Abstract
On the basis of the systematic study on temperature dependence of photoluminescence (PL) properties along with relaxation dynamics we revise a long-accepted mechanism for enhancing absolute PL quantum yields (QYs) of freestanding silicon nanocrystals (ncSi). A hydrogen-terminated ncSi (ncSi:H) of 2.1 nm was prepared by thermal disproportination of (HSiO1.5)n, followed by hydrofluoric etching. Room-temperature PL QY of the ncSi:H increased twentyfold only by hydrosilylation of 1-octadecene (ncSi-OD). A combination of PL spectroscopic measurement from cryogenic to room temperature with structural characterization allows us to link the enhanced PL QYs with the notable difference in surface structure between the ncSi:H and the ncSi-OD. The hydride-terminated surface suffers from the presence of a large amount of nonradiative relaxation channels whereas the passivation with alkyl monolayers suppresses the creation of the nonradiative relaxation channels to yield the high PL QY.