Aiming for a more practical route to highly stable visible photoluminescence (PL) from silicon, a novel approach to produce luminescent silicon nanoparticles (Si-NPs) is developed. Single crystalline Si-NPs; are synthesized by pyrolysis of silane (SiH4) in a microwave plasma reactor at very high production rates (0.1-10gh(-1)). The emission wavelength of the Si-NPs; is controlled by etching them in a mixture of hydrofluoric acid and nitric acid. Emission across the entire visible spectrum is obtained by varying the etching time. it is observed that the air oxidation of the etched Si-NPs profoundly affects their optical properties, and causes their emission to blue-shift and diminish in intensity with time. Modification of the silicon surface by UV-induced hydrosilylation also causes a shift in the spectrum. The nature of the shift (red/blue) is dependent on the emission wavelength of the etched Si-NPs. In addition, the amount of shift depends on the type of organic ligand on the silicon surface and the UV exposure time. The surface modification of Si-NPs; with different alkenes results in highly stable PL and allows their dispersion in a variety of organic solvents. This method of producing macroscopic quantities of Si-NPs with very high PL stability opens new avenues to applications of silicon quantum dots in optoelectronic and biological fields, and paves the way towards their commercialization.