ISRN Nanotechnology

Volume 2013 (2013), Article ID 271545, 4 pages

http://dx.doi.org/10.1155/2013/271545

Research Article

Potentiostatic Deposition and Characterization of Cuprous Oxide Thin Films

A. El-Shaer and A. R. Abdelwahed

Physics Department, Faculty of Science, KafrelSheikh University, KafrelSheikh 33516, Egypt

Received 26 February 2013; Accepted 31 March 2013

Academic Editors: G. Alfieri, D. K. Sarker, and J. J. Suñol

Copyright © 2013 A. El-Shaer and A. R. Abdelwahed. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

Electrodeposition technique was employed to deposit cuprous oxide Cu₂O thin films. In this work, Cu₂O thin films have been grown on fluorine doped tin oxide (FTO) transparent conducting glass as a substrate by potentiostatic deposition of cupric acetate. The effect of deposition time on the morphologies, crystalline, and optical quality of Cu₂O thin films was investigated.

1. Introduction

Cuprous oxide is known as P-type semiconductor with a direct band gap that absorbs solar radiation up to 650 nm [1]. belongs to I–VI semiconductor compounds. has been researched as a potential material for photovoltaic applications for several reasons: source materials are abundant and nontoxic, band gap of 1.9–2.2 eV, which can be possibly adjusted by controlling the compositions [2], can be prepared with simple and cheap methods on large scale, and theoretical solar cell efficiency is approximately 20% [3–5]. All of these properties make a suitable material for many potential applications in solar energy conversion, electrode materials, sensors, and catalysis [6–9]. Various methods have been employed for the synthesis of such as thermal oxidation, thermal evaporation, sol-gel, spray pyrolysis, reactive magnetron sputtering, RF magnetron sputtering, and electrodeposition [10–16]. Among them electrodeposition has shown many advantages; it is a simple, economical method for preparation of large area films with good homogeneity, and it allows a good control for the growth parameters. Electrodeposition of involves two steps: the first step is reduction of ions to ions (1) and the second step is precipitation of ions to because of the solubility limitation of ions (2) [17]

In this study, the effect of deposition time on the morphologies, crystal and optical quality of electrodeposited thin films is investigated.

2. Experimental Details

Electrodeposition of was carried out in a three-electrode setup consisting of platinum wire counter electrode, Ag/AgCl reference electrode, and FTO-coated glass substrate as a working electrode. Before the electrodeposition, the FTO substrates were precleaned by sonication in acetone, isopropanol, and deionized water for 10 minutes, respectively, and then dried at 105°C for several hours. The electrolyte used was composed of 0.02 M cupric acetate and 0.1 M sodium acetate with pH 5.8. The electrodeposition was performed at fixed potential −0.50 V versus Ag/AgCl reference electrode using Bio-Logic SP-50 potentiostat at 60°C. A series of samples were deposited at 5, 10, 15, and 30 minutes.

The morphology of the deposited films at different experimental conditions was characterized by scanning electron microscopy (SEM). Crystal structures and phase compositions of the films were measured by X-ray diffraction analysis using XRD-6000 Shimadzu diffractometer using Cu radiation (40 Kv, 30 mA). Optical studies were carried out by recording the optical absorption spectra of the films using UV-VIS Shimadzu spectrophotometer.

3. Results and Discussion

Figure 1 shows SEM photographs of thin films electrodeposited on FTO substrate at −0.5 V versus Ag/AgCl reference electrode for 5, 10, 15, and 30 minutes. In the beginning of the deposition after 5 min, a small grains starts to nucleate on the substrate surface to form cubic islands as shown in Figure 1(a). As the deposition time increased to 10 min, the density of cube islands increased and they are interconnected with each other to change the surface morphology to be ring-shaped structures as shown in Figure 1(b) [18]. By continuing the deposition process to 15 min, spherical grain started to appear on the surface (Figure 1(c)). Finally after 30 min deposition time, it was found that the density of the spherical grains increased to cover most of the surface as it is clear in Figure 1(d) [19].

