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Metal-insulator-semiconductor (MIS) photocathodes offer a simple alternative to p-n junction photocathodes in photoelectrochemical water splitting. However, the parasitic light absorption of catalysts and metal layers in the MIS junction, as well as the lack of low work function metals to form a large band offset with p-Si, severely limit their performance. This paper describes an MIS photocathode fabricated from n-Si, rather than the commonly used p-Si, to spatially decouple light absorption from reaction sites, which enables the majority carriers, instead of the commonly used minority carriers, to drive the surface reaction, making it possible to place the reaction sites far away from the light absorption region. Thus, the catalysts could be moved to the backside of the MIS junction to avoid light shielding. Moreover, the adoption of n-Si unlocks a variety of high work function materials for photovoltage generation. The obtained n-Si MIS photocathode exhibits an applied bias photon-to-current efficiency of 10.26% with a stability up to 300 h.

Spatial decoupling of light absorption and reaction sites in n-Si photocathodes for solar water splitting