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The Cuprous oxide (CuO) thin film was prepared on texturized Si wafer by a simple sol–gel method to fabricate p-CuO/n-Si heterojunction photoelectric device. The novel sol–gel method is very cheap and convenient. The structural, optical and electrical properties of the CuO film were studied by X-ray diffraction (XRD), Scanning Electron Microscope (SEM), X-ray photoelectron spectroscopy (XPS), UV–Vis spectrophotometer and Hall effect measurement. A good nonlinear rectifying behavior is obtained for the p-CuO/n-Si heterojunction. Under reverse bias, good photoelectric behavior is obtained.