The structural and the photoelectrochemical properties of ZnO–ZnS/ITO 1D hetero-junctions prepared by tandem electrodeposition and surface sulfidation: on the material processing limits

Abstract

ZnO–ZnS 1D hetero-nanostructures were prepared by an easy and scalable processing route. It consists of ZnO nanorod electrodeposition on ITO substrate and surface sulfidation by ion exchange in an aqueous Na₂S solution. Increasing the treatment contact time (t_c) from 8 to 48 h involves different ZnS growth mechanisms leading to different structural and microstructural rod characteristics, even if the overall size does not change significantly. Grazing X-ray diffraction, high-resolution microscopy, energy-dispersive spectrometry and X-ray photoelectron spectroscopy describe the outer surface layer as a poly- and nanocrystalline ZnS blende shell whose thickness and roughness increase with t_c. The ZnO wurtzite–ZnS blende interface goes from continuous and dense, at short t_c, to discontinuous and porous at long t_c, indicating that ZnS formation proceeds in a more complex way than a simple S²⁻/O²⁻ ion exchange over the treatment time. This feature has significant consequences for the photoelectrochemical performance of these materials when they are used as photoanodes in a typical light-assisted water splitting experiment. A photocurrent (J_p) fluctuation of 45% for less than 5 min of operation is observed for the sample prepared with a long sulfidation time while it does not exceed 15% for that obtained with a short one, underlining the importance of the material processing conditions on the preparation of valuable photoanodes.