Defect Engineering of Ta₃N₅ Photoanodes: Enhancing Charge Transport and Photoconversion Efficiencies via Ti Doping

Abstract While Ta₃N₅ shows excellent potential as a semiconductor photoanode for solar water splitting, its performance is hindered by poor charge carrier transport and trapping due to native defects that introduce electronic states deep within its bandgap. Here, it is demonstrated that controlled Ti doping of Ta₃N₅ can dramatically reduce the concentration of deep‐level defects and enhance its photoelectrochemical performance, yielding a sevenfold increase in photocurrent density and a 300 mV cathodic shift in photocurrent onset potential compared to undoped material. Comprehensive characterization reveals that Ti⁴⁺ ions substitute Ta⁵⁺ lattice sites, thereby introducing compensating acceptor states, reducing the concentrations of deleterious nitrogen vacancies and reducing Ta³⁺ states, and thereby suppressing trapping and recombination. Owing to the similar ionic radii of Ti⁴⁺ and Ta⁵⁺, substitutional doping does not introduce lattice strain or significantly affect the underlying electronic structure of the host semiconductor. Furthermore, Ti can be incorporated without increasing the oxygen donor content, thereby enabling the electrical conductivity to be tuned by over seven orders of magnitude. Thus, Ti doping of Ta₃N₅ provides a powerful basis for precisely engineering its optoelectronic characteristics and to substantially improve its functional characteristics as an advanced photoelectrode for solar fuels applications.