i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e8

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Photoelectrochemical characteristics of CuO films

with different electrodeposition time

Asad Mahmood*, Fatih Tezcan, Gulfeza Kardas‚**

Çukurova University, Science and Letters Faculty, Chemistry Department, 01330, Adana, Turkey

article info abstract

Article history: This paper explores the effect of electrodeposition time on microstructure, optical, and
Received 1 February 2017 photoelectrochemical properties of CuO films. CuO films were electrochemically deposited
Received in revised form on tin-doped indium oxide (ITO) substrates using a Cu2O electrodeposition method fol-
8 May 2017 lowed by annealing at 550
C for 2 h. The electrochemical deposition was carried out at
Accepted 1 June 2017 different times (300, 600, 1200, and 1800 s) utilizing a copper sulfate pentahydrate and lactic
Available online xxx acid solution. X-ray diffraction (XRD) and field emission scanning electron microscopy
(FESEM) were used to perform phase and microstructure analysis. Photoluminescence (PL)
Keywords: studies confirmed an increase in emission intensities with increasing deposition time. In
CuO addition, a significant change was observed in photoelectrochemical properties of the film
Photoelectrodes by varying the deposition time. The film deposited for 600 s showed a high photocurrent
Electrodeposition density of 0.55 mA cm2 at 0.5 V. Moreover, a lowest resistance from electrochemical
FESEM impedance spectroscopy (EIS) was recorded for the films electrochemically deposited for
Photocurrent 600 s.
Water splitting © 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

several physical and chemical barriers, such as stability and

Introduction
Photoelectrochemical water splitting is an effective way to
produce and store hydrogen as a clean energy source and to
overcome the energy crisis and environmental hazards such
as global warming and acid rain those are associated with the
hydrogen production from the sources such as coal and nat-
ural gas [1,2]. For this purpose a range of photoelectrode ma-
terials has been reported, i.e., Cu2O, CuO, p-doped Si, CuRhO2,
Cu2ZnSnS4, Fe3O4 and CuBi2O4 [3,4]. Another technique is
electrolysis of alkaline water, which has been investigated in
depth for the hydrogen evaluation reactions (HER) [5,6].
However, adapting the laboratory practices into industry for
the commercial production of hydrogen is still hindered by
economical feasibility. To address these issues, attempts have
been reported to increase the stability of photocathodes in
photocatalytic water splitting reactions and utilization of
earth-abundant materials (copper based oxides, Fe2O3, ZnO,
TiO2, BiVO4) instead of using expensive and heavy metals such
as platinum, iridium, and ruthenium [7,8]. Among these,
owing to its narrow band gap (1.21e2.1 eV), CuO is considered
as one of the most promising semiconductor material for
applications in catalysis, batteries, gas sensing, and photo-
electrochemical cells (PECs) [9,10]. The CuO films and powders
exhibiting different shapes and sizes have been processed by
various synthetic procedures [11e13], such as thermal
decomposition of Cu foil, hydrothermal method, sol-gel
method, solvothermal method, self-catalytic growth, and

