Photocatalytic Hydrogen Generation by CdSe/CdS Nanoparticles.

The photocatalytic hydrogen (H2) production activity of various CdSe semiconductor nanoparticles was compared including CdSe and CdSe/CdS quantum dots (QDs), CdSe quantum rods (QRs), and CdSe/CdS dot-in-rods (DIRs). With equivalent photons absorbed, the H2 generation activity orders as CdSe QDs ≫ CdSe QRs > CdSe/CdS QDs > CdSe/CdS DIRs, which is surprisingly the opposite of the electron-hole separation efficiency. Calculations of photoexcited surface charge densities are positively correlated with the H2 production rate and suggest the size of the nanoparticle plays a critical role in determining the relative efficiency of H2 production.

The influence of continuous vs. pulsed laser excitation on single quantum dot photophysics.

The impact of pulsed versus continuous wave (cw) laser excitation on the photophysical properties of single quantum dots (QDs) has been investigated in an experiment in which all macroscopic variables are identical except the nature of laser excitation. Pulsed excitation exaggerates the effects of photobleaching, results in a lower probability of long ON fluorescence blinking events, and leads to shorter fluorescence lifetimes with respect to cw excitation at the same wavelength and average intensity. Spectral wandering, biexciton quantum yields, and power law exponents that describe fluorescence blinking are largely insensitive to the nature of laser excitation.

Single-molecule studies of a model fluorenone.

Single-molecule fluorescence measurements of 2,7-bis(3,4,5-trimethoxyphenylethenyl)fluorenone (OFOPV) reveal narrow emission spectra concentrated around 540 nm, with weak emission at longer wavelengths. The wide scattering of emission-maximum wavelengths is attributed to varying molecular environments, with dimers or higher-order aggregates contributing to the low-energy emission. This spectral distribution indicates that emission from monomers of this model fluorenone is mostly green, which is consistent with contaminant emission (g-bands) often observed in fluorene- and polyfluorene-based organic light emitting diode (OLED) devices.

Coverage-mediated suppression of blinking in solid state quantum dot conjugated organic composite nanostructures.

Size-correlated single-molecule fluorescence measurements on CdSe quantum dots functionalized with oligo(phenylene vinylene) (OPV) ligands exhibit modified fluorescence intermittency (blinking) statistics that are highly sensitive to the degree of ligand coverage on the quantum dot surface. As evidenced by a distinct surface height signature, fully covered CdSe-OPV nanostructures (approximately 25 ligands) show complete suppression of blinking in the solid state on an integration time scale of 1 s. Some access to dark states is observed on finer time scales (100 ms) with average persistence times significantly shorter than those from ZnS-capped CdSe quantum dots.

Observation of enhanced energy transfer in individual quantum dot-oligophenylene vinylene nanostructures.

The temporal and spectral properties of luminescence from individual CdSe quantum dot-oligophenylene vinylene nanostructures (single quantum dots with conjugated organic ligands coordinated to the surface) are profoundly modified relative to blended films of the same components. These kinds of composite quantum dot-conjugated organic systems have attracted significant interest as a way to improve efficiency in photovoltaic device applications. By direct functionalization of the dot surface with the conjugated organic ligands, we realize a significant enhancement in energy transfer and luminescence stability.