Co-substituted BiFeO3: electronic, ferroelectric, and thermodynamic properties from first principles

Abstract: Bismuth ferrite, BiFeO3, is a multiferroic solid that is attracting increasing attention as a potential photocatalytic material, because the ferroelectric polarisation enhances the separation of photogenerated carriers. With the motivation of finding routes to engineer the band gap and the band alignment, while conserving or enhancing the ferroelectric properties, we have investigated the thermodynamic, electronic and ferroelectric properties of BiCoxFe1 xO3 solid solutions, with 0 < x < 0.13, using density functional theory. We show that the band gap can be reduced from 2.9 eV to 2.1 eV by cobalt substitution, while simultaneously increasing the spontaneous polarisation, which is associated with a notably larger Born effective charge of Co compared to Fe cations. We discuss the interaction between Co impurities, which is strongly attractive and would drive the aggregation of Co, as evidenced by Monte Carlo simulations. Phase separation into a Co-rich phase is therefore predicted to be thermodynamically preferred, and the homogeneous solid solution can only exist in metastable form, protected by slow cation diffusion kinetics. Finally, we discuss the band alignment of pure and Co-substituted BiFeO3 with relevant redox potentials, in the context of its applicability in photocatalysis.