elec-
equivalent circuit and the fitted values of the circuit parameters trode material behaves more like a pseudocapacitor. Pseudoca-
were obtained using ZSimpWin software and are shown in the pacitors, achieve energy storage by rapid faradaic redox
inset of Fig. 7(A) (upper left) and Table 1, respectively. The reaction with the charge transfer at the interface between elec-
equivalent circuit model Rs is the resistance offered by the elec- trode and electrolyte.
trolyte solution and the value is the high frequency intercept of From these values obtained, it is obvious that CuSCN elec-
the semi circle on the real impedance axis. Rct is the charge trodes have high charge-transfer resistance; the 30-cycle elec-
transfer resistance offered at the interface between the elec- trode has a higher value than the 20-cycle electrode. This
trode and the electrolyte and the value is the diameter of the could be one of the reasons for the higher specific capacitance
semi-circle. value obtained at 20 deposition cycles.
The Rct value for 20 and 30 deposition cycles was 1.08 and The plot of the logarithm of frequency against the phase
1.36 kX respectively and is a function of the electronic and angle (the Bode plot) is shown in Fig. 7(B-C). CuSCN electrode
ionic resistances (Dubal et al., 2011; Pandolfo and gave a maximum phase angle of 62° and 68°. These values are
Hollenkamp, 2006). Eq. (11), (Raju and Ozoemena, 2015), characteristic of faradaic reaction and hence confirm the pseu-
defines the impedance of the CPE: docapacitive nature of the electrodes. Pseudocapacitors have
A study on solution deposited CuSCN thin films
maximum phase angles that are usually less than 90° while pure
electric double layer capacitors possess phase angle of 90°
(Nwanya et al., 2014). The slight difference in the phase angle
between the two cycles could be related to the thickness of
the film.
Since the deposited material has proven to possess a good
capacitance value of 760 F g
1 and capacitance retention capa-
bility for over 1000 charge-discharge cycles, it can be possibly
applied in as an electrochemical energy storage material.
4. Conclusion
CuSCN thin films have been successfully synthesized by successive
ionic layer adsorption and reaction (SILAR) method for electrochem-
ical and optical studies. The extinction coefficient, refractive index and
photoluminescence properties of the film were observed to increase
with film thickness. The specific capacitance, Cs of the CuSCN elec-
trode obtained at 20 mV/s was 760 F g
1 for 20 cycles and 729 F g
1
for 30 cycles. While these values are appreciable, the CuSCN electrodes
have high IR drop as well as high charge transfer resistance (Rct). This
could impede its electrochemical energy storage application. However,
the electrode showed good stability maintaining about 94% of the
stored charge for over 1000 charge-discharge cycles. Therefore more
optimization is needed in order to reduce the high IR drop and the
charge transfer resistance. Our future studies on this material will be
geared towards this aspect in order to improve its electrochemical
energy storage capability.
Acknowledgement
We graciously acknowledge the grant for this project by TET-
FUND under contract number TETF/DESS/UNN/NSUKK
A/STI/VOL.I/B4.33. We thank the US Army Research Labora-
tory–Broad Agency Announcement (BAA) for the financial
support given to this research (under Contract number
W911NF-12-1-0588). Also we thank Engr. Emeka Okwuosa
for generous sponsorship of April 2014 and July, 2016 confer-
ence/workshops on applications of nanotechnology to energy,
health & Environment and for providing some research
facilities.
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