Journal of The Electrochemical Society, 164 (14) D999-D1005 (2017) D999

Nucleation Mechanism and Optoelectronic Properties of Cu2 O

onto ITO Electrode in the Electrochemical Deposition Process
Xiaojiao Yu,z Xiyan Tang, Ju Li, Jie Zhang, Song Kou, Jie Zhao, and Binghua Yao
School of Science, Xi’an University of Technology, Xi’an 710048, People’s Republic of China

Cyclic voltammetry and chronoamperometry were used to study the deposition process at the initial stage of Cu2 O electrodeposition
on indium tin oxide-coated glass. The current transient data and predicted values were analyzed by the instantaneous and progressive
nucleation models under different electrolyte concentrations. The effects of the Cu2 O nucleation mechanism on microstructure and
photoelectric properties of Cu2 O were investigated by X-ray photoelectron spectroscopy, X-ray diffractometry, scanning electron
microscopy, ultraviolet visible spectrophotometry and fluorescence spectrophotometry. The results show that the electrochemical
deposition process of Cu2 O is irreversible and controlled by diffusion, and the diffusion coefficient was calculated to be 2.2 × 10−6
cm2 · s−1 . The nucleation mechanism of Cu2 O is related to the electrolyte concentration. When the concentrations of Cu(AC)2 were
5 mM and 15 mM, the nucleation processes of Cu2 O were consistent with the progressive nucleation and instantaneous nucleation
models, respectively. Under the instantaneous nucleation mechanism, the prepared Cu2 O displayed a uniform structure, composed
of sword-shaped dendritic crystal. Compared to the progressive nucleation, the purity of the Cu2 O was higher, the bandgap narrower
(2.006 eV), and the photoluminescence intensity higher. The Cu2 O had a high carrier density (4.9 × 1022 cm−3 ) and a low charge
transfer resistance (127.27 K · cm2 ). It exhibits superior photoelectric performance.
© The Author(s) 2017. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any
medium, provided the original work is properly cited. [DOI: 10.1149/2.1081714jes] All rights reserved.

Manuscript submitted October 16, 2017; revised manuscript received November 22, 2017. Published December 9, 2017.

