A method to give chemically stabilities of photoelectrodes for water splitting: Compositing of a highly crystalized TiO2 layer on a chemically unstable Cu2O photocathode using laser-induced crystallization process

•Highly crystalized TiO2 layers were successfully composited on Cu2O photocathodes.•Crystallization of TiO2 with no damage to Cu2O by laser was due to nanosecond-scale thermal effect.•The obtained TiO2/Cu2O photocathodes had a high chemical stability toward water reduction.•The composition process is applicable for every photoelectrode to raise chemical stability. To prevent the self-reduction of the Cu2O photocathode for solar hydrogen production, we developed a compositing process of a highly crystalized TiO2 layer on the Cu2O photocathode using an excimer-laser-assisted metal-organic deposition (ELAMOD) process. The TiO2 layer was successfully crystalized without oxidation of Cu2O to CuO mainly owing to a photothermal effect with nanosecond duration time induced by laser absorption of the TiO2 precursor while the crystallization of the TiO2 layer by usual furnace heating process was accompanied by oxidation of Cu2O which degrade the water reduction ability. On the TiO2/Cu2O photocathode prepared by ELAMOD process, the self-reduction of Cu2O did not occur and then photocurrent due to water reduction was constant with reaction time while on the bare Cu2O photocathode, the photocurrent decreased owing to the occurrence of the self-reduction. This indicated that reaction stability of the photocathode was largely enhanced after compositing of the crystallineTiO2 layer. This ELAMOD process would be applicable for any kinds of chemically unstable photoelectrodes containing non-oxides such as sulfides and phosphides, and therefore any kinds of photoelectrodes would have potentials toward a practical use by improving their chemical stabilities.