Publications Details

GCMS and FTIR studies of by-product inhibited growth and the rate-limiting step in TEOS-based SiO{sub 2} CVD

Bartram, M.E.

To improve process reliability and deposition methods, it is essential to identify the rate-limiting step in TEOS-based SiO{sub 2} CVD and its dependence on process conditions. For this purpose, experiments designed to evaluate by-product inhibition effects and to identify the rate-limiting step in TEOS decomposition have been carried out in a research reactor using GCMS and FTIR. By repetitively sampling a series of reactions in which TEOS was first mixed with ethylene, ethanol, and water in the gas-phase, GCMS was used to show clearly that these reaction by-products do not inhibit the heterogeneous reaction step on SiO{sub 2} at 1,000K. FTIR was used to determine that ethoxy groups from TEOS dissociative chemisorption have a significant lifetime on the SiO{sub 2} surface at CVD temperatures and have an activation energy for decomposition of 16kcal/mol{+-}4kcal/mol. This is much higher than the activation energy of 6 kcal/mol reported for the initial chemisorption step and is near the 22 kcal/mol reported for the overall activation energy for SiO{sub 2} deposition in a cold-wall reactor. These results suggest that, whether or not surface ethoxy groups inhibit TEOS reactions, their decomposition may be directly related to the rate-limiting step in SiO{sub 2} deposition.