The forbidden bandgap of cuprous oxide (Cu2 O) is 1.9–2.5 eV. Due
to its advantages in abundance, low cost, and nontoxicity, it satisfies
the necessary economy and environmental requirements to be a viable
material for solar energy conversion. In addition, the position of the
conduction band (more negative than −0.7 V vs RHE) provides a large
driving force for proton reduction in photoelectric cells.1–3 Therefore,
Cu2 O can be used in solar cells of high open-circuit voltage in the con-
ventional solid-state configuration.4 Cu2 O also has wide applications
in memory resistors,5 gas sensors6,7 and catalysts.8,9 Cu2 O thin films
have been prepared by various techniques such as thermal oxidation,10
electrodeposition,11–13 radio frequency magnetron sputtering,14,15 and
atomic layer deposition.16 Among these techniques, electrodeposi-
tion has the attractive features of low processing temperature and
low instrumentation cost, making it the most common method for the
fabrication of Cu2 O thin films.
Since the photoelectric conversion efficiency of Cu2 O can reach
20% in theory, many scholars have explored the possibility of its
application in photovoltaic conversion. However, the current highest
photoelectric conversion efficiency is only 5.38%,17,18 due to the high
recombination rate of photoproduction electron holes. Due to its elec-
tronic structure, the bonding, surface energy, and chemical reactivity
of Cu2 O have a direct relationship with its surface morphology and
grain sizes.19,20 Controlling the Cu2 O surface morphology and particle
sizes allows one to decrease the Cu2 O photoproduction electron-hole
recombination rate and thus improve its photoelectric properties. In
the electrochemical deposition process, the deposition potential,21 so-
lution composition,22,23 and pH24 influence the surface morphology
and particle sizes of Cu2 O. Many researchers have focused on vary-
ing the electrochemical deposition parameters to control the surface
morphology and particle sizes of Cu2 O. Fewer have studies the Cu2 O
nucleation and growth mechanisms and their effect on performance.
Nonetheless, the nucleation and growth mechanisms are fundamen-
tal factors. Therefore, it is necessary to explore these mechanisms in
order to improve the photoelectric efficiency of Cu2 O.
This paper studies the Cu2 O electrodeposition process from the
angle of the driving force through cyclic voltammetric and timing
current curves, in order to understand the nucleation mechanism of
Cu2 O. This will help in designing Cu2 O thin film materials. The
results will provide more guidance and predictability in the synthesis
of materials, so as to improve the photoelectric properties of Cu2 O.
In this paper, we performed a comprehensive investigation of the
z
E-mail: yxjw@xaut.edu.cn
electrochemical deposition process of Cu2 O on ITO electrodes. The
effects of deposition potential and electrolyte concentration on the
nucleation mechanisms were investigated. Based on this, the effects of
the nucleation mechanism on Cu2 O structure morphology and optical
properties were discussed, yielding specific insights.
Experimental
Preparation of Cu2 O thin film.—The electrode material used
in the experiment was indium tin oxide-coated glass (ITO, square
resistance≤15/, transmissivity (T%)≥83%, Foshan Junyi Glass
Co., Ltd. China). Electrodeposition experiments were undertaken
at room temperature with a CHI660E electrochemical workstation
(Shanghai Chenhua Co., Ltd. China) using a three-electrode cell ar-
rangement. The working electrode of the ITO was cleaned ultrason-
ically by acetone and ethanol in turn for 15 min, rinsed in deionized
water and dried naturally. The ITO area in contact with the electrolyte
was 4.5 cm2 . Platinum electrodes were used as counter electrodes. A
saturated calomel electrode (SCE) was used as the reference electrode.
Electrolytes of different concentrations were prepared by dissolving
different molar mass copper acetate (Cu(AC)2 ) in 150 mL of distilled
water. The pH of all the electrolytes was adjusted to 4.90 with 5.0
mol/L NaOH solution. The mixing speed was 200 rpm, the electrolyte
temperature was 25◦ C, and the Cu2 O thin film was prepared by 60
min of electrodeposition. The prepared Cu2 O thin film was soaked in
anhydrous ethanol, taken out after 5 min and dried naturally.
Characterization of structure and performance of Cu2 O thin
film.—The crystal structure, banding state, and surface morphology of
Cu2 O thin film were characterized and analyzed using a K-Alpha type
X- ray photoelectron spectroscope (XPS, Thermo Fisher Scientific,
USA), an XRD-7000 type X-ray diffractometer (XRD, Shimadzu,
Japan), and a VEGA3 scanning electron microscope (SEM, TES-
CAN, Czech Republic). The optical properties of the Cu2 O thin film
were determined by a UV-3600 ultraviolet-visible spectrophotome-
ter (UV-Vis, Shimadzu, Japan) and a Fluoromax-4 type fluorescence
spectrophotometer (PL, HORIBA, Japan).
All the electrochemical performance measurements were carried
out in a three-electrode system with a platinum electrode as counter
electrode, an SCE as reference electrode, and the Cu2 O thin films
as working electrodes, using a CHI-660E electrochemical working-
station. A 0.5M Na2 SO4 solution was used as supporting electrolyte.
The electrochemical impedance of the Cu2 O thin film was measured
in the dark state.

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 D1000 Journal of The Electrochemical Society, 164 (14) D999-D1005 (2017)

12 2

1 Lnj
9 Linear Fit of Lnj
Current density/uA ⋅cm-2

-2
6

Lnj/uA ⋅cm
-1
3
a -2
0
-3
-3
b -4
-0.37 -0.36 -0.35 -0.34 -0.33 -0.32 -0.31 -0.30
-6 Overpotential/V vs.SCE
0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6
Potential/V vs.SCE Figure 3. Tafel plot corresponding to the electrochemical reduction reaction,
the scan rate is 1 mV · s−1 .
Figure 1. Cyclic voltammogram of Cu2 O on ITO electrode.
density of the deposition peak versus half the power of the scan rate.
Results and Discussion Fig. 2 shows that the cathodic current increased rapidly, indicating
that the deposition rate of Cu2 O is controlled by diffusion. With the
Cyclic voltammograms of deposition process.—Fig. 1 shows decrease of scan rate, the Cu2 O deposition potential gradually moved
cyclic voltammogram (CV) of the ITO electrode for a blank solu- to a more positive potential and the peak current decreased. The inset
tion with 0.1 M KCl (curve a) and a mixed solution containing 0.1 M shows a good linear relationship between the current density of the
KCl and 10 mM Cu(AC)2 (curve b). The scan rate was 10 mV · s−1 . deposition peak and the scan rate, further indicating that the reduction
As can be seen from curve b, the Cu2 O reduction peak appeared when process is controlled by diffusion.
the potential was about −0.1 V, showing the Cu2+ on the ITO surface The electrode kinetics of Cu2 O deposition can be expressed by the
being reduced to Cu+ . At 0.3 V, the Cu2 O oxidation peak appears, and Butler-Volmer Eq. 2
the Cu+ was oxidized. Meanwhile, for the electron transfer reaction,     
the cathodic transfer coefficient (α) can be calculated using Eq. 125 zF zF
  j = jo exp −α η − exp β η [2]
V p − V p/2  = 1.857RT /nαF [1] RT RT

