Construction of ZnO/ZnS/CdS/CuInS₂ core-shell nanowire arrays via ion exchange: p-n junction photoanode with enhanced photoelectrochemical activity under visible light.

ZnO/ZnS/CdS/CuInS2 core-shell nanowire arrays with enhanced photoelectrochemical activity under visible light were successfully prepared via ion exchange and hydrothermal methods. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-vis absorption, X-ray photoemission spectroscopy, and photoelectrochemical response. As a p-n junction photoanode, ZnO/ZnS/CdS/CuInS2 heterostructure shows much higher visible light photoelectrocatalytic activity toward water splitting than ZnO/ZnS/CdS and ZnO/ZnS films. The ZnO/ZnS/CdS/CuInS2 film with optimal constitution exhibits the highest photocurrent of 10.5 mA/cm(2) and the highest IPCE of approximately 57.7% at 480 nm and a bias potential of 0 V versus Ag/AgCl. The critical roles of CdS and ZnS in ZnO/ZnS/CdS/CuInS2 heterostructure were investigated. ZnS, as a passivation layer, suppresses the recombination of the photogenerated charge carriers at the interface of the oxide and CuInS2. CdS enhances the absorption of visible light and forms p-n junctions with CuInS2, which promotes the transport of charge carriers and retards the recombination of electrons and holes in CuInS2 to improve the photoelectrochemical performance of ZnO/ZnS/CdS/CuInS2 heterostructure.