Pulsed laser ablation (PLA) in inert background gases can synthesize the nanoscaled silicon (Si), for studying its material properties as one of the quantum confinement effects. We report an optimized condition in Si nanocrystalline formation by the PLA in inert background gas, varying processing parameters: pulse energy and width, inert background gas pressure. The optimized process can prepare well-dispersed Si nanocrystallites without any droplets and debris. Furthermore, we investigate the influence of the processing parameters Si nanocrystallites without any droplets and debris. Furthermore, we investigate the influence of the processing parameters on transition from amorphous-like Si thin films to nanocrystallites. It was found that there is a processing window of the inert background gas pressure where the carrier confinement effects become apparent. Next, we have fabricated electroluminescent (EL), diodes with active layers of the Si nanocrystallites. The structure of the EL diodes was semitransparent platinum electrode/Si nanocrystallite layer/p-type Si/Pt electrode. We have observed visible spectra of not only green photoluminescence, but also red EL, at room temperature. Furthermore, we have found that the EL diodes showed strong nonlinear dependence of EL intensity on current density.