Here, VP is the peak potential (V), VP/2 is the potential (V) at half Here, j is the current density (mA · cm−2 ), j0 is the exchange current
peak height, R is 8.314 J · mol−1 · K−1 , the temperature T is 298.15 K, density (mA · cm−2 ), and η is the overpotential (V). The exchange
the quantity n is the number of electrons gained or lost in the reaction, current density can be used to describe the ability to gain or lose
in this case one, and F is the Faraday constant. The value of α was electrons in an electrode reaction, and it reflects the difficulty of
0.74, calculated using Eq. 1. The anodic transfer coefficient (1-α) was the electrode reaction. It can be described by Tafel curves. Fig. 3
0.26. The value of α is much higher than anodic transfer coefficient. illustrates a typical Tafel plot using a 0.1 M KCl and 10 mM Cu(AC)2
This indicates that the reduction process of Cu2+ is easier than the solution on an ITO electrode. The j0 value was estimated at 0.23 ×
oxidation process. The oxidation process is very difficult to induce. 10−3 mA · cm−2 . The exchange current density was relatively large,
indicating that the electroactivity of Cu2+ in surface deposition is
Electrodeposition process analysis of Cu2 O.—Fig. 2 shows a set higher.26
of CVs of Cu2 O deposited on the ITO in the 10 mM Cu(AC)2 solution Fig. 4 shows the potentiostatic current transient curve of the elec-
with different scan rates. The inset is a fitted line plot for the current trodeposition of Cu2 O on the ITO electrode in a 10 mM Cu(AC)2
solution. The deposition potential was −0.1 V, the reverse pulse po-
tential was 0.3 V, and the pulse time was 100 s. The illustration in

0
0.2
-2
Current density/uA ⋅cm-2

-4
-2

0.0
Current density/uA ⋅cm

-6
0 -0.2 -0.3 j
Current density/uA ⋅cm-2

-8
Current density/uA ⋅cm-2

Linear fit of j
-2
-10 1 (mv/s) -0.4
-4 5 (mv/s) -0.4
-12 -6 10 (mv/s) -0.5
50 (mv/s)
-8
-14 0 2 4 6 8 10 100 (mv/s) -0.6 -0.6
0.4 0.5 0.6 0.7
V1/2/(mv⋅s-1)1/2
t-1/2/s-1/2
0.1 0.0 -0.1 -0.2 -0.3 -0.4 0 50 100 150 200
Potential/V vs.SCE Time/s

Figure 2. Cyclic voltammograms of Cu2 O with different scan rates, the inset Figure 4. A potentiostatic current transient at a long time, the inset is the
is fitted line plot. Cottrell plot.

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 Journal of The Electrochemical Society, 164 (14) D999-D1005 (2017) D1001

