Electronic and optical properties of doped TiO2 by many-body perturbation theory

Doping is one of the most common strategies for improving the photocatalytic and solar energy conversion properties of TiO2, hence an accurate theoretical description of the electronic and optical properties of doped TiO2 is of both scientific and practical interest. In this work we use many-body perturbation theory techniques to investigate two typical n-type dopants, niobium and hydrogen, in TiO2 rutile. Using the GW approximation to determine band edges and defect energy levels, and the Bethe-Salpeter equation for the calculation of the absorption spectra, we find that the defect energy levels form nondispersive bands lying similar to 2.2 eV above the top of the corresponding valence bands (similar to 0.9 eV below the conduction bands of the pristine material). The defect states are also responsible for the appearance of low-energy absorption peaks that enhance the solar spectrum absorption of rutile. The spatial distributions of the excitonic wave functions associated with these low-energy excitations are very different for the two dopants, suggesting a larger mobility of photoexcited electrons in Nb-TiO2.