Ultrathin (8–23 Å) silicon oxynitrides have been studied in the temperature range of 560–1000 °C in 4 Torr of NO using a sequential growth and analysis approach. X-ray photoelectron spectroscopy indicates that with increasing growth temperature and time, a bonding structure with predominantly Si–O rather than Si–N formation is favored. Simultaneously, the average volume fraction of N (N/N+O) in the dielectric decreases, as a consequence of which the N1sbinding energy increases by 0.2–0.8 eV from its initial value of 397.8 eV at a thickness of 8 Å. A correlation of the electrical characteristics of NO grown oxynitrides with nitrogen content and location has been made. A film growth mechanism that takes into account the removal of previously incorporated N by NO is also proposed. ©1997 American Institute of Physics.