In-situ X-ray diffraction studies of time and thickness dependence of crystallization of amorphous TiO₂ thin films and stress evolution

Remarkable properties of titanium dioxide films such as hydrophilicity or photocatalytic activity depend largely on their phase composition, microstructure and in particular on the crystallinity. By in-situ X-ray diffraction studies of isochronal and isothermal annealing of amorphous films with different thickness at different temperatures it was found that the crystallization process can be quite well described by the Johnson-Mehl-Avrami- Kolmogorov formula modified by the introduction of crystallization onset. This and other parameters of the formula strongly depend on the film thickness. For thickness below about 500 nm the crystallization is very slow. Simultaneously, the appearance and increase of tensile stresses with the annealing time were observed and these stresses were confirmed by detailed studies by both total pattern fitting and sin²ψ method on post-annealed samples. The stresses rapidly increase with decreasing thickness of the films. It seems that there is a strong correlation between the stresses and crystallization onset and/or crystallization rate. Tensile stresses that are generated during crystallization further inhibit crystallization and cause significant thickness dependence of the crystallization. The temperature and time dependence of microstructure of crystallized amorphous films differ significantly from those obtained for as-deposited nanocrystalline films or nanocrystalline powders. During annealing, quite large crystallites are formed quickly with the preferred orientation (001) that is suppressed with the proceeding time.