The scattering spectra of single gold nanorods with aspect ratios between 2 and 4 have been examined by dark field microscopy. The results show that the longitudinal plasmon resonance (electron oscillation along the long axis of the rod) broadens as the width of the rods decreases from 14 to 8 nm. This is attributed to electron surface scattering. Analysis of the data using gamma = gamma(bulk) + Anu(F)/L(eff), where L(eff) is the effective path length of the electrons and nu(F) is the Fermi velocity, allows us to determine a value for the surface scattering parameter of A = 0.3. Larger rods with widths of 19 and 30 nm were also examined. These samples also show spectral broadening, which is attributed to radiation damping. The relative strengths of the surface scattering and radiation damping effects are in excellent agreement with recent work on spherical gold nanoparticles by Sönnichsen et al., Phys. Rev. Lett., 2002, 88, 077402; and by Berciaud et al., Nano Lett., 2005, 5, 515.
Gold nanoparticles and nearby fluorophores interact via electromagnetic coupling upon light excitation. We determine the distance and wavelength dependence of this coupling theoretically and experimentally via steady-state and time-resolved fluorescence spectroscopy. For the first time, the fluorescence quenching of four different dye molecules, which absorb light at different wavelengths across the visible spectrum and into the near-infrared, is studied using a rigid silica shell as a spacer. A comprehensive experimental determination of the distance dependence from complete quenching to no coupling is carried out by a systematic variation of the silica shell thickness. Electrodynamic theory predicts the observed quenching quantitatively in terms of energy transfer from the molecular emitter to the gold nanoparticle. The plasmonic field enhancement in the vicinity of the 13 nm gold nanoparticles is calculated as a function of distance and excitation wavelength and is included in all calculations. Relative radiative and energy transfer rates are determined experimentally and are in good agreement with calculated rates. We demonstrate and quantify the severe effect of dye-dye interactions on the fluorescence properties of dyes attached to the surface of a silica nanoparticle in control experiments. This allows us to determine the experimental conditions, under which dye-dye interactions do not affect the experimental results.
Many potential applications of quantum dots (QDs) can only be realized once the luminescence from single nanocrystals (NCs) is understood. These applications include the development of quantum logic devices, single-photon sources, long-life LEDs, and single-molecule biolabels. At the single-nanocrystal level, random fluctuations in the QD photoluminescence occur, a phenomenon termed blinking. There are two competing models to explain this blinking: Auger recombination and surface trap induced recombination. Here we use lifetime scaling on core-shell chalcogenide NCs to demonstrate that both types of blinking occur in the same QDs. We prove that Auger-blinking can yield single-exponential on/off times in contrast to earlier work. The surface passivation strategy determines which blinking mechanism dominates. This study summarizes earlier studies on blinking mechanisms and provides some clues that stable single QDs can be engineered for optoelectronic applications.
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