Photoelectrochemical hydrogen production from solar energy and water offers a clean and sustainable fuel option for the future. Planar III/V material systems have shown the highest efficiencies, but are expensive. By moving to the nanowire regime the demand on material quantity is reduced, and new materials can be uncovered, such as wurtzite gallium phosphide, featuring a direct bandgap. This is one of the few materials combining large solar light absorption and (close to) ideal band-edge positions for full water splitting. Here we report the photoelectrochemical reduction of water, on a p-type wurtzite gallium phosphide nanowire photocathode. By modifying geometry to reduce electrical resistance and enhance optical absorption, and modifying the surface with a multistep platinum deposition, high current densities and open circuit potentials were achieved. Our results demonstrate the capabilities of this material, even when used in such low quantities, as in nanowires.

Semiconductor nanowire arrays are expected to be advantageous for photoelectrochemical energy conversion due to their reduced materials consumption. In addition, with the nanowire geometry the length scales for light absorption and carrier separation are decoupled, which should suppress bulk recombination. Here, we use vertically aligned p-type InP nanowire arrays, coated with noble-metal-free MoS3 nanoparticles, as the cathode for photoelectrochemical hydrogen production from water. We demonstrate a photocathode efficiency of 6.4% under Air Mass 1.5G illumination with only 3% of the surface area covered by nanowires.

The factors affecting transfer of nanowire arrays from their substrates into flexible PDMS films have been systematically investigated. Experiments were carried out on gallium phosphide nanowires with a standard length of 10 μm with varying pitch (0.2-1.5 μm). The important factors were found to be penetration of the PDMS within the nanowire arrays and the strength/rigidity of the PDMS film. The PDMS penetration between wires in the arrays is affected by both the viscosity of the PDMS solution and the presence of air pockets trapped within nanowire arrays, particularly at small pitches. Dilution with hexane and curing in a vacuum desiccator solve the wire penetration problem, and an increase in cure/base ratio increases the rigidity and strength of the PDMS. The procedures for preparation and deposition of the PDMS solution are optimized and a high yield, up to 95%, of wire transfer across a range of nanowire pitches has been obtained.