Sulfur-doping of rutile-titanium dioxide by ion implantation: Photocurrent spectroscopy and first-principles band calculation studies

Sulfur (S)-doped titanium dioxide (TiO2) was synthesized by ion implantation and subsequent thermal annealing. The S ions were implanted into the single crystals of rutile TiO2 at a fluence of 8x10(15) ions/cm(2). According to the results of Rutherford backscattering spectroscopy and ion channeling analysis, the irradiation damage recovered by annealing at 600 degreesC in air. In the annealed crystal, the S atoms occupied oxygen sites for form Ti-S bonds, as confirmed by x-ray photoelectron spectroscopy. Compared to the pure TiO2, a photocurrent was observed in the lower-energy regions for the S-doped TiO2. Based on the theoretical analyses by the first-principles band calculations using the full potential linearized augmented plane-wave methods within the generalized gradient approximation, the mixing of the S 3p states with the valence band (VB) was found to contribute to the increasing width of the VB. This leads to the band gap narrowing in the S-doped TiO2. Therefore, the photon-to-carrier conversion was induced during irradiation by visible light above 420 nm (<2.9 eV). (C) 2003 American Institute of Physics.