In
the current paper, we provide direct evidence of a controlled
structure of silicon nanocrystals (SiNCs). The photoluminescence quantum
yields (PLQYs) are considerably enhanced by ligand exchange between
the hydrogen atoms and hydrocarbon chains. To systematically study
this phenomenon, we prepared SiNCs by thermal disproportionation of
amorphous hydrogen silsesquioxane that was derived from triethoxysilane,
which was followed by hydrofluoric etching and hydrosilylation of
1-alkenes. The estimated PLQY was 56% at maximum. The near-infrared
(NIR) PL spectra of the specimens can be tuned by accurately controlling
their diameters to engineer the fundamental gap. Through a combination
of X-ray diffraction, Raman spectroscopy, and scanning transmission
electron microscopy, we elucidated that the alkyl monolayers provide
an anchor that prevents the lattice distortion of the diamond cubic
lattice of Si, thus inhibiting the creation of nonradiative channels.
This anchoring effect is responsible for the high PLQYs. The emissions
were sufficiently strong for the fabrication of NIR light-emitting
diodes that operate in the first biological window (650–900
nm) where the light absorption of water and the tissues including
hemoglobin is minimal.