A comparative first-principles investigation on the defect chemistry of TiO2 anatase

Abstract

Understanding native point defects is fundamental in order to comprehend the properties of TiO2 anatase in technological applications. The previous first-principles reports of defect-relevant quantities, such as formation energies and charge transition levels, are, however, scattered over a wide range. We perform a comparative study employing different approaches based on semilocal with Hubbard correction (DFT+U) and screened hybrid functionals in order to investigate the dependence defect properties on the employed computational method. While the defects in TiO2 anatase, as in most transition-metal oxides, generally induce the localization of electrons or holes on atomic sites, we notice that, provided an alignment of the valence bands has been performed, the calculated defect formation energies and transition levels using semilocal functionals are in a fair agreement with those obtained using hybrid functionals. A similar conclusion can be reached for the thermochemistry of the Ti-O system and the limit values of the elemental chemical potentials. We interpret this as a cancellation of error between the self-interaction error and the overbinding of the O2 molecule in semilocal functionals. Inclusion of a U term in the electron Hamiltonian offers a convenient way for obtaining more precise geometric and electronic configurations of the defective systems.