SiO2 films deposited on Si and on thermal SiO2 by tetraethylorthosilicate [TEOS, Si(OC2H5)4]/O3 atmospheric-pressure chemical vapor deposition (APCVD) were analyzed by thermal desorption spectra (TDS). The TDS results show that more silanols were incorporated during deposition and more water was absorbed during and after deposition in films deposited on Si substrates than on thermal oxide substrates. The latter result indicates that the elimination of water by-products is not the limiting step in TEOS/O3 APCVD. Based on the former result, a silanol model was proposed for the surface processes. On surfaces with a uniform and high density of silanol sites, or on which silanols readily form under TEOS/O3 APCVD conditions, the active silanol groups in the gas phase contribute to film formation and replenish silanol sites, resulting in continuous, high growth rates. On surfaces with few silanol sites, it is difficult to form silanol sites and the nonsilanol-containing polysiloxanes contribute to film formation, resulting in continuous, low growth rate. This model explains well both the surface dependence and the memory effect of TEOS/O3 APCVD. © 1999 American Institute of Physics.