We present an experimental and theoretical study of the fluorescence rate of a single molecule as a function of its distance to a laser-irradiated gold nanoparticle. The local field enhancement leads to an increased excitation rate whereas nonradiative energy transfer to the particle leads to a decrease of the quantum yield (quenching). Because of these competing effects, previous experiments showed either fluorescence enhancement or fluorescence quenching. By varying the distance between molecule and particle we show the first experimental measurement demonstrating the continuous transition from fluorescence enhancement to fluorescence quenching. This transition cannot be explained by treating the particle as a polarizable sphere in the dipole approximation.

We demonstrate that the fluorescence rate from a single molecule with near-unity quantum yield can be enhanced by a factor of ≈10 by use of a single laser-irradiated noble metal nanoparticle. The increased fluorescence rate is primarily the result of the local field enhancement. However, at particle-molecule distances shorter than 2 nm, nonradiative decay of the excited molecule due to energy transfer to the metal dominates over the local field enhancement giving rise to fluorescence quenching. These counteracting processes depend on the wavelength-dependent dielectric function of the particle antenna. In this study, we quantitatively compare single-molecule fluorescence enhancement near 80 nm gold and silver nanoparticles excited at a fixed wavelength of λ = 637 nm. In accordance with theory we find similar enhancements for both gold and silver nanoparticles.

This Minireview discusses novel insights into the electronic structure of carbon nanotubes obtained using single-molecule fluorescence spectroscopy. Fluorescence spectra from single nanotubes are well described by a single, Lorentzian lineshape. Nanotubes with identical structures fluoresce with different energies due to local electronic perturbations. Carbon nanotube fluorescence unexpectedly does not-show any intensity or spectral fluctuations at 300 K The lack of intensity blinking or bleaching demonstrates that carbon nanotubes have the potential to provide a stable, single-molecule infrared photon source, allowing for the exciting possibility of applications in quantum optics and biophotonics.

We report on chemically specific, subsurface imaging with high spatial resolution. Using tip-enhanced Raman spectroscopy, we probe carbon nanotubes buried beneath a host dielectric media. We demonstrate our ability to map and resolve specific vibrational modes with 30 nm spatial resolution for dielectric layers with different thicknesses.