(a)

(b)

(c)

(d)

Figure 1: SEM photographs of thin films deposited at various deposition times: (a) 5, (b) 10, (c) 15, and (d) 30 min.

To identify the crystal structure of the deposited films XRD measurements were carried out. These measurements indicated that all samples are crystalline and the crystallographic phase of the films is cubic as it is clear from the well-defined peaks in Figure 2. At the deposition time of 5 min and 10 min, besides the characteristic peaks of the FTO glass substrate, three characteristic diffraction peaks of the thin film at 2 values of 36.62, 42.54, and 62.14, respectively, corresponding to the reflections from the (111), (200), and (220) planes are observed (Figures 2(a) and 2(b)). Except for the diffraction of and FTO substrate, there are no other peaks observed, which means that pure can be obtained through electrodeposition and no impurity phase was observed.

(a)

(b)

(c)

(d)

Figure 2: XRD pattern of deposited film in electrolyte containing 0.02 M copper acetate and 0.1 M sodium acetate at pH 5.8 for (a) 5, (b) 10, (c) 15, and (d) 30 min (* refers to FTO substrates).

As the deposition time increased to 15 min, in addition to XRD peaks of , the diffraction peak related to (111) plane of Cu metal appears as shown in Figure 2(c). With increasing the deposition time to 30 min, the intensity of the Cu metal peak increased (Figure 2(d)). These XRD results are in good agreement with the SEM results where some spherical grains started to appear at 15 min of growth. We observed before in SEM results that some spherical grains started to appear at 15 min which is the same time when Cu metallic characteristic peak appears in XRD chart. From both SEM and XRD one can explain that these spherical grains are metallic copper. Song et al. have proved this explanation with XPS (X-ray Photoelectron Spectra) measurements [19].

The optical absorption of electrodeposited films was recorded using a double-beam spectrophotometer in the wavelength region 200–800 nm.

The absorption coefficient satisfies the equation for a direct band gap material. The band gap () is obtained by extrapolation of the plot of versus where is the absorption coefficient as shown in Figure 3 and was found to be 1.99 eV–2.16 eV for the deposited films, which agrees well with the values reported earlier [1].

(a)

(b)

(c)

(d)

Figure 3: The variation of against photon energy (eV) for deposited films at different deposition times: (a) 5, (b) 10, (c) 15, and (d) 30 min.

4. Conclusion

In this work, we report the electrochemical deposition of thin films on FTO substrate by cathodic reduction of cupric acetate. The applied potential was −0.5 V versus Ag/AgCl reference electrode. We found that the deposition time has strong effect on the composition and crystal quality of the thin films and 10 minutes is the preferable time for the deposition of high-quality thin films. Optical absorption measurements indicate that the band gap of thin films is 1.9–2.1 eV.

Acknowledgment

This study was supported by Egyptian Science and Technological Development Fund (STDF), call name: Renewable Energy Research Program, Project ID: 1473.

References

W. Septina, S. Ikeda, M. A. Khan et al., “Potentiostatic electrodeposition of cuprous oxide thin films for photovoltaic applications,” Electrochimica Acta, vol. 56, no. 13, pp. 4882–4888, 2011.

L. Wan, Z. Wang, Z. Yang, W. Luo, Z. Li, and Z. Zou, “Modulation of dendrite growth of cuprous oxide by electrodeposition,” Journal of Crystal Growth, vol. 312, no. 21, pp. 3085–3090, 2010.

L. C. Olsen, F. W. Addis, and W. Miller, “Experimental and theoretical studies of Cu₂O solar cells,” Solar Cells, vol. 7, no. 3, pp. 247–279, 1982.

E. Fortin and D. Masson, “Photovoltaic effects in Cu₂OCu solar cells grown by anodic oxidation,” Solid State Electronics, vol. 25, no. 4, pp. 281–283, 1982.

