Manipulating quantum dot fluorescence by utilizing Brownian induced near-field interactions with plasmonic nanoparticles.

摘要

Quantum dots (QDs) are semiconductor nanocrystals with size-dependent optical properties; thus making them supreme fluorophores. Plasmonic nanoparticles (PNPs), such as gold and silver nanoparticles, support localized surface plasmons on their surface. When the localized surface plasmons are excited, a highly concentrated electromagnetic field is formed near the particle. Therefore, if a QD is within the near-field of a PNP, the emission or excitation of the QD can be enhanced. However, due to Forster Resonance Energy Transfer (FRET), the QD fluorescence could instead be quenched by the proximity of PNPs. Whether enhancement or quenching occurs, is dependent upon the distance and geometry of the nanoparticles. Enhanced QD fluorescence would be helpful in biomedical sensing and imaging and solar energy conversion applications. In addition, quenched QD fluorescence caused by FRET could be applied to FRET-based sensing and imaging in medical diagnosis.;This master's thesis first theoretically models the stochastic movement of QDs and PNPs in an aqueous solution. The simulation is based upon the Direct Simulation Monte Carlo method coupled with Langevin equations. Using this simulation, we were able to predict the percentage of QDs in the near-field region of PNPs. The percentage of QDs in the near-field region of GNPs for a concentration of 1 × 1013 QDs/mL and 5 × 108 GNPs/mL, is a very small percentage of 2 × 10-5%. Yet, the concentration of QDs in the near-field region of GNPs was calculated to be 1,510,000 QDs mL-1.;In addition, this master's thesis experimentally explores the enhancement and quenching of QD emission for different concentrations and sizes of PNPs in aqueous solutions. The fluorescence spectra of two types of QD-PNP mixtures were measured. The first mixture was QDs and gold nanoparticles (GNPs) dispersed in distilled water, where the emission wavelength of the QDs matches the localized surface plasmon excitation wavelength of the GNPs. The second mixture was QDs and silver nanoparticles (SNPs) dispersed in distilled water, where localized surface plasmons affect the excitation of the QDs. For both experiments, the QD emission spectra were monitored while changing the concentration of the PNPs for a fixed concentration of QDs. At low PNP concentrations, the QD emission was enhanced by ∼ 20% for 30 nm GNPs and 80 nm SNPs; however, at high PNP concentrations, the QD emission was usually quenched. This research reveals the QD fluorescence is dependent upon the concentration and size of PNPs and concentration of QDs. Additionally, the enhancement factor was found to be dependent upon the QD concentration and independent upon temperature.