Synthesis and Size-separation of Colloidally-stable Silicon Nanocrystals for the Investigation of their Size-dependent Optical Properties

Silicon nanocrystals (ncSi) possess unique optical properties that vary predictably with crystal size, which means they can be tailored to suit specific requirements for use in optoelectronic devices and biological applications. The work presented in this thesis outlines contributions made in developing size-separation methods to obtain uniform-sized samples of colloidally-stable ncSi from non-uniform ensembles, which result from most common syntheses that produce colloidally-stable particles. Non-uniform samples of ncSi were prepared using the straightforward thermal processing of sol-gel glasses, followed by HF etching to liberate hydride-capped ncSi from an encapsulating matrix. Thermal hydrosilylation was employed to passivate the ncSi surface with both allylbenzene and 1-decene. Density gradient ultracentrifugation and size-selective precipitation methods were used to isolate size-separated ncSi, which enabled definitive characterization of size-dependent optical properties including photoluminescence (PL), PL absolute quantum yields, and PL lifetimes. A detailed investigation of the chemical reactivity of allylbenzene-capped ncSi with different gaseous atmospheres as probed by in situ luminescence spectroscopy, conducted under both continuous and intermittent illumination, helped elucidate the roles of O2, H2O and mixtures of O2/H2O, with respect to oxidation of ncSi as a function of size. The results presented in this thesis have played a crucial role towards obtaining a complete understanding of ncSi, a most promising material, and providing vital information that will aid in developing and tailoring perceived applications in advanced materials and biomedical devices.Ph.D