Materials Science Forum Online: 2016-03-20

ISSN: 1662-9752, Vol. 848, pp 519-524

doi:10.4028/www.scientific.net/MSF.848.519
© 2016 Trans Tech Publications, Switzerland

Preparation of N-type Cuprous Oxide Films via Electrodeposition

Method and their Photoelectrochemical Activities
Yuan Wena, Yuanzhuang Zoub, Siyi Wenc and Fei Hud*
School of materials science and engineering, Jingdezhen Ceramic Institute, Taoyang Road,
Jingdezhen City, Jiang Xi Province, 333403, China.
a
737210660@qq.com, b494061885@qq.com, cmansy0618@126.com, dmfhufei@126.com

Keywords: Electrochemical deposition, N-type cuprous oxide, Photoelectrochemical activity,

Annealing.

Abstract. The n-type Cu2O films were deposited on ITO substrate by three-electrode
electrochemical deposition method in a CuSO4-lactic acid electrolyte. The effects of electrolyte pH,
bath temperature, and annealing treatment on films’ conductivity and their photoelectrochemical
activity were investigated by X-ray diffraction (XRD), photocurrent (I-t) and mott-schottky (M-S)
plots. The results show that the n-type Cu2O could be electrodeposited at electrolyte pH of 8.5, 9
and 10, and the electrolyte temperature did not change the films’ conductivity. The highest n-type
photocurrent density of 0.014 mA /cm2 and carrier concentration of 2.3×1019 cm-3 was obtained
when the electrolyte pH was 8.5 and the bath temperature was 60℃. With increasing annealing
temperature from 150℃ to 400℃, the photocurrent density and carrier concentration of n-type
Cu2O thin films correspondingly increased, indicating that heat treatment is helpful to improve the
photoelectrochemical activity.

Introduction
Cuprous oxide (Cu2O) is abundant, non-toxic, and stable p-type semiconductor with band gap of
1.9~2.2 eV. It is of great potential for applying on solar cells for its theoretical efficiency can reach
to 20% [1,2], but the highest Cu2O-base solar cell is up to 5.38% [3], which is much lower than the
theoretical efficiency. Some research groups believe that the lattice mismatch in the heterojunction
solar cell is one of the main reasons for its poor efficiency, and a homojunction cell might be more
favorable for improving the solar cell performance. In this paper, we demonstrated an effective
method to control the conductivity of Cu2O semiconductors and their properties. There are many
methods to prepare Cu2O thin film, such as magnetron sputtering [4], sol-gel method [5],
solvothermal [6], electrochemical deposition [7,8] and so on. Electrochemical deposition process is
a simple and low cost method for fabricating Cu2O[9-11]. In this study, we investigated the
possibility of the growth of n-type Cu2O films via electrodeposition and effects of the the
photocurrent density and carrier concentration.

Experimental
ITO conductive glass was used as substrates, which was rinsed in acetone and ethanol for 5 min
under ultrasonic irradiation, and then washed in deionized water. Electrochemical deposition was
performed in a three-electrode cell with a Pt counter electrode, a saturated calomel electrode (SCE)
as reference electrode, and ITO substrates as the working electrode with dimension of 1×3 cm2.
Electrochemical deposition solution contained 0.4 mol / L copper sulfate and 3 mol / L-lactic acid,
and the solution pH was adjusted from 8.5 to 12.0 by carefully addition of 4 M sodium hydroxide.
Cu2O thin films were prepared at a deposition potential of −0.3 V versus SCE and the film depth
was controlled by keeping the coulomb amount for 1 C. After deposition, the films were washed by
distilled water.
The thin film structures were studied by X-ray diffraction (XRD, Bruker). The photocurrent (I-t)
and mott-schottky plots were obtained in 0.5 mol/L Na2SO4 solution by an electrochemical
workstation (CHI660D, Shanghai Chen Hua).

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520 Functional and Functionally Structured Materials

Results and Discussion

The deposition of Cu2O thin films. Fig. 1 is the linear sweep voltammetry in a CuSO4-lactic acid
electrolyte. A current peak is observed at potential of -0.45 V, and when potential lower than -0.75
V, the current increase sharply. This indicates that the deposition reactions in the electrolyte might
involve two steps: the reduction of Cu2+ to Cu+ , and reduction of Cu+ to metallic Cu.

