Fabrication and photoelectrochemical properties of ordered Si nanohole arrays

•Large-area highly ordered SiNH arrays have been fabricated by the combination of nanosphere lithography and metal assisted electroless etching.•The diameter, length of individual nanohole, and the center-to-center distance between the neighbor nanoholes were precisely controlled through varying the conditions of nanosphere lithography and the wet etching.•The SiNH arrays exhibited a higher photoelectrochemical hydrogen generation performance superior to that of a planar Si.•The Pt/SiNH photocathode exhibited a high photovoltage of 0.12V. Large-area highly ordered silicon nanohole (SiNH) arrays on Si substrate have been fabricated by the combination of nanosphere lithography and metal assisted electroless etching. The diameter, length of nanoholes, and the center-to-center distance of adjacent nanoholes, can be accurately controlled by nanosphere lithography and metal assisted electroless etching conditions. The sub-wavelength structure of SiNH arrays had excellent antireflection property with a low reflectance of 3.5% within the wavelength range of 300–1000nm. Compared to the planar Si, the SiNH samples exhibited a higher photoelectrochemical hydrogen generation performance. The improved performance was attributed to SiNH arrays providing an effective light-trapping and a higher semiconductor/electrolyte interface areas which reduce the overpotential required for photoelectrochemical hydrogen reaction. Furthermore, decorating the SiNH arrays with platinum nanoparticles (PtNPs) yielded a significantly high photovoltage of 0.12V. The photoconversion efficiency of Pt-decorated SiNH (Pt/SiNH) arrays was 22% under the illumination of 100mW/cm2, higher than that of SiNH arrays (15.5%) and the planar Si (8.1%).