Fe-doped and Mn-doped titanium dioxide thin films

Thin films of TiO₂ doped with Fe and Mn were deposited on F-doped SnO₂-coated glass by spin coating. Dopant concentrations of 3–7 wt% (metal basis) were used. The structural, chemical, and optical characteristics of the films were investigated. Laser Raman microspectroscopy and glancing angle X-ray diffraction data showed that the films consisted of the anatase polymorph of TiO₂. X-ray photoelectron spectroscopy data indicated the presence of Fe³⁺, Mn⁴⁺, and Mn³⁺ in the doped films, as predicted by calculated thermodynamic stability diagrams, and the occurrence of atomic disorder and associated structural distortion. Ultraviolet–visible spectrophotometry data showed that the optical indirect band gap of the films decreased significantly with increasing dopant levels, from 3.36 eV (undoped) to 2.95 eV (7 wt% Fe) and 2.90 eV (7 wt% Mn). These improvements are attributed to single (Fe) or multiple (Mn) shallow electron/hole trapping sites associated with the dopant ions.     

Effect of annealing temperature on titania thin films prepared by spin coating

Essentially fully dense titania thin films were spin coated on fused quartz substrates under identical conditions and subjected to annealing over the range 750°–900°C. The films were of a consistent ~400 nm thickness. The anatase → rutile phase transformation temperature was between 750°C and 800°C, with first-order kinetics; annealing at 900°C yielded single-phase rutile. Silicon contamination from the fused quartz substrate was considered to be critical since it suppressed both titania grain growth (maintaining constant grain size) and the phase transformation (occurring at an unusually high temperature); its presence also was considered to be responsible for the formation of lattice defects, which decreased the transmittances and the band gaps.