Anionic or Cationic S-Doping in Bulk Anatase TiO2: Insights on Optical Absorption from First Principles Calculations

Abstract

Using first principles calculations, we investigate the structural, electronic, optical, and energetic properties of S-doped anatase TiO2 bulk systems. To ensure accurate band gap predictions, we use the HSE06 exchange correlation functional, and the absorption spectra are obtained with density functional perturbation (DFPT) theory by employing HSE06. Various oxidation states (anionic and cationic) of sulfur are considered depending on the location in bulk TiO2: in interstitial position or in substitution for either oxygen or titanium atoms. Among the explored structures, two anionic and one cationic configurations induce an improved optical absorption response in the visible region as observed experimentally. Moreover, we undertake a thermodynamic analysis as a function of the chemical potential of oxygen and considering three relevant sulfur chemical doping agents (S2, H2S, and thiourea). It highlights that cationic configurations (S4+ and S6+) are strongly stabilized in a wide range of oxygen chemical ...