Alkyl‐Functionalized Oxide‐Free Silicon Nanoparticles: Synthesis and Optical Properties

Highly monodisperse silicon nanoparticles (1.57 ± 0.21 nm) are synthesized with a covalently attached alkyl monolayer on a gram scale. Infrared spectroscopy shows that these silicon nanoparticles contain only a few oxygen atoms per nanoparticle. XPS spectra clearly show the presence of unoxidized Si and attached alkyl chains. Owing to the relatively efficient synthesis (yields ≈100‐fold higher than of those previously reported) the molar extinction coefficient ε can be measured: ε max  = 1.7 × 10 −4  M −1 cm −1 , only a factor of 4 lower than that of CdS and CdSe nanoparticles of that size. The quantum yield of emission ranges from 0.12 (C 10 H 21 ‐capping) to 0.23 (C 16 H 33 ‐capping). UV/Vis absorption and emission spectroscopy show clear vibrational progressions (974 ± 14 cm −1 ; up to five vibrational bands visible at room temperature), resembling bulk SiC phonons, which support the monodispersity observed by TEM. This was also confirmed by time‐resolved fluorescence anisotropy measurements, which display a strictly monoexponential decay that can only be indicative of monodisperse, ball‐shaped nanoparticles.