Organically functionalized mesoporous silica films were prepared by a novel synthesis procedure. The synthesis procedure involves a vapor infiltration technique for mesostructured silica films prepared through a spin-coating process. Organic-functional groups were incorporated into the mesochannel wall by the vapor infiltration treatment using organosiloxanes. The structural stability of spin-on mesostructured silica films is generally low, resulting in a structural shrinkage or a collapse of the mesostructure under calcination process. On the other hand, the treated films did not contract during calcination, indicating high structural stability. A contact angle of water on the treated film was large, showing high hydrophobicity. FTIR analysis suggested that the residual silanol groups were replaced with the organosilyl groups after vapor infiltration treatment. The increase in the film thickness was hardly observed under vapor infiltration, suggesting no deposition of organosiloxanes vapor on the surface of the film.

A novel synthesis route for mesostructured silica films is reported. Nano-phase transition from lamellar phase of surfactant to hexagonal phase of silica-surfactant nanocomposite was found under vapor infiltration. Vapor infiltration was performed using HCl as catalyst source and tetraethoxysilane (TEOS) as framework source. Highly ordered mesostructured silica films are obtained using alkyltrimethylammonium bromide CnTAB (the carbon number in the alkyl chain; n = 8, 10, 12, 14, 16, 18) as templating agent. The d values of the mesostructured silica films increase with increasing the length of the alkyl chain and are controllable by the synthetic temperature. The vapor infiltration synthesis is a simpler process compared to conventional sol-gel techniques and attractive for mass production of a variety of organic-inorganic composite materials and inorganic porous materials. This novel synthetic method provides opportunities for the creation of new materials technologies.

TiN films deposited by CVD utilizing TiCl4 and NH3 are widely used in ULSI processes. The residual chlorine in the film is one of the major issues of TiCl4 based chemistry [1–5]. We have examined the kinetics of TiN-CVD using TiCl4 and NH3 as precursors to determine method for controlling the residual chlorine concentration.

We analyzed the deposition rate profiles obtained from a simple tubular isothermal reactor. Deposition was performed over the temperature range from 300°C to 500°C and with varying initial concentrations of TiCl4 and NH3. We found that the deposition rate was independent of the TiCl4 concentration at higher concentrations. The deposition rate was proportional to the TiCl4 concentration in the low concentration range. This phenomenon can be well explained by a Langmuir-Hinshelwood type mechanism. Examination of the deposition rate dependence on the concentration of NH3 showed that both the maximum deposition rate at high TiCl4 concentrations and the first order kinetic rate constant in the lower TiCl4 concentration range were proportional to the NH3 concentration. These results indicate that the deposition was controlled by the Eley-Rideal mechanism. The residual chlorine concentration was found to be proportional to the surface coverage factor of adsorbed TiCl4. We conclude that the best way to obtain good quality TiN films can be obtained theoretically through these kinetic studies.