R. J. Iwanowski and D. Trivich, “Enhancement of the photovoltaic conversion efficiency in Cu/Cu₂O schottky barrier solar cells by H⁺ ion irradiation,” Physica Status Solidi A, vol. 95, no. 2, pp. 735–741, 1986.

I. Rodriguez, P. Atienzar, F. Ramiro-Manzano, F. Meseguer, A. Corma, and H. Garcia, “Photonic crystals for applications in photoelectrochemical processes: photoelectrochemical solar cells with inverse opal topology,” Photonics and Nanostructures, vol. 3, no. 2-3, pp. 148–154, 2005.

R. W. J. Scott, S. M. Yang, G. Chabanis, N. Coombs, D. E. Williams, and G. A. Ozin, “Tin dioxide opals and inverted opals: near-ideal microstructures for gas sensors,” Advanced Materials, vol. 13, no. 19, pp. 1468–1472, 2001.

M. Acciarri, R. Barberini, C. Canevali et al., “Ruthenium(platinum)-doped tin dioxide inverted opals for gas sensors: synthesis, electron paramagnetic resonance, Mössbauer, and electrical investigation,” Chemistry of Materials, vol. 17, no. 24, pp. 6167–6171, 2005.

K. H. Yoon, W. J. Choi, and D. H. Kang, “Photoelectrochemical properties of copper oxide thin films coated on an n-Si substrate,” Thin Solid Films, vol. 372, no. 1, pp. 250–256, 2000.

M. J. Siegfried and K.-S. Choi, “Directing the architecture of cuprous oxide crystals during electrochemical growth,” Angewandte Chemie International Edition, vol. 44, no. 21, pp. 3218–3223, 2005.

A. L. Daltina, A. Addadb, and J. P. Choparta, “Potentiostatic deposition and characterization of cuprous oxide films and nanowires,” Journal of Crystal Growth, vol. 282, p. 414, 2005.

B. Balamurugan and B. R. Mehta, “Optical and structural properties of nanocrystalline copper oxide thin films prepared by activated reactive evaporation,” Thin Solid Films, vol. 396, no. 1-2, pp. 90–96, 2001.

L. Gou and C. J. Murphy, “Solution-phase synthesis of Cu₂O nanocubes,” Nano Letters, vol. 3, no. 2, pp. 231–234, 2003.

Z. Wu, M. Shao, W. Zhang, and Y. Ni, “Large-scale synthesis of uniform Cu₂O stellar crystals via microwave-assisted route,” Journal of Crystal Growth, vol. 260, no. 3-4, pp. 490–493, 2004.

Z. Z. Chen, E. W. Shi, Y. Q. Zheng, W. J. Li, B. Xiao, and J. Y. Zhuang, “Growth of hex-pod-like Cu₂O whisker under hydrothermal conditions,” Journal of Crystal Growth, vol. 249, no. 1-2, pp. 294–300, 2003.

P. Taneja, R. Chandra, R. Banerjee, and P. Ayyub, “Structure and properties of nanocrystalline Ag and Cu₂O synthesized by high pressure sputtering,” Scripta Materialia, vol. 44, no. 8-9, pp. 1915–1918, 2001.

M. Pourbaix, Atlas of Electrochemical Equilibrium in Aqueous Solutions, National Association of Corrosion Engineers, Houston, Tex, USA, 2nd edition, 1974.

Y. Tang, Z. Chen, Z. Jia, L. Zhang, and J. Li, “Electrodeposition and characterization of nanocrystalline cuprous oxide thin films on TiO₂ films,” Materials Letters, vol. 59, no. 4, pp. 434–438, 2005.

Y.-J. Song, S.-B. Han, H.-H. Lee, and K.-W. Park, “Size-controlled Cu₂O nanocubes by pulse electrodeposition,” The Korean Electrochemical Society, vol. 13, no. 1, pp. 40–44, 2010.