A new synthetic method was developed to produce robust, highly crystalline, organic-monolayer passivated silicon (Si) nanocrystals in a supercritical fluid. By thermally degrading the Si precursor, diphenylsilane, in the presence of octanol at 500 degrees C and 345 bar, relatively size-monodisperse sterically stabilized Si nanocrystals ranging from 15 to 40 A in diameter could be obtained in significant quantities. Octanol binds to the Si nanocrystal surface through an alkoxide linkage and provides steric stabilization through the hydrocarbon chain. The absorbance and photoluminescence excitation (PLE) spectra of the nanocrystals exhibit a significant blue shift in optical properties from the bulk band gap energy of 1.2 eV due to quantum confinement effects. The stable Si clusters show efficient blue (15 A) or green (25-40 A) band-edge photoemission with luminescence quantum yields up to 23% at room temperature, and electronic structure characteristic of a predominantly indirect transition, despite the extremely small particle size. The smallest nanocrystals, 15 A in diameter, exhibit discrete optical transitions, characteristic of quantum confinement effects for crystalline nanocrystals with a narrow size distribution.