Fig. 4 shows that, during the first 100 s, the transient curve shape
1/2
4.6733
was a typical response curve of an electrochemical process of nu- tm =
cleation and growth without double layer charging. Due to the form πAN0 K D
of the new phase and the increase of nucleation number on the ITO jm = 0.4615z F D 3/4 c(K AN0 )1/4 [7]
electrode surface, the current increased rapidly. Each Cu2 O crystal
nucleus formed a diffusion zone. The current increased continuously Therefore, the dimensionless Scharifker-Hills mathematical model
with the expansion of these areas. The current reached its maximum can be expressed by Eq. 8 for instantaneous nucleation and Eq. 9 for
when the surrounding diffusion fields exhibited coalescence. Then, the progressive nucleation:
diffusion current of the electrode began to decay to equilibrium.27 The
2  
2
charges of the reduction process (QC ) and oxidation process (QA ) were j 1.9542 t
= t 1 − exp −1.2564 [8]
calculated by integrating the reduction and the oxidation branches of jm tm
tm
the current transients curve. The values of QC and QA were 419.7 ×
10−6 and 287.5 × 10−6 C, respectively. The value of QC is greater than
2  
2
2
the value of QA , indicating that the electrodeposition process of Cu2 O
on ITO was irreversible.
The diffusion of electroactive Cu2+ in the solution can be quanti-
tatively expressed by the diffusion coefficient (D). It can be estimated
by analyzing the current density (j) of the direct pulse transient stage
versus time (t) plot (Fig. 4 inset). The relationship between j and t
satisfied the Cottrell Eq. 3 in the case of constant potential:
1
It nF D 2 c
jt = = 1 1
[3]
A π2 t 2
Here, I is the current, n is the charge number (the value of n is
1), A is the effective area of the electrode (2.7 cm2 ), F is Faraday
constant, and c is the concentration of Cu2+ in the solution (10 mM).
Before the limiting current is reached, by drawing a Cottrell curve
with |j| = f (t−1/2 ) on one axis, a linear graph should be obtained
when the maximum width of the growing diffusion layer is achieved.
Fig. 4 inset shows the linear part of the experimental Cottrell plot and
the corresponding data fit. The diffusion coefficient was calculated by
Cottrell curve data fitting. The value of D is 2.2 × 10−6 cm2 · s−1 , which
is the approximate diffusion coefficient of Cu2+ as an electroactive
substance in other solutions.28–30
Nucleation mechanism analysis of Cu2 O.—To further analyze the
deposition mechanism of Cu2 O on ITO electrode, the potentiostatic
transient curves were recorded in different concentrations of Cu(AC)2 ,
as shown in Fig. 5. Fig. 5 shows that the deposition mechanism of
Cu2 O can be analyzed by a Scharifker and Hills mathematical model
of three-dimensional growth.31–33 Since the electrodeposition process
of Cu2 O is controlled by diffusion, the potentiostatic transient curves
in Figs. 5a, 5b and 5c can be analyzed by the instantaneous nucleation
Eq. 4 or the progressive nucleation Eq. 5 of three-dimensional growth
zF D 2  
1
j= 1 − exp (−N0 πt K D) [4]
1 1
π2 t 2
1 
 sity of Cu2 O under different deposition conditions. Table I shows that
z FcD 2 2AN0 πt 2 K D
j= 1 1
1 − exp − [5]
π2 t 2 3
Here, N0 is the nucleation density on the substrate surface (cm−2 ), A
is steady state nucleation rate constant (s−1 ), K is the non-dimensional
growth rate constant of crystal nucleus, and defined by K = (8πcM/)1/2 .
To discuss the mechanism of the nucleation process, both experi-
mental data and theoretical data were transformed to non-dimensional
coordinate curves, normalized by the maximum current density (jm )
and its corresponding time(tm ). The experimental data of jm and tm
were obtained from the potentiostatic transient curves, and the theo-
retical maximum values can be calculated by Eq. 6 for instantaneous
nucleation and Eq. 7 for progressive nucleation
1.2564
tm =
N0 πK D
jm = 0.6382z F Dc(K N0 )1/2 [6]
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j 1.2254 t
= t 1 − exp −2.3367 [9]
jm tm
tm
The potentiostatic current transient curves of Cu2 O deposition in
three different concentrations of Cu(AC)2 solutions are shown in Figs.
5a, 5b and 5c. Figs. 5a, 5b and 5c show that, with applied potentials
applied, the current increased rapidly to its peak in the potentiostatic
current transient curves under different conditions. Then it gradually
decayed to a stable state and remained there. This is because, in the
current rising process, Cu2+ discharge nucleation and the growth of
crystals occurs on the electrode surface, and thus the cathodic cur-
rent density increases. This reaction occurs until the current density
has reached a peak of nucleation current density. Then, because of
overlap between the crystal nucleus, the current attenuation reaches
a balance between current increase and decay. Under the same depo-
sition potential, the peak current and equilibrium current decreased
with increasing Cu(AC)2 concentration. This shows that the discharge
nucleation was enhanced and the nucleation number increased. Under
the same Cu(AC)2 concentration, the peak current and its time of ar-
rival increased with the increase of deposition potential. In addition,
the time for the peak current to weaken to equilibrium prolongs, indi-
cating that the duration of the crystal nucleus formation stage extends
with the increase of deposition potential.
The non-dimensional plots transformed from the curves of Figs. 5a,
5b and 5c using Eqs. 8 and 9 are shown in Figs. 5a , 5b and 5c ). In
Figs. 5a , 5b and 5c , the curves i and the curves p are the theoretical
curves for instantaneous and progressive nucleation, respectively. In
Fig. 5a (5 mM Cu(AC)2 ), the nucleation process curves conformed
well to the nucleation theory curve of the progressive nucleation at
different potentials. In Fig. 5b (10 mM Cu(AC)2 ) shows that the
nucleation process fell between the progressive nucleation and instan-
taneous nucleation at different potentials. In Fig. 5c shows that the
nucleation mode on the ITO electrodes in a 15 mM Cu(AC)2 solu-
tion was close to the instantaneous nucleation at different potentials.
This indicates that the electrolyte concentration has a significant in-
fluence on the nucleation mechanism of Cu2 O, while the deposition
potential has no obvious impacts. Table I shows the nucleation den-
the nucleation density of Cu2 O under the instantaneous nucleation
mechanism is much higher than the nucleation density under the pro-
gressive nucleation mechanism. In the same nucleation mechanism,
the nucleation density shows a decreasing trend with the decrease of
the deposition potential.
The structure and surface morphology analysis of Cu2 O thin
film.—Fig. 6 shows the XRD patterns of Cu2 O thin films at differ-
ent electrolyte concentrations. All diffraction peaks for three samples
accord well with the standard powder diffraction patterns of cuprite
Cu2 O (JCPDSNo.05-0667). The diffraction peaks were observed at 2θ
29.55◦ , 36.42◦ , 42.30◦ , 61.34◦ , 74.40◦ , and 77.75◦ , which correspond
to the Cu2 O (110), (111), (200), (220), (311), and (222) crystal planes,
respectively. No other diffraction peaks were observed, indicating that
pure Cu2 O can be obtained through electrodeposition. Three samples
were characterized by (111) crystal plane preferred orientation. This
can be attributed to different growth rates along different crystal planes
of the Cu2 O crystal. This is because the value of the surface energy of
 D1002 Journal of The Electrochemical Society, 164 (14) D999-D1005 (2017)

