Chalcopyrite Thin Film Materials for Photoelectrochemical Hydrogen Evolution from Water under Sunlight

Copper chalcopyrite is a promising candidate for a photocathode material for photoelectrochemical (PEC) water splitting because of its high half-cell solar-to-hydrogen conversion efficiency (HC-STH), relatively simple and low-cost preparation process, and chemical stability. This paper reviews recent advances in copper chalcopyrite photocathodes. The PEC properties of copper chalcopyrite photocathodes have improved fairly rapidly: HC-STH values of 0.25% and 8.5% in 2012 and 2015, respectively. On the other hand, the onset potential remains insufficient, owing to the shallow valence band maximum mainly consisting of Cu 3d orbitals. In order to improve the onset potential, we explored substituting Cu for Ag and investigate the PEC properties of silver gallium selenide (AGSe) thin film photocathodes for varying compositions, film growth atmospheres, and surfaces. The modified AGSe photocathodes showed a higher onset potential than copper chalcopyrite photocathodes. It was demonstrated that element substitution of copper chalcopyrite can help to achieve more efficient PEC water splitting.