2Cu2++2OH-+2e- = Cu2O+H2O (1)

Cu2++2e-= Cu (2)

Therefore, we chose -0.3 V as deposition potential in this experiment to obtain good Cu2O film
with high purity and suitable deposition rate.
•
• ♦ (111) (a) −♦− Cu2O
0
♦ (200)
Photocurrent density(mA/cm )

pH=12 • ♦ (220) − •− ITO

2

1 pH=11
Intensity
2
pH=10

3 pH=9

pH=8.5
4

5
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 20 30 40 50 60 70 80
Potential(V) 2 θ ( °)
Fig. 1 Linear sweep voltammetry of solution Fig. 2 XRD patterns of Cu2O films deposited
of copper sulfate-lactic acid. at different pH.

Effect of pH. Fig. 2 shows the XRD results of Cu2O films at solution pH of 8.5, 9, 10, 11, 12 in a
bath temperature keeps 60℃. The diffraction peaks appeared 2θ at 36.46 °, 42.40 ° and 61.38 °
respectively corresponding to (111), (200) and (220) planes ( PDF # 05-0667). The diffraction
intensity of the (111) plane increases with increasing electrolyte pH, which shows that the pH
values helping for the growth of the (111) plane. Fig. 3 shows the SEM images of Cu2O films at
solution pH of 8.5, 9, 10, 11, 12 in a bath temperature of 60℃. When the solution pH is 8.5, the
grain size is 360 nm, and the film thickness is 630 nm. With decreasing the solution pH, the grain
size increases. When the solution pH is 12, the grain size reached the maximum of 650 nm. The
film thickness is substantially unchanged.
Photocurrent verifies the conductive types of these Cu2O films. Photocurrent generated upon
illumination is anodic for n-type semiconductors and cathodic for p-type. Samples deposited at
solution pH of 8.5, 9, 10, 11 and 12 were selected for photocurrent density characterization and the
results are shown in Fig. 4(a). It is shown the films deposited at pH of 8.5, 9, 10 are anodic
photocurrents, indicating n-type conductivity, and the films deposited at pH of 11, 12 shows a
cathodic photocurrent, indicating p-type conductivity. The reason of n-type Cu2O generated may be
related to the concentration of OH- (or pH value). From the electrodeposition process in an alkaline
solution is: 2Cu2+ + 2OH-+2e-→Cu2O+H2O, it can be inferred that the higher the pH, the greater the
concentration of hydroxide ions, and the reaction occurs more easily, and more oxygen enters the
Cu2O film to be a point defect (e.g. Cu doped or oxygen vacancy), generating an electron carrier
and n-type semiconductor.
 Materials Science Forum Vol. 848 521

A B C

D E F

Fig. 3 SEM images of Cu2O films deposited at different pH. A: pH 8.5,

B: pH 9, C: pH 10, D: pH 11, E: pH 8.5, F: film thickness of pH 8.5.
pH8.5
(a) (b)
0.030
Photocurrent density(mA/cm2)

pH9
Photocurrent density (mA/cm )
2

0.025
pH10

0.020
0
pH11
0.015

pH12 0.010

8 9 10 11 12
0 100 200 300
Time(s) pH
Fig. 4 Photocurrent response of Cu2O films deposited at pH value of 8.5, 9, 10, 11 and 12.
The mott–schottky plots are measured and shown in Fig. 5. It can be seen that mott-schokky curve
slope for films deposited at pH of 8.5, 9, 10 is positive, indicating n-type conductivity. The
mott-schottky curve slope for films deposited at pH of 11, 12 is negative, indicating p-type
conductivity, which is in consistent with the results of photocurrent-time results. The carrier
concentrations for the Cu2O films are calculated from the mott-shottky plots, and the highest value
of 2.86 × 1018 cm-3 is obtained at pH of 8.5. The reason for carrier concentration variation may be
due to the concentration of OH− that controls the oxygen concentration and intrinsic point defects of
Cu2O films. The conductive of n-type Cu2O film is mainly determined by the oxygen vacancies.
When the pH value increases, more oxygen atoms enter into the film, resulting in reduction of the
carrier concentration.
9
1.0x10
9
1.4x10 3.0
pH=12 (a) pH=10 (b) 2.8
(c)
pH=11 9
carrier concentration(1018cm-3)

