We have studied the photoluminescence (PL) mechanism of photo- and electroluminescent amorphous silicon oxynitride films grown by plasma enhanced chemical vapor deposition. The composition of the films was determined by Rutherford backscattering spectrometry and monitored by the index of refraction with single-wavelength ellipsometry. Two sets of samples were grown, each with different reactant gas residence times in the deposition chamber. For samples grown with a residence time of about 5 s, the energy of the PL peak for 2.54 eV excitation is 2.3 eV for stoichiometric films and redshifts with increasing silicon content to 1.7 eV for the most silicon-rich films. The energy of the PL peak for 3.8 eV excitation is 2.8 eV for stoichiometric films and 2.1 eV for the most silicon-rich films. For stoichiometric films, the PL intensity is independent of temperature between 80 and 300 K using 2.54 eV excitation, but the PL intensity decreases by a factor of two over the same temperature range for 3.8 eV excitation. The authors interpret these aspects of the PL as consistent with tail-state recombination. Other results imply the PL is due to a specific luminescence center related to Si-Si or Si-H bonding. A 450°C anneal reduces the paramagnetic defect density in the films, as detected by electron paramagnetic resonance, by an order of magnitude, but does not increase the PL intensity, while a 950°C anneal increases both the defect density and the PL intensity. In addition, films in a second set of samples, grown with a residence time of 1.8 s, display very different PL behavior than samples in the first set with the same composition. Samples near stoichiometry in the second set have a PL peak at 2.06 eV and are 20 times less intense than stoichiometric samples in the first set. Optical absorption measurements indicate both types of samples contain Si-Si bonds, with the second set containing many more Si-Si bonds than the first. Fourier-transform infrared measurements indicate the presence of a Si-H bond that is stable at temperatures of 950°C in the first set, but not in the second set. Thus, the study as a whole suggests a complete picture of luminescence in our silicon oxynitride films must incorporate elements of both tail-state and luminescence center models. The relation of the results to other PL studies in silicon alloys and porous silicon is discussed. © 1999 American Institute of Physics.