Paving the road toward the use of β-Fe2O3 in solar water splitting: Raman identification,phase transformation and strategies for phase stabilization

Although β-Fe₂O₃ has a high theoretical solar-to-hydrogen efficiency because of its narrow band gap, the study of β-Fe₂O₃ photoanodes for water splitting is elusive as a result of their metastable nature. Raman identification of β-Fe₂O₃ is theoretically and experimentally investigated in this study for the first time, thus clarifying the debate about its Raman spectrum in the literature. Phase transformation of β-Fe₂O₃ to α-Fe₂O₃ was found to potentially take place under laser and electron irradiation as well as annealing. Herein, phase transformation of β-Fe₂O₃ to α-Fe₂O₃ was inhibited by introduction of Zr doping, and β-Fe₂O₃ was found to withstand a higher annealing temperature without any phase transformation. The solar water splitting photocurrent of the Zr-doped β-Fe₂O₃ photoanode was increased by 500% compared to that of the pure β-Fe₂O₃ photoanode. Additionally, Zr-doped β-Fe₂O₃ exhibited very good stability during the process of solar water splitting. These results indicate that by improving its thermal stability, metastable β-Fe₂O₃ film is a promising photoanode for solar water splitting.