Thermal nitridation of SiO2 in ammonia gas at elevated temperatures has been found to be useful for forming reliable thin gate insulators. Interfacial characteristics of MOS diodes with thermally nitrided SiO~ (nitroxide) films are significantly influenced by the nitridation conditions. At around 900~ hydrogen gas produced by the dissociation of ammonia gas deteriorates the quality of the starting SiO2 film, resulting in a negative shift of flatband voltages. Nitridation above 1100~ provides excellent properties for MOS diodes. The high field instability, which occurs just prior to dielectric breakdown, is avoided. A surface state density of lower than 1010 cm -2 eV -I is obtained at the Si midgap and the insulator charge becomes negligible. A strong barrier against contamination is formed on the SiO2 film. The mobile ion density of MOS diodes is reduced to the negligible range even if sodiumcontaminated gates are used. These features are attributable to not only the surface nitrided region of the nitroxide film but also the improved structure at the Si/SiO2 interface through the nitridation process.