Spectral dependence of fluorescence near plasmon resonant metal nanoparticles

The optical properties of fluorophores are significantly modified when placed within the near field (0--100 nm) of plasmon resonant metal nanostructures, due to the competition between increased decay rates and "hotspots" of concentrated electric fields. The decay rates and effective electric field intensities are highly dependent on the relative position of dye and metal and the overlap between plasmon resonance and dye absorption and emission. Understanding these dependencies can greatly improve the performance of biosensing and nanophotonic devices. In this dissertation, the fluorescence intensity of organic dyes and CdSe quantum dots near single metal nanoparticles is studied as a function of the local surface plasmon resonance (LSPR) of the nanoparticle. Single metal nanoparticles have narrow, well-defined, intense local surface plasmon resonances that are tunable across the visible spectrum by changes in size and shape.;First, we show that organic dyes can be self-assembled on single silver nanoprisms into known configurations by the hybridization of thiolated DNA oligomers. We correlate the fluorescence intensity of the dyes to the LSPR of the individual nanoprism to which they are attached. For each of three different organic dyes, we observe a strong correlation between the fluorescence intensity of the dye and the degree of spectral overlap with the plasmon resonance of the nanoparticle. On average, we observe the brightest fluorescence from dyes attached to metal nanoparticles that have a LSPR scattering peak 40--120 meV higher in energy than the emission peak of the fluorophore.;Second, the plasmon-enhanced fluorescence from CdSe/CdS/CdZnS/ZnS core/shell quantum dots is studied near a variety of silver and gold nanoparticles. With single-particle scattering spectroscopy, the localized surface plasmon resonance spectra of single metal nanoparticles is correlated with the photoluminescence excitation (PLE) spectra of the nearby quantum dots. The PLE spectra closely track the scattering spectra of the metal nanoparticles. By taking advantage of the ability to excite quantum dots across a wide range of wavelengths while detecting a single emission wavelength, we measure an excitation enhancement factor for single metal nanoparticles. The data also provide a calculation of a lower-bound of experimentally attainable enhancement factors solely due to increased near-field excitation. This factor was found to range from ∼3 to 10 for Au spheres, Ag cubes and Ag nanoprisms.