Controlling Catalyst–Semiconductor Contacts: Interfacial Charge Separation in p-InP Photocathodes

Charge-carrier-selective interfaces between electrocatalyst particles and semiconductor light absorbers are critical for solar photochemistry, but controlling their properties is challenging. Using thin films and nanoparticle arrays of Pt hydrogen-evolution catalysts on p-InP (a high-performance photocathode material), along with macroscopic and nanoscopic electrical and chemical analysis, we show how hydrogen alloying, the pinch-off effect for nanoscale contacts, and the formation of a native surface oxides all play different roles in creating charge-carrier-selective junctions. The new insights can be broadly applied to photocathodes, photoanodes, and overall water-splitting systems to control charge-carrier selectivity and improve performance.