Excimer laser processing as a tool for photocatalytic design of sol-gel TiO2 thin films

Nanostructured sol-gel TiO₂ thin films spin coated on silicate glass plates are subjected to excimer (KrF^*) pulsed laser irradiation in order to tailor their structure and photocatalytic properties. The surface morphology of virgin and laser-processed films are followed applying electron optical imaging and atomic force microscopy. The evolution of the surface roughness and pore formation are shown to be accompanied by optical absorption edge shift to infrared wavelength range. Conventional X-ray diffraction analysis and high-resolution transmission electron imaging are applied in order to obtain information on the phase composition. Co-existence of amorphous and anatase TiO₂ phases in nonirradiated sol-gel films is found. It is established that after laser processing the most intense XRD anatase peak is shifted to lower 2θ range. The analysis of high-resolution transmission electron images of film profiles evidences for the laser induced phase transitions. Formation of rutile and brookite TiO₂ accompanied by evolution of oxygen deficient Ti_nO_2n−1 phases are identified in the subsurface region. The contribution of laser processing for increasing the photocatalytic efficiency of laser-modified films toward the oxidation of methylene blue water solution is demonstrated. The results obtained reveal a novel-processing route for designing sol-gel titania films with improved photocatalytical activity.