The effect of deposition conditions on the structure and composition of plasma deposited silicon nitride films was studied using x‐ray photoelectron spectroscopy. Plasma deposited silicon nitride films were transferred directly from the deposition chamber into a surface analysis system, thereby permitting analysis of as‐deposited films without modification due to ion sputtering. Plasma deposited silicon nitride films with N:Si ratios from 1.8–0.3 were deposited using SiH4, NH3, N2, and H2as the source gases. The N:Si ratio in the films increased with increasing nitrogen concentration in the gas phase. Changes in the deposition power or the substrate temperature also influenced the N:Si ratio. Large differences in the film structure were observed for plasma deposited silicon nitride films formed with NH3compared to N2with respect to deposition temperature variations.