A hydrogen‐terminated silicon surface was successfully converted to a surface covered with a monolayer of nitrogen. Nitridation was carried out in a vacuum chamber using either dimethylhydrazine [H2N–N(CH3)2] or ammonia at a pressure of 1 mTorr and at temperatures ranging from 400 to 600 °C.Insitux‐ray photoelectron spectroscopy measurements revealed that the binding energy and the full width at half‐maximum in the nitrogen spectra are the same as those in bulk Si3N4. Nitrogen content at the surface increased as the nitridation time increased and, below 500 °C, saturated at a value that approximately corresponds to a monolayer thickness. These results show the effectiveness of dry chemical processes for preparing uniform Si surfaces terminated with specific atoms or molecules other than hydrogen. ©1995 American Institute of Physics.