The syntheses of colloidal silicon nanocrystals (Si-NCs) with dimensions in the 3-4 nm size regime as well as effective methodologies for their functionalization with alkyl, amine, phosphine, and acetal functional groups are reported. Through rational variation in the surface moieties we demonstrate that the photoluminescence of Si-NCs can be effectively tuned across the entire visible spectral region without changing particle size. The surface-state dependent emission exhibited short-lived excited-states and higher relative photoluminescence quantum yields compared to Si-NCs of equivalent size exhibiting emission originating from the band gap transition. The Si-NCs were exhaustively characterized using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Fourier transformed infrared spectroscopy (FTIR), and their optical properties were thoroughly investigated using fluorescence spectroscopy, excited-state lifetime measurements, photobleaching experiments, and solvatochromism studies.

The role of surface species in the optical properties of silicon nanocrystals (SiNCs) is the subject of intense debate. Changes in photoluminescence (PL) energy following hydrosilylation of SiNCs with alkyl-terminated surfaces are most often ascribed to enhanced quantum confinement in the smaller cores of oxidized NCs or to oxygen-induced defect emission. We have investigated the PL properties of alkyl-functionalized SiNCs prepared using two related methods: thermal and photochemical hydrosilylation. Photochemically functionalized SiNCs exhibit higher emission energies than the thermally functionalized equivalent. While microsecond lifetime emission attributed to carrier recombination within the NC core was observed from all samples, much faster, size-independent nanosecond lifetime components were only observed in samples prepared using photochemical hydrosilylation that possessed substantial surface oxidation. In addition, photochemically modified SiNCs exhibit higher absolute photoluminescent quantum yields (AQY), consistent with radiative recombination processes occurring at the oxygen-based defects. Correlating spectrally- and time-resolved PL measurements and XPS-derived relative surface oxidation for NCs prepared using different photoassisted hydrosilylation reaction times provides evidence the PL blue-shift as well as the short-lived PL emission observed for photochemically functionalized SiNCs are related to the relative concentration of oxygen surface defects.

One-pot syntheses of surface functionalized germanium nanocrystals (GeNCs) based upon traditional hot injection and microwave-assisted heating of a Ge(II) dihydride single source precursor have been developed. The reported procedures offer in situ hydrogermylation-based covalent attachment of alkene/alkyne derived surface moieties that give access to hydrophobic or hydrophilic GeNCs.

Time-resolved photoluminescence spectroscopy reveals a charge transfer state dynamics responsible for the size-independent blue emission observed from dodecylamine and ammonia functionalized silicon nanocrystals.