0.0 1.0
a a'
Current density/uA ⋅cm-2 -0.1 -0.10 (V) i
0.8
-0.11 (V)
-0.2 -0.12 (V)
p
0.6

(j/jm)2
-0.3
0.4
-0.4 -0.10 (V)
0.2 -0.11 (V)
-0.5 -0.12 (V)

-0.6 0.0
0 5 10 15 20 0.4 0.8 1.2 1.6 2.0 2.4
Time/s t/tm

0.0 1.0

b b’
-0.1 i
0.8
Current density/uA ⋅cm-2

-0.2
-0.10 (V)
0.6

(j/jm)2
-0.3 -0.11 (V) p
-0.12 (V)
-0.4 0.4
-0.10 (V)
-0.5 -0.11 (V)
0.2 -0.12 (V)
-0.6

-0.7 0.0
0 5 10 15 20 0.4 0.8 1.2 1.6 2.0 2.4
Time/s t/tm

-0.4 1.0

-0.5 c c’
i
Current density/uA ⋅cm-2

0.8
-0.6

-0.7 -0.10 (V)

0.6
-0.11 (V) p
(j/jm)2

-0.8 -0.12 (V)

-0.9 0.4
-0.10 (V)
-1.0 -0.11 (V)
0.2 -0.12 (V)
-1.1

-1.2 0.0
0 5 10 15 20 0.4 0.8 1.2 1.6 2.0 2.4
Time/s t/tm

Figure 5. The potentiostatic current transients curves for electrodeposition Cu2 O on ITO electrodes in (a) 5 mM, (b) 10 mM, and (c) 15 mM Cu(AC)2 solution,
Figures 5a , 5b and 5c are corresponding non-dimensional plots of (j/jm)2 versus (t/tm).

Cu2 O each crystal is (100) > (110) > (111). The high surface energy
crystal face grows faster and the low surface energy crystal face grows
slower in the vertical direction. Therefore the crystal faces of high sur-
face energy decreased and the areas of crystal faces with low surface
energy increased.34,35 Therefore, the prepared Cu2 O in most cases has
(111) preferential orientation. Fig. 6 shows that the diffraction peak
intensities of the three samples were different. This may be related to
Table I. The nucleation density of Cu2 O thin film under different
electrolyte concentration.
N/105 cm−2 −0.10 V
5 mM 0.18977
15 mM 6.46274
the nucleation mechanism under different electrolyte concentrations.
This indicates that the change of electrolyte concentration has little in-
fluence on the intensity of the diffraction peak, and it does not change
the preferential orientation of Cu2 O thin films. It has been proven that
the (111) crystal plane of Cu2 O has a high catalytic activity.36
Fig. 7a shows the XPS spectra of the Cu2 O thin film. Fig. 7a
shows that there were Cu elements, O elements, and a small amount
of adsorbed C elements in the samples. Fig. 7b, showing the Cu-
resolution XPS spectra, shows that there were two peaks at 932.5 and
952.2 eV, which respectively correspond to the Cu 2p3/2 and Cu 2pl/2
binding energies of Cu2 O. In addition, the FWHM at the peak energy
for Cu 2p3/2 (1.2 eV) was not more than 1.5 eV, and the satellite peak
does not appear between the Cu 2p3/2 and Cu 2pl/2 energy peaks,
−0.11 V −0.12 V indicating that no Cu or CuO are present in the Cu2 O thin film. Fig.
0.07609 0.07350 7c shows the O-resolution XPS spectra. Fig. 7c shows that there was
4.51206 2.90771 a broad peak at 531.7eV corresponding to the O 1s binding energy,

