Single and bi-excitonic characteristics of ligand-modified silicon nanoparticles as demonstrated via single particle photon statistics and plasmonic effects

Silicon nanoparticles (Si NPs) are of great interest to researchers due to their fluorescence properties, low toxicity, and the low cost of the Si precursor. Recent studies have shown that Si NPs surface-modified with secondary aryl amine ligands emit light at wavelengths ranging from cyan to yellow and with quantum yields of up to 90%. The predominant emitting state in these species has been assigned to a charge-transfer (CT) transition from the ligand to the Si particle as the emission wavelength is determined by the dipolar properties of the ligand rather than the size of the Si core. This contribution focuses on the single-molecule emission properties of Si NPs functionalized with a 1,2,3,4-tetrahydrocarbazole-4-one ligand (Te-On) which have a peak emission wavelength of 550 nm and a quantum yield of 90%. In single-particle dispersed emission spectra, a weak long-wavelength sideband is seen in addition to the dominant yellow emission derived from the CT state. The photon statistical behavior of single Si NPs in the red emission region is consistent with that of a state having collective or bi-excitonic character. In contrast, the yellow emission exhibits predominantly CT character. Deposition of the sample onto a thin gold film causes the CT emission to be quenched whereas that attributed to a bi-exciton state of the Si core is enhanced. These results provide new insights into the mechanism of single-molecule intensity fluctuation in these surface-modified silicon nanoparticles that will benefit proposed applications in biological labeling and as single-photon sources.