Structural studies of spray pyrolysis synthesized oxygen deficient anatase TiO2 thin films by using X-ray absorption spectroscopy

The present work focuses on synthesis and X-ray absorption studies of single phase oxygen deficient anatase TiO2 thin films. These films are prepared in a two-step method viz. the synthesis of near stoichiometric anatase TiO2 films using an open atmospheric spray pyrolysis method followed by vacuum annealing at their corresponding synthesis temperatures (Ts = 450 °C, 500 °C) for different time durations (t = 2, 4, 6, 8 hours). XRD and Raman studies of these films ascertained the formation and retention of the anatase phase post annealing, indicating that there was no phase change due to prolonged annealing. Extended X-ray absorption spectra (EXAFS) and X-ray absorption near edge spectra (XANES) revealed the presence of an oxygen vacancy and its effect on the local co-ordination. The co-ordination number obtained from EXAFS analysis revealed that the number density of the oxygen vacancy is higher in the case of thin films synthesized at 450 °C than in the case of the films synthesized at 500 °C. As the oxygen vacancy leads to changes in local co-ordination, which in turn have a profound effect on the pre-edge features of the X-ray absorption spectra (XAS), theoretically simulated XAS spectra of pure anatase TiO2 and oxygen deficient anatase TiO2 were generated using FEFF and were found to match with the experimentally observed spectra. In addition, the ambiguities in whether a change in the metal–oxygen bond length has any effect on the pre-edge features or not were delineated in the present study by comparing the pre-edge peak positions of the oxygen deficient TiO2 films. Our results matched with those of some of the researchers who have studied the rutile phase TiO2, wherein it was concluded that in the case of the titanium–oxygen system, the mean Ti–O bond length does have an effect on the pre-edge peak position. It was observed that as the Ti–O mean bond length increases, the pre-edge peak positions shift towards lower energy, which is in concurrence with the literature available for other Ti–O systems with similar geometry. The second pre-edge peak intensity, which is a measure of disorder, is higher for TiO2450 °C-2 h and TiO2500 °C-2 h thin films. This is attributed to the annealing effect, which suggests that TiO6 octahedrons are the most disordered for thin films annealed for 2 h and become more ordered upon annealing for longer times.