8
1.2x10 pH=9
8.0x10 2.6
9
1.0x10
pH=8.5 2.4
8
6.0x10 8 2.2
8.0x10
1/(Cs*Cs)
1/(Cs*Cs)

2.0
8
4.0x10 8
6.0x10 1.8

8
8
4.0x10 1.6
2.0x10
1.4
8
2.0x10
0.0 1.2
0.0 1.0
-0.40 -0.35 -0.30 -0.25 -0.20 -0.15 -0.10 -0.05 0.00 -0.1 0.0 0.1 0.2 0.3 0.4 8 9 10 11 12
the value of pH
Potential(V) Potential(V)

Fig. 5 Mott–Schottky plots of Cu2O films deposited at different pH. (a): pH 11,
12. (b): pH 8.5, 9, 10. (c): carrier concentration.
522 Functional and Functionally Structured Materials

Effect of temperature. Fig. 6(a) and Fig. 6(b) shows the XRD results and photocurrent density of
Cu2O films at temperature of 40℃, 50℃, 60℃, 70℃, 80℃ in a solution pH of 8.5. It is shown that
pure Cu2O films are deposited, and the (111), (200) plane orientation increases with increasing of
temperature. This result is in agreement with the results obtained by Zhou Yanchun[12]. The
photocurrent density is measured for films deposited at temperature of 40℃, 50℃, 60℃, 70℃ and
80℃ as shown in Fig. 6(b). The anodic current indicates n-type characteristics. When the deposition
temperature of the solution changes from 40℃ to 80℃, the photocurrent density changes from
0.012 to 0.025 mA/cm2. This shows that the change of deposition temperature has little effect on
Cu2O film photocurrent.
-♦- Cu2O (a) (b) 80°C
-•- ITO • (111 )(200)

photocurrent density(mA/cm2)
• •(220) 80°C
70°C
70°C
Intensity

60°C 60°C

50°C
50°C
40°C
Ι 0.012mA/cm2 40°C

20 30 40 50 60 70 80 0 100 200 300

2θ( ° ) Time(s)

Fig. 6 XRD patterns(a) and photocurrent response(b) of Cu2O films deposited at

different temperatures
The motts-chottky plots for samples deposited at temperature of 40℃, 50℃, 60℃, 70℃, 80℃ are
presented in Fig. 7. It is shown that the mott-schokky slope for films deposited are positive,
indicating that these Cu2O films are n-type semiconductors. These mott-schokky results are in
consistent with the I-t results. According to mott–schottky plots the carrier concentration for the
Cu2O films is calculated and the highest value of 2.3 × 1019 cm-3 is obtained at temperature of 60℃,
by estimating dielectric constant of 6.3 for cuprous oxide.
9
9x10 60 ° C
9
8x10 80 ° C
9
7x10
9
6x10 50 ° C
1/(Cs*Cs)

9
5x10 40 ° C
9
4x10
3x10
9 70 ° C
9
2x10
9
1x10
0
0.0 0.1 0.2 0.3 0.4
Potential(v)

Fig. 7 Mott–Schottky plots of Cu2O films deposited at different temperatures

Effect of Annealing. The annealing is believed to helpful for the crystalline growth and also the
photoelectron-chemical properties. Fig. 8 shows the SEM images of Cu2O films at different
annealing temperature of 150℃, 250℃，350℃，400℃ for the samples prepared at condition of pH
8.5, 60℃. When the annealing temperatures are 150℃, 250℃, 350℃, 400℃, the grain sizes are 150
nm, 200 nm, 300 nm, 270 nm and the film thicknesses are 180 nm, 210 nm, 720 nm, 630 nm,
respectively. With decreasing the annealing temperature, the grain size and the film thickness
increase.
The photocurrent density and mott–schottky plots of films before and after annealing are shown
in Fig. 9 and the highest value of photocurrent density of 0.049 mA/cm2 and the highest carrier
concentration of 2.86 × 1018 cm-3 is obtained at 400℃. It shows that the photocurrent density and
carrier concentration of n-type Cu2O thin films increase with increasing of annealing temperature
 Materials Science Forum Vol. 848 523

The reason of photocurrent density and carrier concentration variation may be due to a more order
and complete crystal structure. This could increase the diffusion rate in the crystals, and reduce the
carrier recombination and also the carrier transmission resistance, thus improve the
photoelectron-chemical activities.
A B

