Publication date: 15th December 2014
Nickel oxide containing thin-films were formed on silicon supports by metal-organic electrochemical deposition under cathodic conditions. The metal oxides are interspersed as nano-scaled clusters in a carbon-rich host phase which serves for protection of sensitive photoactive semiconductor electrodes against their degradation in aqueous electrolytes. Short-term stability measurements for 24 hours (at pH13) demonstrate that this integrative approach, where electrocatalytic and protective properties are combined in a single film, opens the route for novel silicon-based heterojunction designs for photo-assisted splitting of water. Functional and structural analysis is provided by X-ray absorption measurements and EXAFS simulations. Chemical properties are discussed by XPS and EDX results. Optimization strategies will be outlined such as improved band alignment at the oxide/silicon interface, oxide doping as well as increase of the active surface area of the electrocatalytic films by advanced oxide core-shell heterojunctions. Finally, the interchangeable use of molecular precursors or single-process preparation from solid metals will be demonstrated.