• Energy Research
• 2016-2025close

Photoluminescence (PL) spectra were measured for dodecene-capped Si nanocrystals with a wide range of average diameters, from 1.8 to 9.1 nm. Nanocrystals larger than 3 nm exhibited relatively high PL quantum yields of 30%-45%. Smaller nanocrystals exhibited lower quantum yields that decreased significantly with reduced size. Because smaller nanocrystals also have lower optical absorption there is a significant biasing of the PL spectra by the larger nanocrystals. We show that with proper accounting of polydispersity and size-dependent quantum yields and optical absorption the effective mass approximation (EMA) accurately estimates the average diameter of silicon (Si) nanocrystals from experimentally determined PL emission peak energies. A finite confinement model is presented that explains the decreased PL quantum yields of the smaller diameter nanocrystals.

The interfacial structure in "giant" PbS/CdS quantum dots (QDs) was engineered by modulating the Cd:S molar ratio during in situ growth. The control of the gradient interfacial layer could facilitate hole transfer, regulate the transition from double- to single-color emission, as a consequence. These QDs are optically active close-to-the near-infrared (NIR) spectral region and are candidates as absorber materials in solar energy conversion. Photoinduced charge transfer from "giant" QDs to electron scavenger can still take place despite the ultra-thick (~5 nm) shell. The hybrid architecture based on a TiO2 mesoporous framework sensitized by the "giant" QDs with alloyed interface can produce a saturated photocurrent density as high as ~5.3 mA/cm2 in a photoelectrochemical (PEC) cell under 1 Sun illumination, which is around 2 times higher than that of bare PbS and core/thin-shell PbS/CdS QDs sensitizer. The as-prepared PEC device presented very good stability thanks to the "giant" core/shell QDs architecture with tailored interfacial layer and a further coating of the ZnS shell. 78% of the initial current density is kept after 2-h irradiation at 1 Sun. Engineering of electronic band structure plays a key role in boosting the functional properties of these composite systems, which hold great potential for H2 production in PEC devices.