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

• Published in: Journal of physical chemistry. C 2013-05, Vol.117 (17), p.8892-8902
• Main Authors: Harb, M, Sautet, P, Raybaud, P
• Format: Article
• Language: English
• Subjects: Condensed matter: electronic structure, electrical, magnetic, and optical properties; Electron states; Exact sciences and technology; Methods of electronic structure calculations; Optical properties and condensed-matter spectroscopy and other interactions of matter with particles and radiation; Optical properties of bulk materials and thin films; Physics
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/jp312197g

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 potential (including standard conditions), whereas anionic species are stabilized only at very low chemical potential of oxygen. The metastable cationic Ti(1–2x)O2S2x system involving the presence of S4+ species in substitution for Ti4+, with the formation of SO2 units, should offer the best compromise between the thermodynamic conditions and the expected optical properties.