The strong photoluminescence (PL) of SiOx:H prepared by plasma enhanced chemical vapor deposition has been systematically studied in conjunction with infrared and micro-Raman spectra. We have found that each PL spectrum is comprised of two Gaussian components, a main band and a shoulder. The main band might originate from amorphous silicon clusters embedded in die SiOx network, and its redshift with annealing temperature is due to expansion of the silicon clusters. The shoulder remains at about 835 nm in spite of the annealing temperature and possibly comes from luminescent defect centers. The enhanced PL spectra after 1170 degrees C annealing are attributed to the quantum confinement effects of nanocrystalline silicon embedded in the SiO2 matrix. (C) 1998 American Institute of Physics.