Semiconducting Transition-Metal Oxides Based on D5 Cations: Theory for MnO and Fe2O3

Transition-metal oxides with partially filled d shells are typically Mott or charge-transfer insulators with notoriously poor transport properties due to large effective electron/hole masses or due to carrier self-trapping. Employing band-structure calculations and ab initio small-polaron theory for MnO and Fe ₂O ₃, we explore the potential of d5 oxides for achieving desirable semiconducting properties, e.g., in solar energy applications. The quantification of self-trapping energies and the trends with the coordination symmetry suggest strategies to overcome the main bottlenecks, i.e., the tendency for self-trapping of holes due to Mn(II) and of electrons due to Fe(III).