Influences of rapid thermal process on solution-deposited Ti-silicate/Si films: Phase segregation, composition and interface changes, and dielectric properties

Ti-silicate/Si films were synthesized using a solution deposition route, and the effects of a rapid thermal process (RTP) on the microstructure, chemical bonding state, and interfacial layer (IL) properties were investigated and correlated to the permittivity of the films. The precursor solution was prepared from Ti(IV)-isopropoxide and tetraethylorthosilicate, spin-coated on HF-treated Si substrates, dried, pyrolyzed (400 °C), and subjected to the RTP at 700 °C-1000 °C. The Ti-silicate film consisted of Ti-rich and Si-rich silicates after the pyrolysis and phase segregation became significant as the RTP temperature increase. The silicates segregated into TiO2-like nanocrystals and Si-richer silicate at up to 850 °C, and the TiO2-like nanocrystals grew remarkably while the Si-richer silicate was converted into nearly pure SiO2 at 1000 °C. In addition, the Ti content in the Ti-silicate layer decreased due to Ti out-diffusion to the IL and substrate. Based on HRTEM, FT-IR, XPS, and SIMS analyses, we suggest a model of phase segregation with Ti diffusion and demonstrate that the Ti diffusion can be a critical issue in applications of Ti-silicate/Si systems, in addition to other well-known phenomena, including phase segregation, TiO2 precipitation, or interface properties.