First-principles study of Hematite (α-Fe2O3) surface structures doped with Copper (Cu), Titanium (Ti), nickel (Ni) and manganese (Mn)

Abstract

Hematite has attracted research interest for many years due to its application in water splitting. Despite its attractive characters such as a reasonable optical band gap, the semiconductor is still faced with great uncertainty for the accomplishment of hematite based photoelectrochemical cells for water splitting. Doping with transition metals has shown to be a practical solution to overcome some of the limitations faced with hematite by modifying the energy band to improve its photo-electrochemical (PEC) activity. This study explored two surface structures of pure and transition metals (Ti, Cu, Ni and Mn) doped- α-Fe2O3 oriented in the directions (001) and (101). Calculations via the first principle using the density functional theory (DFT) were adopted, the results show that the doping of transition metals in α-Fe2O3 has an effect in modifying both the valence and conduction band edges. Specifically, doping Ti introduces more electrons in the conduction band and fills the unoccupied 3d states, which could improve the rate of charge transportation and likely enhance the electrical conductivity of α-Fe2O3. Doping with Mn, Ni, and Cu has effectively improved the absorption coefficient for α-Fe2O3 (001) and (101) surfaces, in the visible light region. The overall analysis of the results shows an opportunity for a successful photo-electrochemical water splitting application.