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Quantum dot clusters as single-molecules: deciphering collective fluorescence and energy transfer signatures




Ryan, Duncan P., author
Gelfand, Martin P., advisor
Van Orden, Alan, advisor
Roberts, Jacob L., committee member
Prieto, Amy L., committee member

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Applications of quantum dot nanocrystals span from the individual single-molecule use to large, densely-packed bulk solids. Already, the fluorescence behavior of individual particles is complex and nuanced, particularly involving the blinking phenomenon. When particles are combined into higher-order structures where interaction may occur, a complete description becomes intractable. However, clusters---between two and ten particles---can be effective model systems to explore the local behaviors that occur in larger networks. A benefit of small clusters is the viability of using single-molecule spectroscopic techniques, which are often more informative than bulk measurements. In this work we combine fluorescence microscopy with structure-probing electron microscopy to elucidate the fluorescence dynamics clusters of semiconductor nanocrystals. The spectral characteristics of clusters are explored in the context of an energy transfer model showing low-intensity emission is blue-shifted, corresponding to the weaker emission from donor particles with a larger band gap. Because energy transfer depends intimately on the specific topographical structure of the cluster, the inter-particle spacing, and relative alignment, characterization of specific cluster behavior is better informed by correlated measurements. Next, we present the mapping results from super-resolution microscopy where the spatial distributions of fluorescence in the sub-10 nanometer realm is clearly correlated with scanning electron microscopy imaging of the same clusters. Stochastic blinking events enable such observations. The enhanced blinking associated with energy transfer has practical implications for donor and acceptor roles in clusters. Finally, the dynamic evolution of the emission dipole orientation for single nanocrystals and nanocrystal clusters is measured. The orientation signature suggests coupling strengths and constitutes a first-step towards determining corrections to Förster resonant energy transfer theory involving nanocrystals.


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