Reactions of N2+ ion beams with oxide surfaces of α-Al2O3(0001) single crystal and chemical vapor deposition (CVD) SiO2, and reactions of O2+ ion beams with a nitride surface of Si-rich CVD Si3N4 were investigated as a function of ion beam energy (200–1000 V) and dose (1×1015–1×1017/cm2). The thickness modified by the irradiation of a reactive low kinetic energy ion beam was measured using high resolution cross-sectional images of transmission electron microscopy (HR-XTEM), and the formation of new bonding induced by chemical reaction was analyzed by x-ray photoelectron spectroscopy (XPS). New bonding of Al–O–N on α-Al2O3(0001) started to be observed at 600 V N2+ ion energy and a dose of 1×1016/cm2, and Al–N bonding could be found at an ion beam energy of 1 keV. The thickness of the aluminum oxynitride layer after 800 V N2+ bombardment has been determined to be 10–50 Å by HR-XTEM analysis. In the case of CVD SiO2 surface modification, new bonding related to nitrogen was not clearly resolved in the XPS spectra, irrespective of the change of ion beam energy from 200 to 1000 V and ion dose from 1×1015 to 1×1017/cm2.<- - /formula> However, widening of the full width at half maximum of Si 2p core-level XPS spectra for the modified SiO2 surface and the peak position of N 1s around 399 eV were evidence of the existence of nitrogen-related bonding like Si–O–N in the modified CVD SiO2 surfaces. Moreover, it was very interesting that the Si 2p peak of elemental Si appeared in the sample irradiated at a dose of 1×1017/cm2. Its occurrence was considered to be due mainly to the preferential sputtering effect, and was found to be largely dependent on the ion beam energy as well as on the ion dose. In the surface modification of low-pressure CVD Si3N4 by direct ken O2+ ion irradiation, Si–O–N bonding could be successfully created at an ion beam energy of 200 V and it evolved significantly at ion beam energies higher than 500 V. From the above results, low energy reactive ion beam irradiation can successfully create new bonding structures on oxide and nitride surfaces due to a surface chemical reaction like nitridation or oxidation, and is expected to be very useful for the formation of new ultrathin functional layers on ceramic surfaces. © 1999 American Vacuum Society.