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The oxidation of Si(100) in N20 has been studied at temperatures in the range from 950 to 1200°C using secondary ion mass spectroscopy, Auger electron spectroscopy, and x-ray photoelectron spectroscopy. During oxidation N became incorporated into the oxide film, the amount increasing with increasing temperature to 1100°C and then falling to a lower value at 1200°C. The N was concentrated as a thin N-rich layer near the SiOrSi interface inhibiting the influx of oxidant, leading to a reduction in the extent of oxidation compared with that in pure 02. The oxidant species is believed to be NO, which is stable under the conditions of the experiments. The N-rich phase was shown to have a composition of Si3N4 surmounted by N-rich oxynitride.