* Corresponding author.
** Corresponding author.
E-mail addresses: amkhan036@yahoo.com (A. Mahmood), gulfeza@cu.edu.tr (G. Kardas‚).
http://dx.doi.org/10.1016/j.ijhydene.2017.06.003
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Mahmood A, et al., Photoelectrochemical characteristics of CuO films with different electrodeposition
time, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.06.003
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e8
electrodeposition [14e18], and reference therein. Chiang et al.
[19] synthesized CuO nanoparticles utilizing flame spray py-
rolysis. The processing parameters such as precursor con-
centration, gas flow, and temperature were studied in detail.
The variation in precursor concentration from 0.5 to 35% w/w
resulted in a corresponding increase in particles diameter
from 7 ± 2 to 20 ± 11 nm. In addition, the particles grown in the
low gas flow showed a significant increase in diameter, which
was associated with more retention time in high-temperature
zone. Shaislamov et al. [20] developed CuO/ZnO photo-
electrode utilizing a two-step synthesis route. The films
morphology and PEC performance were studied in depth. In
the initial step, CuO nanorods were developed by thermal
oxidation of the already electrodeposited CuO films. Next, ZnO
nanobranches were grown on the surface of the initially
deposited CuO films using a hydrothermal synthesis route.
The durability test showed an increase in stability of the
electrode up to 90%. Similar studies suggest that microstruc-
ture plays an important role in materials' performance. For
example, a high hydrogen storage capacity of 220 and
180 mAh/g has been reported for Cu(OH)2 and CuO nano-
ribbons [21]. Among these, electrodeposition has been
considered as the best technique to develop homogeneous
thin films with precise control over film thickness and
microstructure. Further, the method is economical due to the
use of inexpensive precursor sources and simple experi-
mental setup [14,22,23]. The microstructure of film, grain
morphology, and surface topography plays an important role
in the photoinduced processes [22,24]. The surface features
affect the interaction of light with film surface and conse-
quently, the electron transport mechanism; therefore, it is
important to optimize the microstructure-property relation-
ship in these optoelectronic devices. The properties of CuO
have been extensively reported; however, no attempt has
been reported to investigate the effect of electrodeposition
time on the CuO film microstructure and the PEC performance
to our best knowledge.
In this paper, we have studied the effect of electrodeposi-
tion time on surface morphology of ITO/CuO films and the
corresponding effect on the photoelectrochemical properties.
For efficient absorption of light, an optimum value of film
thickness is required for better PEC performance. The XRD and
FESEM were used for the phase and microstructure investi-
gation, respectively. Furthermore, the optical properties and
photocatalytic response were studied to investigate the CuO
films' electrodeposition time on the photocurrent in water
splitting reactions.
Experimental procedure
Copper sulfate pentahydrate (CuSO4$5H2O; Aldrich), lactic
acid (C3H6O3; Aldrich) and deionized water were used as the
starting materials and solvent. The CuO films were deposited
on ITO substrates by using a galvanostatic deposition method.
Prior to deposition, ITO substrates were washed with a hot
detergent solution, acetone, and ethanol for 10 min each.
Then, the substrates were dried with a nitrogen blow. The
precursor solution was prepared by using a 0.5 M CuSO4$5H2O
and 1.3 M lactic acid. During the electrodeposition, the
Please cite this article in press as: Mahmood A, et al., Photoelectrochemical characteristics of CuO films with different electrodeposition
time, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.06.003
temperature was kept constant at 60
C, while the pH was
maintained around 10e12 by using a 5.0 M NaOH solution. The
electrodeposition was carried out for 300, 600, 1200 and 1800 s
which corresponds to notation S1, S2, S3, and S4, respectively,
by applying a current density of 0.3 mA cm2. A 50.0 mL of
fresh precursor solution was used for each experiment. After
deposition, the Cu2O films were washed with distilled water
and subsequently dried in an oven at 60
C for 24 h. The dried
Cu2O films were annealed at 550
C for 2 h in air in order to
achieve CuO films.
Thin film deposition was carried out using Gamry Instru-
ment (Galvaniostatic-potentiostatic; Gamry Interface 1000).
Thermo-FTIR spectrometer (Model: smart UR diamond
attenuated total reflection (ATR)) was used to determine the
phase and the nature of the atomic bond in the films.
UVevisible NIR (Model: Cary 7000 Universal Measurement
Spectrophotometer (UMS)) was used to study the absorption
behavior of the thin films. The surface morphology was
investigated by using a FESEM (Model: Zeiss/Supra 55 VP). The
phase of CuO films was studied by using X-ray diffraction
(XRD, Model: Rigaku Miniflex 600) with a step size of 5
min1.
The PEC characteristics of films were measured by using a CHI
analyzer (Model: CHI 660D electrochemical). The scan rate
linear sweep voltammetry (LSV) of 5 mV s1 was applied be-
tween 0 and 0.5 V range. The EIS measurements were per-
formed in the frequency range of 105 Hz and 103 Hz at open
