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Nitridation of hydrogen-terminated silicon with N2:N2O has been studied by x-ray photoemission spectroscopy. Our analysis has given evidence that the broad N(1s) peak at 398–399 eV, usually reported in the literature, is preceded by the formation of a narrow peak at 397.5 eV, attributed to the moiety Si3N in which silicon is only marginally oxidized, and two other peaks at 400.0 eV and 401.5 eV, attributed to the moieties Si2NOSi and SiNO, respectively.

The early oxidation stages of hydrogen-terminated single-crystalline (100) silicon exposed to a diluted N2 : N2O atmosphere at 850°C for different durations have been studied by x-ray photoemission spectroscopy, following the evolution of the Si 2p signal. Evidence is given that the usual analysis, in terms of five pairs of peaks attributed to silicon in the oxidation states from 0 to +4, does not account for the observed Si 2p signal. An explanation for silicon in unusual oxidation states is proposed.