Tuning the Dimensionality of Excitons in Colloidal Quantum Dot Molecules.

Electrically coupled quantum dots (QDs) can support unique optoelectronic properties arising from the superposition of single-particle excited states. Experimental methods for integrating colloidal QDs within the same nano-object, however, have remained elusive to the rational design. Here, we demonstrate a chemical strategy that allows for the assembling of colloidal QDs into coupled composites, where proximal interactions give rise to unique optoelectronic behavior.

Competition of Charge and Energy Transfer Processes in Donor-Acceptor Fluorescence Pairs: Calibrating the Spectroscopic Ruler.

Sensing strategies utilizing Förster resonance energy transfer (FRET) are widely used for probing biological phenomena. FRET sensitivity to the donor-acceptor distance makes it ideal for measuring the concentration of a known analyte or determining the spatial separation between fluorescent labels in a macromolecular assembly. The difficulty lies in extracting the FRET efficiency from the acceptor-induced quenching of the donor emission, which may contain a significant non-FRET contribution.

One-Dimensional Carrier Confinement in "Giant" CdS/CdSe Excitonic Nanoshells.

The emerging generation of quantum dot optoelectronic devices offers an appealing prospect of a size-tunable band gap. The confinement-enabled control over electronic properties, however, requires nanoparticles to be sufficiently small, which leads to a large area of interparticle boundaries in a film. Such interfaces lead to a high density of surface traps which ultimately increase the electrical resistance of a solid.

Tracking the Energy Flow on Nanoscale via Sample-Transmitted Excitation Photoluminescence Spectroscopy.

Tracking the energy flow in nanoscale materials is an important yet challenging goal. Experimental methods for probing the intermolecular energy transfer (ET) are often burdened by the spectral crosstalk between donor and acceptor species, which complicates unraveling their individual contributions. This issue is particularly prominent in inorganic nanoparticles and biological macromolecules featuring broad absorbing profiles.

Direct observation of triplet energy transfer from semiconductor nanocrystals.

Triplet excitons are pervasive in both organic and inorganic semiconductors but generally remain confined to the material in which they originate. We demonstrated by transient absorption spectroscopy that cadmium selenide semiconductor nanoparticles, selectively excited by green light, engage in interfacial Dexter-like triplet-triplet energy transfer with surface-anchored polyaromatic carboxylic acid acceptors, extending the excited-state lifetime by six orders of magnitude. Net triplet energy transfer also occurs from surface acceptors to freely diffusing molecular solutes, further extending the lifetime while sensitizing singlet oxygen in an aerated solution.

Photocatalytic Applications of Colloidal Heterostructured Nanocrystals: What's Next?

Recent progress in the colloidal synthesis of inorganic nanocrystals has led to the realization of complex, multidomain nanoparticle morphologies that give rise to advanced optoelectronic properties. Such nanocomposites are particularly appealing for photocatalytic applications where tunable absorption, extensive charge separation, and large surface-to-volume ratios are important. To date, heterostructured nanocrystals featuring a metal catalyst and a semiconductor "chromophore" component have shown compelling efficiencies in photoreduction reactions, including sacrificial hydrogen production.

Mapping the exciton diffusion in semiconductor nanocrystal solids.

Colloidal nanocrystal solids represent an emerging class of functional materials that hold strong promise for device applications. The macroscopic properties of these disordered assemblies are determined by complex trajectories of exciton diffusion processes, which are still poorly understood. Owing to the lack of theoretical insight, experimental strategies for probing the exciton dynamics in quantum dot solids are in great demand.

Enhanced lifetime of excitons in nonepitaxial Au/CdS core/shell nanocrystals.

The ability of metal nanoparticles to capture light through plasmon excitations offers an opportunity for enhancing the optical absorption of plasmon-coupled semiconductor materials via energy transfer. This process, however, requires that the semiconductor component is electrically insulated to prevent a "backward" charge flow into metal and interfacial states, which causes a premature dissociation of excitons. Here we demonstrate that such an energy exchange can be achieved on the nanoscale by using nonepitaxial Au/CdS core/shell nanocomposites.