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The excellent properties of titanium dioxide films (e.g. photocatalytic activity, hydrophilicity) largely depend on their phase composition, crystallinity and microstructure. Crystallization of amorphous films with different thickness (50-2000 nm) was investigated by insitu isochronal and isothermal annealing at different temperatures and compared with the post-annealing of both amorphous and nanocrystalline films. The X’Pert Pro with MRI high-temperature chamber in parallel beam was used. The time dependences of crystallization were studied at low temperatures (180, 220°C). They could be well described by modified Avrami equation applied to the intensities of diffraction peaks I = 1-exp[-b(t-t0))]. The exponent n was in the range 2-2.5 and slightly increasing with the film thickness. The initial time t0 of crystallization (non-zero intensity) increases nearly exponentially with the decreasing thickness while the slope b increases significantly for thicker films. Typical time necessary for the crystallization of the whole film volume at the above temperature varied from several hours for thicker layers to about ten days for the thinnest films. Fast crystallization of the order of minutes appeared at 230 °C for thicker films and went up to 290°C for the thin film (below 100 nm). Weak texture was changing during the crystallization. Significant shifts of diffraction peaks with the temperature were observed and tensile residual stresses were confirmed by the sinψ method for different diffraction peaks. They decrease with the increasing film thickness. Line profile analysis shown the growth of relatively large crystallites (100 nm) already at the beginning of crystallization. Reflectivity indicates increase of surface roughness with the thickness.

Compositional analysis of LaMnO3–LaCoO3–LaNiO3thin-film thermoelectric property diagrams

Compositional analysis of LaMnO₃–LaCoO₃–LaNiO₃thin-film thermoelectric property diagrams