Hardness of Nanocrystalline TiO2 Thin Films

In this work results of hardness investigations of nanocrystalline TiO2 thin films are presented. Thin films were prepared by low pressure hot target reactive sputtering (LPHTRS) and high energy reactive magnetron sputtering (HERMS). In both processes a metallic Ti target was sputtered under low pressure of oxygen working gas. After deposition by LPHTRS TiO2 thin films with anatase structure were obtained and after additional post-process annealing at 1070 K, these films recrystallized into the rutile structure. Annealing also resulted in an increase of average crystallite size from 33 nm (for anatase) to 74 nm (for rutile). The HERMS process is a modification of the LPHTRS process with the addition of an increased amplitude of unipolar voltage pulses, powering the magnetron. This effectively increases the total energy of the depositing particles at the substrate and allows dense, nanocrystalline (8.7 nm crystallites in size) TiO2 thin film with the rutile structure to be formed directly. The hardness of the films was determined by nanoindentation. The results showed that the nanocrystalline TiO2-rutile thin film as-deposited using HERMS had high hardness (14.3 GPa), while the TiO2-anatase films as-deposited by LPHTRS, were 4-times lower (3.5 GPa). For LPHTRS films recrystallized by additional annealing, the change in thin film structure from anatase to rutile resulted in an increase of film hardness from 3.5 GPa to only 7.9 GPa. The HERMS process can therefore produce the TiO2 rutile structure directly, with hardness that is 2 times greater than rutile films produced by LPHTRS with additional annealing step.