Using high-resolution angle-resolved x-ray photoelectron spectroscopy (ARXPS) measurements, the chemical bonding, and valance-band offset of ultrathin (16 and 24 Angstrom) N2O-grown oxide were studied. We confirmed that the composition of N2O-grown oxide is mainly silicon oxide with both the concentration and band offset values measured using ARXPS. The surface density of nitrogen is about (3 +/- 1) X 10(14) cm(-2) near the Si/dielectric interface. The valence- and conduction-band offsets for N2O-grown oxide are the same as those for the Si/SiO2 interface because the nitrogen content is too low to have any pronounced effects. In addition, we found that most of the nitrogen atoms at the interface appeared in the form of Si-N bonding instead of N-O bonding. (C) 2003 American Vacuum Society.