Hole Polaron Migration in Bulk Phases of TiO₂ Using Hybrid Density Functional Theory

Understanding charge-carrier transport in semiconductors is vital to the improvement of material performance for various applications in optoelectronics and photochemistry. Here, we use hybrid density functional theory to model small hole polaron transport in the anatase, brookite, and TiO₂-B phases of titanium dioxide and determine the rates of site-to-site hopping as well as thermal ionization into the valance band and retrapping. We find that the hole polaron mobility increases in the order TiO₂-B < anatase < brookite and there are distinct differences in the character of hole polaron migration in each phase. As well as having fundamental interest, these results have implications for applications of TiO₂ in photocatalysis and photoelectrochemistry, which we discuss.