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 Journal of The Electrochemical Society, 164 (14) D999-D1005 (2017) D1003

5mM Cu(AC)2 0.75

(111) 10mM Cu(AC)2 5mM Cu(AC)2
15mM Cu(AC)2 0.60 10mM Cu(AC)2
(200)
(220)
15mM Cu(AC)2
(110) (311) (222)
0.45

Absorbance
Intensity/a.u.

1.2

0.30 1.0 Eg=2.035eV

0.8
Eg=2.018eV
Eg=2.006eV
0.6
0.15
0.4

0.2
0.00 0.0
1.8 1.9 2.0 2.1 2.2 2.3 2.4

200 300 400 500 600 700 800

20 30 40 50 60 70 80 Wavelength/nm
2θ/degree
Figure 9. UV-Vis spectra of Cu2 O thin films, the inset is bandgap energy of
Figure 6. XRD patterns of the Cu2 O thin films. Cu2 O.

and the shoulder was not detected along with the peak, indicating that films can be calculated according to Eq. 1037
the basic elements of O come from Cu2 O. Thus, the prepared Cu2 O  m/2
thin film shows high purity. This is consistent with XRD analysis K hν − E g
A= [10]
results. hν
Fig. 8 shows the SEM images of the Cu2 O thin films. The ori- Here, A is absorbance, K is a constant, m is 1, photon energy (eV)
entation characteristics of the three samples are clear from Fig. 8. for the abscissa, (Ahv)2 for the ordinate, taking the absorbing boundary
Under instantaneous nucleation (Fig. 8c), the grains had a sword-like tangent, the intersection of the tangent and the horizontal axis is the
dendritic shape, and the crystal grains were regular in density. Under bandgap energy. Usually the bandgap energy between the valence
progressive nucleation (Fig. 8a), in addition to the sword-shape den- band and the conduction band of semiconductors increases with the
dritic crystals, there were many irregular grains and the grain size was decrease in particle size.38 The bandgap energy of the Cu2 O thin films
nonuniform. Fig. 8b shows that the surface morphology of the Cu2 O were 2.006 (15 mM Cu(AC)2 ), 2.018 (10 mM Cu(AC)2 ), and 2.035
was composed of dendritic crystals and irregular grains, and the grain eV(5 mM Cu(AC)2 ), respectively. This result is consistent with the
size was relatively uniform. reported bandgap energy of Cu2 O thin film. The Cu2 O has the smallest
bandgap energy under the instantaneous nucleation mechanism (15
Optical performance analysis of Cu2 O thin film.—The UV-Vis mM Cu(AC)2 ), indicating that in this case the Cu2 O has the largest
diffuse reflectance spectra of the Cu2 O thin film are shown in Fig. particle size. This is consistent with the results shown in Fig. 8. This
9. Fig. 9 indicates that the absorption intensity of Cu2 O thin films indicates that the nucleation mechanism has a slight effect on the
does not change with the change in electrolyte concentration, with the bandgap energy of Cu2 O thin film. The prepared Cu2 O thin films can
absorbing boundary at about 640 nm. The bandgap energy of the thin absorb solar energy effectively.

(a) (b) 932.5eV (c) 531.7eV

O1s
Cu 2p3/2 Cu 2p3/2
Cu 2p1/2
Intensity/a.u.
Intensity/a.u.

Intensity/a.u.

O1s 952.2eV
Cu 2p1/2

C1s

0 200 400 600 800 1000 1200 925 930 935 940 945 950 955 960 965 525 530 535 540
Binding energy/eV Binding energy/eV Binding energy/eV

Figure 7. (a) XPS spectra, (b) Cu 2p XPS spectra, and (c) O1s XPS spectra of Cu2 O thin film.

