Identifying Performance-Limiting Deep Traps in Ta₃N₅for Solar Water Splitting

Ta3N5 is a promising semiconductor for solar-driven photocatalytic or photoelectrochemical (PEC) water splitting. However, the lack of an in-depth understanding of its intrinsic defect properties limits further improvement of its performance. In this study, comprehensive spectroscopic characterizations are combined with theoretical calculations to investigate the defect properties of Ta3N5. The obtained electronic structure of Ta3N5 reveals that oxygen impurities are shallow donors, while nitrogen vacancies and reduced Ta centers (Ta3+) are deep traps. The Ta3+ defects are identified to be most detrimental to the water splitting performance because their energetic position lies below the water reduction potential. Based on these findings, a simple H2O2 pretreatment method is employed to improve the PEC performance of the Ta3N5 photoanode by reducing the concentration of Ta3+ defects, resulting in a high solar-to-hydrogen conversion efficiency of 2.25%. The fundamental knowledge about the defect properties of Ta3N5 could serve as a guideline for developing more efficient photoanodes and photocatalysts.