The effect of postdeposition annealing in vacuum and in dry O2 on the atomic transport and chemical stability of chemical vapor deposited ZrSixOy films on Si is investigated. Rutherford backscattering spectrometry, narrow nuclear resonance profiling, and low energy ion scattering spectroscopy were used to obtain depth distributions of Si, O, and Zr in the films. The chemical environment of these elements in near-surface and near-interface regions was identified by angle-resolved x-ray photoelectron spectroscopy. It is shown that although the interface region is rather stable, the surface region presents an accumulation of Si after thermal annealing. © 2001 American Institute of Physics.