circuit potential and with an amplitude of 5 mV. A 0.5 M
Na2SO4 solution was used to study the photocatalytic activity
of CuO films on water splitting. A solar simulator (SunliteTM
Solar Simulators; M-SLSS) was used to illuminate the samples.
The PEC performance was measured in three electrode system
using Ag/AgCl (3.0 M KCl solution) as reference electrode, a
platinum sheet (2 cm2) as counter electrode and CuO film
samples as the working electrode.
Results and discussions
Fig. 1(a) shows XRD profiles for the ITO/CuO films annealed in
air at 550
C for 2 h. The peak profiles were matched to the
monoclinic CuO phase (JCPDS card: 048-1548), where the
diffraction peaks at 2q ¼ 32.48, 35.74, 38.96, 48.75, 53.02 and
58.64 were indexed to (110), (111), (111), (202), (020) and (202)
crystal planes, respectively [23,25]. No impurities such as Cu2O
and Cu3O4 were observed, which further confirmed that the
Cu2O was converted to CuO on ITO substrates. The relative
intensities were observed to increase with increasing depo-
sition time, which might be due to enhanced crystallinity
related to the high deposition time [26]. Fig. 1(b) shows FT-IR
spectrum of the ITO/CuO films annealed at 550
C for 2 h.
The peaks in the wave number range from 420 to 610 cm1,
which can be resolved in three modes, i.e., Au and Bu modes,
and other Bu modes of the CuO. The strong peaks around
597 cm1 and 699 cm1 are the characteristic Cu (II)eO
stretching vibration peaks. The peaks around 538 cm1 and
607 cm1 were assigned to CueO stretching vibration [14,27].
Similar peaks were observed for all the samples.
Fig. 2 shows PL spectra of the ITO/CuO films annealed at
550
C for 2 h. So far the origin of luminescence in CuO has not
been fully established. The near band edge emission for the
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e8
Fig. 1 e (a) XRD and (b) FTIR for the ITO/CuO films annealed at 550
C for 2 h in air. The (*) represent peaks associated with the
substrates.
Fig. 2 e Photoluminescence spectra for the ITO/CuO films
annealed at 550
C for 2 h in air.
CuO has been reported at different wavelengths (l) by various
researchers, i.e., 365, 300, 395 and 467 nm [28] and references
therein. This characteristic peak of the band emission was
observed around 386 nm in the current study. All the samples
showed a second emission peak at 780 nm, which were
associated with the near band emission. The photo-
luminescence peak for the Cu2O around 626 nm was not
observed, which further suggested absence of the Cu2O pha-
ses [29]. The relative intensities of the emission peaks were
observed to increase for the samples S1 to S4 with increasing
electrodeposition time. UV-NIR absorption measurements
were performed to study the absorption mechanism of elec-
trodes (Fig. 3(a) and (b)). The optical band gap (Eg) was calcu-
lated using Eq. (1) [30]:
(ahu)r ¼ A(hn  Eg)
Please cite this article in press as: Mahmood A, et al., Photoelectrochemical characteristics of CuO films with different electrodeposition
time, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.06.003
3
where a is absorption coefficient, hv is the photo energy, A is
constant, and r represents an indirect transition. The value of
absorption can be calculated by Eq. (2).
absorbance
a ¼ 2; 303 (2)
d
where d is thickness of the CuO film on ITO. The band gap
values were calculated by extrapolation of the curve to the x-
axis. Sample S4 showed a high absorbance value in contrast to
the rest of the samples, which is associated with the high
thickness value. The calculated band values were 1.41 eV,
1.40 eV, 1.43 eV and 1.44 eV for S1, S2, S3 and S4, respectively.
The lowest band gap value of S2 suggests more active sites on
the electrode surface which can efficiently utilize light for
water splitting reaction.
Fig. 4 shows surface morphology of the ITO/CuO films
annealed at 550
C for 2 h. It has been established that Cu2O
deposits in the form of pyramid structures in the given
experimental conditions. At high temperature (500
C), Cu2O
is converted to CuO and the color of film changes from reddish
brown to black [31]. All the samples showed a heterogeneous
grain growth. No considerable defects were observed on the
film's surface, which is generally associated with the solution
based processed films. Sample S1 showed an empty surface
area among the particles due to an incomplete surface
coverage related with the limited deposition time. The surface
was covered completely by increasing the deposition time for
samples S2, S3, and S4. In addition, a small particle size was
observed for the film deposited for 300 s. The particle size was
observed to increase with increasing deposition time such as
600, 1200, and 1800 s. This behavior might be due to an in-
crease in volume diffusion and coalescence, which resulted in
bigger particles and more compactness. The corresponding
average thickness for samples S1, S2, S3, and S4 were
measured to be 233, 627, 816, and 980 nm, respectively (Fig. 5).
Initially, the rate of deposition is high as evident from the
respective thicknesses of sample S1 and S2; however, the
films' thickness did not increase significantly with increasing
deposition time (S3, S4). This may be associated with the
decreasing electrolyte concentration. The first step in elec-
(1) trodeposition is the formation of Cu(I)[C3H6O3] in the
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e8

