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Stimulated emission has been observed from oxide structure of silicon when optically excited by 514 nm laser. The photoluminescence (PL) pulse has a Lorentzian shape with a full width at half maximum (FWHM) of 0.5–0.6 nm. The twin peaks at 694 nm and 692 nm are dominated by stimulated emission which can be demonstrated by its threshold behavior and transition from sub-threshold to linear evolution in light emission. The gain coefficient from the evolution of the peak-emission intensity as a function of the optically pumped sample length has been measured. The oxide structure was fabricated by laser irradiation and annealing treatment on silicon. A model for explaining the stimulated emission has been proposed in which the trap states of the interface between oxide of silicon and porous nanocrystal play an important role.