Figure 8. SEM images of the Cu2 O thin films (a) 5 mM Cu(AC)2 , (b) 10 mM Cu(AC)2 , and (c)15 mM Cu(AC)2 .

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 D1004 Journal of The Electrochemical Society, 164 (14) D999-D1005 (2017)

250000 5mM Cu(AC)2

5mM Cu(AC)2
10mM Cu(AC)2 10mM Cu(AC)2

15mM Cu(AC)2 200000 15mM Cu(AC)2

Intensity/a.u.

150000

100000

50000

470 475 480 485 490 495 500 0

0 100000 200000 300000 400000 500000 600000
Wavelength(nm)

Figure 10. Photoluminescence spectra of the samples.

Figure 12. Nyquist plot of the samples, the inset is the equivalent circuit.

Fig. 10 shows the photoluminescence (PL) spectra of the samples,

with the excitation wavelength at 360 nm. Fig. 10 shows that the PL
spectra of the different samples were essentially identical in shape
and position, indicating that electrolyte concentration does not have
an influence on the shape and position of the PL spectra. The PL
intensity of the prepared Cu2 O in 15 mM Cu(AC)2 electrolyte was
strongest, indicating that it had the best optical performance.39,40
Electrochemical impedance analysis of Cu2 O thin film.—To find
the charge carrier density of Cu2 O, the Cu2 O electrodes were char-
acterized by electrochemical impendence spectroscopy (Fig. 11). The
potential sweep was performed at a fixed frequency (1 kHz) with a
scan speed of 10 mV/s. The charge carrier density can be extracted
from the slope of the plot between the reciprocal of the square of
capacitance per unit area (1/C2 ) versus the applied potential (V) ac-
cording to the Mott-Schottky Eq. 1141,42
Fig. 11 shows the Mott-Schottky plot for the Cu2 O electrodes in
a 0.5 M Na2 SO4 solution. Fig. 11 shows that the slopes of the Mott-
Schottky curves of all three samples were positive, indicating that
the three Cu2 O thin films were n-type semiconductors.44,45 This indi-
cates that the change of electrolyte concentration does not influence
the conductive type of the prepared Cu2 O semiconductor thin films.
According to the Mott-Schottky Eq. 11 and Fig. 11, the estimated
charge carrier densities of the Cu2 O were 2.1 × 1022 , 3.2 × 1022 ,
and 4.9 × 1022 cm−3 for the Cu2 O thin films electrodeposited, when
electrolyte concentration were 5 mM Cu(AC)2 , 10 mM Cu(AC)2 , and
15 mM Cu(AC)2 , respectively. Under the instantaneous nucleation
mechanism, the Cu2 O has higher charge carrier densities. The highest
majority carrier density of the Cu2 O thin film signifies a fast charge
transfer, and thus an enhanced photoelectrochemical performance.45,46
Nyquist curves can be used to analyze the process of charge trans-

1 2 KB T fer between the Cu2 O electrodes and the electrolyte interface. Fig. 12
= V − Vfb − [11] shows the Cu2 O electrodes’ Nyquist plots. The Nyquist plots were
C2 eεε0 A2 ND e
measured at an open-circuit potential of 0.005 V, with a frequency
Here, C is the charge layer’s capacitance, e is the electronic charge, range of 10 kHz to 1 Hz under dark conditions. In Fig. 12, the points
ε is the relative permittivity of Cu2 O (ε∼7.5),43 ε0 is the permittivity were experimental values, while continuous lines were simulated data
of vacuum, A is working electrode area, ND is the charge carrier according to the equivalent circuit. The equivalent circuit diagram is
density, V is the applied potential, VFB is the flatband potential of shown in the inset of Fig. 12, where Rs is the solution resistance, R1
semiconductor, KB is Boltzmann’s constant, and T is the absolute is the charge transfer resistance of the electrode/electrolyte interface,
temperature. According to Mott-Schottky theory, the slope of the R2 is the thin film resistance of the electrode, and CPE1 and CPE2 are
linear region (linear part) of the Mott-Schottky curve is negative, constant phase components. The diameter of the semicircle indicates
indicating that the measurement sample is a p-type semiconductor the interfacial charge transfer resistance R1 and thin film resistance
and the hole is the majority carrier, while a positive slope reveals an R2 .47 Table II shows that the fitted values of Rs were almost con-
n-type semiconductor where the electron is the majority carrier. stant for all cases in the dark, which may be ascribed to deviations
in the position of the reference electrode.48 The fitted values show
that the thin film resistance follows the order of R2 (353.22 K · cm2 ,
1.2 15 mM Cu(AC)2 ) < R2 (486.90 K · cm2 , 10 mM Cu(AC)2 ) < R2
(545.09 K · cm2 , 5 mM Cu(AC)2 ). The prepared Cu2 O under the
5mM Cu(AC)2
1.0 instantaneous nucleation mechanism shows the lowest R2 value. The
10mM Cu(AC)2 fitted values of R1 were 127.27, 138.32, and 206.22 K · cm2 for
15mM Cu(AC)2 the prepared electrodes in 15 mM Cu(AC)2 , 10 mM Cu(AC)2 , and
14

