Maximizing Solar Water Splitting Performance by Nanoscopic Control of the Charge Carrier Fluxes across Semiconductor-Electrocatalyst Junctions

Protective insulating layers between a semiconductor and an electrocatalyst enable otherwise unstable semiconductors to be used in photocatalytic water splitting. It is generally argued that in these systems the metal electrocatalyst must have work function properties that set a high inherent barrier height between the semiconductor and electrocatalyst and that the insulating layer should be as thin as possible. In this study we show that, for systems which suffer from inherently low barrier heights, the photovoltage can be significantly improved by tuning the thickness of the insulating layer. We demonstrate this in a case study of a system consisting of n-type silicon, a hafnium oxide protective layer (thickness 0-3 nm), and a Ni electrocatalyst. By optimizing the protective layer thickness, we observe increased efficiencies for photocatalytic oxygen evolution with a thick Ni electrocatalyst supported on n-Si. Our findings open avenues for the use of inexpensive electrocatalysts with favorable electrocatalytic and optical properties but poor work function characteristics.