C D

800
E
700

600
Thickness(nm)

500

400

300

200

100
-50 0 50 100 150 200 250 300 350 400 450
Temperature(°C)
Fig. 8 SEM images of Cu2O films deposited at different annealing temperature. A: 150℃.
B: 250℃. C: 350℃. D: 400℃. E: film
1.60E+019
10
7x10 400°C 0.05
400°C 1.40E+019
Photocurrent density(mA/cm2)
Photocurrent density(mA/cm2)

carrier concentration(cm-3)

10
6x10
350°C 0.04 1.20E+019
10
5x10
1.00E+019
1/(Cs*Cs)

350°C 10
4x10 0.03
photocurrent 8.00E+018
10
250°C 2 3x10 250°C
I 0.008mA/cm 0.02
6.00E+018
10
2x10 150°C
150°C 0.01 4.00E+018
10
1x10 before
before carrier concentration 2.00E+018
0 0.00
-0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0 100 200 300 400
0 50 100 150 200 250 300
Potential(V) Annealing temperature(°C)
Time(s)

Fig. 9 Photocurrent response(a), Mott–Schottky plots(b) and Current density and Carrier
concentration(c) of Cu2O films deposited at different annealing temperature.
524 Functional and Functionally Structured Materials

Conclusion
In this experiment, the n-type Cu2O film was prepared by three-electrode electrochemical
deposition in a CuSO4-lactic acid electrolyte. The results shown as the following:
1. When the electrolyte pH of 8.5, 9 and 10, the n-type Cu2O could be electrodeposited, and the
p-type Cu2O film was prepared when the pH of 11 and 12.
2. The electrolyte temperature does not change the conductivity type of the Cu2O film, but it will
affect the carrier concentration. When the electrolyte pH is 8.5 and the bath temperature is 60℃, the
films with highest photocurrent density of 0.014 mA/cm2 and the carrier concentration of 2.3
×1019cm-3 were obtained .
3. It is found that the photocurrent density and carrier concentration of n-type Cu2O thin films
increases with increasing of annealing temperature When the annealing temperature is 400℃,
photocurrent density and carrier concentration reached a maximum of 0.049 mA/cm2, and
1.43×1019 cm-3 respectively.

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Functional and Functionally Structured Materials
10.4028/www.scientific.net/MSF.848

Preparation of N-Type Cuprous Oxide Films via Electrodeposition Method and their
Photoelectrochemical Activities
10.4028/www.scientific.net/MSF.848.519

DOI References
[1] A. E Rakhshani, Preparation characteristics and photovoltaic properties of cuprous oxide-a review, Solid
State Electron. 29(1986) 7-17.
10.1016/0038-1101(86)90191-7
[3] T. Minami, Y. Nishi, T. Miyata, Preparation of p-type and n-type Cu2O film by electrochemical
deposition, Appl. Phys. Express 6 (2013) 044101.
10.7567/apex.6.044101
[7] J. N. Nian, C.C. Hu, H. Teng, Electrodeposited p-type Cu2O for H2 evolution from photoelectrolysis of
water under visible light illumination, Hydrogen Energy. 33(2008) 2897-2903.
10.1016/j.ijhydene.2008.03.052
[8] S. Somasundaram, C.R.N. Chenthamarakshan, N.R. Tacconi. et al., Photocatalytic production of hydrogen
from electrodeposited p-Cu2O film and sacrificial electron donors, Hydrogen Energy, 32(2007) 4661-4669.
10.1016/j.ijhydene.2007.06.028
[9] K. M. D. C. Jayathilaka, V. Kapaklis, W. Siripala, et al. Ammonium sulfide surface treatment of
electrodeposited p-typecuprous oxide thin films, Electron. Mater. 10(2014) 379-382.
10.1007/s13391-013-3099-x
[10] L. Wang, T. Meng, Fabrication and characterization of p-n homojunctions in cuprous oxide by
electrochemical deposition, Electrochemical and Solid-State Letters. 10(2007) H248-H250.
10.1149/1.2748632
[11] X. F. Han, K. Han, M. Tao, Characterization of Cl-doped n-type Cu2O Prepared by electrodeposition ,
Thin solid films. 518(2010) 5363-5367.
10.1016/j.tsf.2010.03.085