The growth mechanism of silicon nanocrystals (Si NCs) synthesized at a high rate by means of expanding thermal plasma chemical vapor deposition technique are studied in this letter. A bimodal Gaussian size distribution is revealed from the high-resolution transmission electron microscopy images, and routes to reduce the unwanted large Si NCs are discussed. Photoluminescence and Raman spectroscopies are employed to study the size-dependent quantum confinement effect, from which the average diameters of the small Si NCs are determined. The surface oxidation kinetics of Si NCs are studied using Fourier transform infrared spectroscopy and the importance of postdeposition passivation treatments of hydrogenated crystalline silicon surfaces are demonstrated.