Stability of non-metal dopants to tune the photo-absorption of TiO at realistic temperatures and oxygen partial pressures: A hybrid DFT study.

TiO anatase is considered to play a significant importance in energy and environmental research. However, for developing artificial photosynthesis with TiO, the major drawback is its large bandgap of 3.2 eV. Several non-metals have been used experimentally for extending the TiO photo-absorption to the visible region of the spectrum. It's therefore of paramount importance to provide theoretical guidance to experiment about the kind of defects that are thermodynamically stable at a realistic condition (e.g. Temperature (T), oxygen partial pressure ([Formula: see text]), doping). However, disentangling the relative stability of different types of defects (viz. substitution, interstitial, etc.) as a function of charge state and realistic T, [Formula: see text] is quite challenging. We report here using state-of-the-art first-principles based methodologies, the stability and meta-stability of different non-metal dopants X (X = N, C, S, Se) at various charge states and realistic conditions. The ground state electronic structure is very accurately calculated via density functional theory with hybrid functionals, whereas the finite T and [Formula: see text] effects are captured by ab initio atomistic thermodynamics under harmonic approximations. On comparing the defect formation energies at a given T and [Formula: see text] (relevant to the experiment), we have found that Se interstitial defect (with two hole trapped) is energetically most favored in the p-type region, whereas N substitution (with one electron trapped) is the most abundant defect in the n-type region to provide visible region photo-absorption in TiO. Our finding validates that the most stable defects in X doped TiO are not the neutral defects but the charged defects. The extra stability of [Formula: see text] is carefully analyzed by comparing the individual effect of bond-making/breaking and the charge carrier trapping energies.