Fig. 3 e (a) UV-NIR absorption spectra and (b) Tauc plot of the ITO/CuO films annealed at 550
C for 2 h in air.

Fig. 4 e FESEM surface micrograph for the ITO/CuO films (S1, S2, S3, S4) annealed at 550
C for 2 h in air. The average grain
size diameter has been presented by the digital scale from the instrument software.

precursor solution by Eq. (3), which in the basic media, Cu(I)
[C3H6O3] is further converted to Cu2O film structures in the
second step (Eq. (4)). The second step is critical in determining
the size of the pyramid shaped structures, which are formed
as result of the mass migration of the Cu(I)[C3H6O3] from the
solution boundary to the electrode surface. Furthermore, the
average particle (agglomerates) size increased with increasing
deposition time, which might be due to high mass migration
with increasing deposition time. CuO is the most stable phase
compared to Cu2O, which is achieved at high temperatures
(Eq. (5)) [32].
Cu(II) [C3H6O3]2 þ e / Cu(I) [C3H6O3] þ [C3H5O3]
2Cu(I) [C3H6O3] þ 2OH / Cu2O þ H2O þ 2[C3H5O3] (4)
550
C
Cu2 O ƒƒ! CuO (5)
Fig. 6(a) shows Nyquist plots of the ITO/CuO films at room
temperature in 0.5 M Na2SO4 solution as electrolytes under
illumination. All the samples showed a single semicircular arc
except sample S2 (two semicircles), which can be used to
study the resistive and capacitive nature of materials. The
nature of the semicircular arcs was also confirmed from the
phase angle diagrams (Fig. 6(c)). The behavior of the semicircle
can be used to interpret the mobility of electrons in the bulk of
material as well as at the interface of electrode and electrolyte
[24, 33]. Sample S1 showed the highest resistance while
(3)
sample S2 showed a low resistance. From these results, it can

Please cite this article in press as: Mahmood A, et al., Photoelectrochemical characteristics of CuO films with different electrodeposition
time, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.06.003
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e8 5

Fig. 5 e FESEM surface micrograph of the cross sections for the ITO/CuO films (S1, S2, S3, S4) annealed at 550
C for 2 h in air.
The vertical line bar demonstrate the average thickness of the films.

Fig. 6 e Complex impedance analysis of the ITO/CuO films in 0.5 Na2SO4 solutions at room temperature; (a) Nyquist plots for
the samples S1, S2, S3, S4, (b) and (c) shows jZj vs. logf and Phase angle vs. frequency for the ITO/CuO films, respectively.

be inferred that the electron mobility at the electrode-
electrolyte interface increases with increasing deposition
time [34, 35]. This decrease in charge transfer resistance might
be due to an increase in the number of carrier species accu-
mulated at the electrode-electrolyte interface with increasing
deposition time or thickness. In addition, the lowest resis-
tance observed in the sample S2 might be associated with the
optimum particle size and film thickness. Generally, electrons
from the bulk of particles move to the surface of grains, which
further contribute to the reaction; thus, bigger particles
suggest that more time is required for the electrons to come to
the grain surface in contrast to the smaller particles. More-
over, bigger particles might exhibit a high number of defects
such as oxygen vacancies, which act as electron sinks and are
involved in electron hoping mechanism, which results in low
conductivity in contrast to sample S2. Also, the two semi-
circles observed in sample S2 indicates the catalytic surface
for hydrogen evaluation reaction. This behavior was further
studied by the jZj vs. log frequency (log f) plots in Fig. 6(b) Here,
jZj is the complex number which has both the real (Z0 ) and

Please cite this article in press as: Mahmood A, et al., Photoelectrochemical characteristics of CuO films with different electrodeposition
time, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.06.003
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e8
imaginary (Z00 ) components of impedance. The sample S2
showed a low magnitude for the jZj compared to the rest of the
samples. Fig. 6(c) presents the phase angle vs. log f plot. All the
samples showed a broad phase angle around the frequency
range from 104 to 103 Hz. Generally, the peak in the low-
frequency regime belongs to the electron diffusion within
the electrolytes while the peaks at high frequency are asso-
ciated with the resistance in semiconductors [24]. Sample S2
showed resolved peaks, which clearly identified the electron
transfer phenomena dependence on both within the electrode
and electrolyte interface and diffusion in electrolytes. The
phase angle was observed to decrease from 80
to 60
. The
less negative phase angles for the CuO thin films compared to
the perfect capacitor (90
) confirmed a low resistance to
charge mobility in the vicinity of the semiconductor and at
electrolyte and electrode interface [36].
Fig. 7 shows the Mott-Schottky plots for the CuO films
electrochemically deposited on the ITO substrates and sub-
sequently annealed at 550
C for 2 h in air. The flat band po-
tential (Vfb) was measured using Mott-Schottky equation in
order to understand the intrinsic properties of CuO films,
which were conducted utilizing 5 mV AC amplitude at 500 Hz
frequency. The calculated capacitance of CuO at electrode/
electrolyte interface at various potentials depend on the
following equation:
 