0.8
10

5 mM Cu(AC)2 electrolytes, respectively. The efficient charge trans-

fer at the interface between photoelectrode/electrolyte impeded the
4

0.6 charge recombination and led to the high charge transport of electrons
F cm

through the films.47,49 Thus, the prepared Cu2 O electrode in the 15

-2

0.4 mM Cu(AC)2 electrolyte has the lowest R1 , showing a very good rate
2

of charge transfer. The R1 of the prepared electrode in the 10 mM

1/C

0.2 Cu(AC)2 electrolyte was only slightly larger than the prepared elec-
trode in the 15 mM Cu(AC)2 electrolyte. Thus, the charge transfer rate
0.0 of the both electrode were similar. It has been reported38,49 that a com-
-0.12 -0.08 -0.04 0.00 0.04 0.08 0.12 pact structure thin film exhibits much less charge transfer resistance
E/V vs.SCE than a porous one for the same chemical composition. Therefore, the
difference of charge transfer resistance may be attributed to the differ-
Figure 11. Mott-Schottky analysis of the samples in 0.5 M Na2 SO4 solution. ences of the surface structure of the prepared thin films under different

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 Journal of The Electrochemical Society, 164 (14) D999-D1005 (2017)
Table II. Fitting parameters according to the equivalent circuit of Fig. 12.
RS /K · cm2 R1 /K · cm2 CPE1/10−5 usn / · cm2
5 mM 5.3586 206.22 1.145
10 mM 5.2689 138.32 0.555
15 mM 5.3088 127.27 11.166
nucleation mechanisms. This is consistent with the results of this ex-
periment. The results show that the prepared Cu2 O thin film has higher
charge carrier densities and lower resistance under the instantaneous
nucleation mechanism. This indicates that the nucleation mechanism
has a significant effect on the charge carrier density and resistance of
the prepared Cu2 O thin film. Accordingly, the right choice of mecha-
nism can help such thin films make more efficient use of solar energy
and boost their prospects in practical applications.
Conclusions
The electrodeposition process of Cu2 O thin film on ITO surface
was studied by electrochemical techniques. The results show that
the electrodeposition process of Cu2 O is an irreversible diffusion-
controlled process. The nucleation mechanism of Cu2 O is associated
with the electrolyte concentration. When the Cu(AC)2 concentrations
are 5 mM and 15 mM, the nucleation processes of Cu2 O fit the pro-
gressive nucleation and instantaneous nucleation theory models, re-
spectively. The nucleation density under the instantaneous nucleation
mechanism is much higher than the nucleation density under the pro-
gressive nucleation mechanism. For the same nucleation mechanism,
the nucleation density decreases with as the applied potential de-
creases.
The nucleation mechanism of the Cu2 O has a significant impact on
the structure, morphology, and optoelectronic properties of Cu2 O thin
film. Under the instantaneous nucleation mechanism, the Cu2 O crystal
morphology is more uniform, with sword-shaped dendritic crystals,
and the bandgap energy is 2.006 eV, less than the 2.035 eV under
progressive nucleation mechanism. Compared with the progressive
nucleation mechanism, the prepared Cu2 O under the instantaneous
nucleation mechanism shows stronger PL properties, higher carrier
concentration (4.9 × 1022 cm−3 ), and smaller equivalent resistances
R2 (353.22 K · cm2 ) and R1 (127.27 K · cm2 ). It exhibits a more
regular morphology and superior photoelectric properties. However,
the change in electrolyte concentration does not influence the con-
ductive type of the prepared Cu2 O. The Cu2 O thin film has potential
applications in the field of solar energy.
Acknowledgments
This work was supported by the National Science Foundation of
China (Nos. 21576220, 21276208), the Natural Science Foundation of
Shaanxi Province (No. 2015JZ005) and the Key Laboratory Research
Project of Education Department of Shaanxi Province (No. 17JS085).
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