In order to fill high quality insulators into narrower spaces in advanced metallizationthe digital CVD (Chemical Vapor Deposition) of multilayer stacked Si oxide and nitride films was studied. Reaction of TES (triethylsilane) with hydrogen (H) atoms was also found to lead to conformal CVD of Si film involving organic species. This reaction took place only on the surface reaction. In-situ FTIR studies reveal that H atoms react with Si-C2H5 bonds in TES and thus generate strong Si-CH3 bonds and weak Si-H bonds, thereby liberating H2 and forming the organic Si film on the surface, and the surface reaction is dominated by the thermal effect from the substrate. Then Si oxide or nitride films were formed by the digitaCVD which repeated a cycle of deposition of this film with subsequent oxidation or nitridation. Oxide film integrity was improved greatly by removing included organic bonds in the TES/H reaction film by exposing the film to H atoms before the oxidation step. Thus electrically excellent multilayer stacked oxide and nitride films were obtained in a deep trench.