Thin film dielectrics have been prepared in a cluster processing system with chambers for plasma-assisted, rapid-thermal processing, and on-line Auger electron spectroscopy (AES). A low-thermal budget process for the formation of homogeneous silicon oxynitride (OXN) alloy films is presented. This Na2-based plasma-CVD process has (i) increased process latitude for the formation of N-rich alloys, and (ii) results in lower bonded-H concentrations, in comparison with a similar NH3-based process. Gate dielectric formation consists of (i) a 300°C plasma-assisted oxidation for removal of residual hydrocarbons, and formation of an Si-SiO2 interface protected by ∼0.5-0.6 nm of oxide, (ii) a 300°C plasma-assisted CVD of oxynitride films from N2O, N2, and SiH4, and (iii) a 30 s, 900°C post-deposition rapid-thermal anneal in an ambient that contains sufficient oxygen to prevent decomposition of the Si/SiO2 interface. On-line AES and off-line infrared (IR) spectroscopy have been used to characterize chemical bonding, showing that the deposited films are pseudo-binary alloys lying on a join-line from SiO2 and Si3N4 in a ternary composition diagram. Electrical characterization of MOS capacitors, consisting of O-OXN-O structures, using C-V techniques is discussed.