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Silicon oxynitride films were deposited using a plasma-enhanced chemical vapor deposition process. The bond configurations of the constituent atoms in the deposited film were analyzed using x-ray photoelectron spectroscopy. Analysis of the Si 2p spectra showed the presence of nonstoichiometric silicon oxide and silicon oxynitride. Analysis of the binding energy shifts induced by Si–O and Si–N bond formation indicated an O–Si–N complex was present in the film matrix. Component balance analysis indicated that second-nearest-neighbor bond interactions were not the cause of these energy shifts and supported the presence of an O–Si–N complex