Surface chemistry of luminescent colloidal silicon nanoparticles

Luminescent colloidal silicon particles are obtained by burning silane and slowly etching the product with hydrogen fluoride. Depending on their size, the particles emit red-orange or blue-green light with decay times between 28 ys and < 0.1 ys, respectively. The quantum yield of the red luminescence is found to be 35%, i.e., much higher than the 7% previously reported, and the yield of the blue-green luminescence is 18%. The luminescence of the colloidal particles is quenched upon the attack of their surface by free radicals, oxygen-centered radicals being more efficient than carbon-centered ones. It is concluded from the dependence of the luminescence wavelength on the etching time and the dependence of the luminescence lifetime on the wavelength that the mechanism of the photoluminescence undergoes a change with decreasing particle size. The red luminescent particles exhibit amphiphilic properties, such as unusual wetting phenomena. This effect is understood in terms of the existence of few polar groups on the otherwise nonpolar surface of the particles, possibly Si-OH groups, which also act as centers of the red luminescence.