Nanosecond pulsed laser deposition of TiO2: nanostructure and morphology of deposits and plasma diagnosis

Nanostructured TiO2 films on Si (100) substrates have been grown by nanosecond pulsed laser deposition at the wavelengths of 266, 355 and 532 nm using a Q-switched Nd:YAG laser and TiO2 sintered rutile targets. The effect of laser irradiation wavelength, the temperature of the substrate and the presence of O2 as background gas on the crystallinity and surface structure of deposits were determined, together with the composition, expansion dynamics and thermodynamic parameters of the ablation plume. Deposits were analyzed by X-ray photoelectron spectroscopy, X-ray diffraction, environmental scanning electron microscopy and atomic force microscopy, while in situ monitoring of the plume was carried out and characterized with spectral, temporal and spatial resolution by optical emission spectroscopy. Stoichiometric, crystalline deposits, with nanostructured morphology were obtained at substrate temperatures above 600 °C. Microscopic particulates were found overimposed on the nanostructured films but their size and density were significantly reduced by operating at short wavelength (266 nm) and upon addition of a low pressure of oxygen (0.05 Pa). The dominant crystalline phase is rutile at 355 and 532 nm. At the short irradiation wavelength, 266 nm, the preferred phase in the presence of oxygen is rutile, while anatase is preferably observed under vacuum. The narrowest size distribution and smallest nanoparticle diameters, of around 25 nm, were found by deposition at 266 nm under 0.05 Pa of oxygen.