Cu2O and CuO are attractive photocatalytic materials for water splitting due to their earth abundance and low cost. In this paper, we report the deposition of Cu2O and CuO thin films by a sol-gel spin-coating process. Sol-gel deposition has distinctive advantages such as low-cost solution processing and uniform film formation over large areas with a precise stoichiometry and thickness control. Pure-phase Cu2O and CuO films were obtained by thermal annealing at 500 °C in nitrogen and ambient air, respectively. The films were successfully incorporated as photocathodes in a photoelectrochemical (PEC) cell, achieving photocurrents of -0.28 mA cm(-2) and -0.35 mA cm(-2) (for Cu2O and CuO, respectively) at 0.05 V vs. a reversible hydrogen electrode (RHE). The Cu2O photocurrent was enhanced to -0.47 mA cm(-2) upon incorporation of a thin layer of a NiOx co-catalyst. Preliminary stability studies indicate that CuO may be more stable than Cu2O as a photocathode for PEC water-splitting.

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Cupric oxide (CuO) thin film was sputtered onto fluorine-doped tin oxide (FTO) coated glass substrate and incorporated into a photoelectrochemical (PEC) cell as a photocathode. Through in situ nanocrystal engineering, sputtered CuO film shows an improvement in its stability and photocurrent generation capability. For the same CuO film thickness (150 nm), films deposited at a sputtering power of 300 W exhibit a photocurrent of ∼0.92 mAcm(-2) (0 V vs RHE), which is significantly higher than those deposited at 30 W (∼0.58 mAcm(-2)). By increasing the film thickness to 500 nm, the photocurrent is further enhanced to 2.5 mAcm(-2), which represents a photocurrent conversion efficiency of 3.1%. Systematic characterization using Raman, XRD, and HR-TEM reveals that the high sputtering power results in an improvement in CuO film crystallinity, which enhances its charge transport property and, hence, its photocurrent generation capabilities.