1 2 kB T
¼ V  Vfb 
C2 q 20 2s ND q
where εs is the dielectric constant of CuO, ε0 is the permittivity
of free space, q is an electronic charge, T is the absolute
temperature, and kB is the Boltzman's constant [37]. The curve
is extrapolation on the x-axis to define Vfb values of electrodes.
The Mott-Schottky plot of CuO in 0.5 M Na2(SO4) demonstrate
a negative slope, providing proof of CuO as a p-type semi-
conductor. Vfb values of þ0.6634 V, þ0.536 V, þ0.685 V, and
þ0.611 V were obtained at different deposition times including
300 s, 600 s, 1200 s and 1800 s, respectively [38, 39].
Fig. 8 shows photocurrent density as a function of voltage
for the ITO/CuO films. The photocatalytic performances of
Fig. 7 e Mott-Schottky plots of ITO/CuO films
electrochemically deposited for different times.
Please cite this article in press as: Mahmood A, et al., Photoelectrochemical characteristics of CuO films with different electrodeposition
time, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.06.003
Fig. 8 e Variation of current density vs. reference electrode
(Ag/AgCl) for the ITO/CuO films in light. The inset figure
presents current density vs. AgAgCl reference electrode in
the dark.
the samples were measured in a three-electrode cell system.
The measurements were conducted in the light of an artificial
(6) solar illumination with a voltage that varied from 0 to 0.5 V.
The photocurrent density was observed to increase for all the
samples in light. A high photocurrent density in light
compared to the dark confirmed the well photocatalytic ac-
tivity for water splitting as a photocathode. The photocurrent
density is associated with the proton reduction and photo-
generation of electrons. Further, it also confirmed the p-
type semiconductive nature of the CuO [40]. The sample S1
showed a low photocurrent response compared to rest of the
samples. Generally, the photogenerated electrons are
responsible for the hydrogen production which must be
sufficiently available to reduce hydrogen. However, the
electrons transfer mechanism in a semiconductor is a com-
plex phenomenon. In the current experimental scenario, it is
assumed that the microstructure played a major role in
variation of the photocurrent response in CuO films exhibit-
ing different thicknesses. An increase in thickness and
average grain size might be responsible for high absorption
due to increasing number of CuO particles which provides a
greater number of mobile electrons and surface roughness,
respectively. However, in order to reduce hydrogen, the
electrons must be available on the grain surface, which de-
pends on the movement of electrons from the bulk of grains
to the surface of grains. The current study suggests that the
larger grains exhibit some defects such as oxygen vacancies
and porosity which diminished the flow of electrons in
contrast to the CuO films deposited at 600 s. In addition, the
possibility of oxygen vacancies in the larger grains is high
which might act as sinks for electrons and hence decrease
the mobility of electrons. A high photocurrent density of
0.55 mA cm2 was recorded for the sample S2 at 0.5 V. In
addition, sample S2 showed a 91.9% increase in the PEC ef-
ficiency in light compared to the dark. These IeV results are
in good agreement with the EIS results.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e8
Conclusion
Copper oxide films were successfully electrodeposited on ITO
substrates by varying the deposition time from 300 to 1800 s and
subsequently annealed at 550
C for 2 h. The XRD pattern
confirmed the monoclinic phase for CuO films. FTIR studies
showed Au and Bu modes, and other Bu modes for the CuO
films. The average grain growth was observed to increase with
increasing deposition time. The optical band gap was observed
to increase with increasing deposition time while the sample S2
showed the lowest band gap value (Eg ¼ 1.4 eV). In addition, the
Mott Schottky results suggested the p-type semiconductor na-
ture of the CuO films irrespective of their deposition time. Ac-
cording to EIS results, sample S2 exhibited the lowest total
resistance. Moreover, S2 showed the highest current density
(0.55 mA cm2) at 0.5 V at the LSV measurements, which
further confirmed the EIS results. In the current study, 600 s (S2)
proved to be an optimum electrodeposition time for the better
photocurrent density of the ITO/CuO films as a photocathode
for water splitting reaction via solar light irradiation.
Acknowledgement
The authors acknowledge the financial support by the Scien-
tific and Technological Research Council of Turkey (TUBITAK
Project No: 116C035) under the 2236-Co-Funded Brain Circu-
lation Scheme.
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