ABSTRACT
Fabricating nanocavities in which optically active single quantum emitters are precisely positioned is crucial for building nanophotonic devices. Here we show that self-assembly based on robust DNA-origami constructs can precisely position single molecules laterally within sub-5 nm gaps between plasmonic substrates that support intense optical confinement. By placing single-molecules at the center of a nanocavity, we show modification of the plasmon cavity resonance before and after bleaching the chromophore and obtain enhancements of ≥4 × 103 with high quantum yield (≥50%). By varying the lateral position of the molecule in the gap, we directly map the spatial profile of the local density of optical states with a resolution of ±1.5 nm. Our approach introduces a straightforward noninvasive way to measure and quantify confined optical modes on the nanoscale.
Subject(s)
Carbocyanines/chemistry , DNA/chemistry , Fluorescent Dyes/chemistry , Gold/chemistry , Metal Nanoparticles/chemistry , Nanostructures/chemistry , Metal Nanoparticles/ultrastructure , Nanostructures/ultrastructure , Nanotechnology , Optics and Photonics , Surface Plasmon ResonanceABSTRACT
We study the optical response of individual nm-wide plasmonic nanocavities using a nanoparticle-on-mirror design utilised as an electrode in an electrochemical cell. In this geometry Au nanoparticles are separated from a bulk Au film by an ultrathin molecular spacer, giving intense and stable Raman amplification of 100 molecules. Modulation of the plasmonic spectra and the SERS response is observed with an applied voltage under a variety of electrolytes. Different scenarios are discussed to untangle the various mechanisms that can be involved in the electronic interaction between NPs and electrode surfaces.
ABSTRACT
We study in real time the optical response of individual plasmonic nanoparticles on a mirror, utilized as electrodes in an electrochemical cell when a voltage is applied. In this geometry, Au nanoparticles are separated from a bulk Au film by an ultrathin molecular spacer. The nanoscale plasmonic hotspot underneath the nanoparticles locally reveals the modified charge on the Au surface and changes in the polarizability of the molecular spacer. Dark-field and Raman spectroscopy performed on the same nanoparticle show our ability to exploit isolated plasmonic junctions to track the dynamics of nanoelectrochemistry. Enhancements in Raman emission and blue-shifts at a negative potential show the ability to shift electrons within the gap molecules.
