Mapping and Optically Writing Nanogap Inhomogeneities in 1-D Extended Plasmonic Nanowire-on-Mirror Cavities.

Tightly confined plasmons in metal nanogaps are highly sensitive to surface inhomogeneities and defects due to the nanoscale optical confinement, but tracking and monitoring their location is hard. Here, we probe a 1-D extended nanocavity using a plasmonic silver nanowire (AgNW) on mirror geometry. Morphological changes inside the nanocavity are induced locally using optical excitation and probed locally through simultaneous measurements of surface enhanced Raman scattering (SERS) and dark-field spectroscopy.

Influence of Quadrupolar Molecular Transitions within Plasmonic Cavities.

Optical nanocavities have revolutionized the manipulation of radiative properties of molecular and semiconductor emitters. Here, we investigate the amplified photoluminescence arising from exciting a dark transition of β-carotene molecules embedded within plasmonic nanocavities. Integrating a molecular monolayer into nanoparticle-on-mirror nanostructures unveils enhancements surpassing 4 orders of magnitude in the initially light-forbidden excitation.

Extensive photochemical restructuring of molecule-metal surfaces under room light.

The molecule-metal interface is of paramount importance for many devices and processes, and directly involved in photocatalysis, molecular electronics, nanophotonics, and molecular (bio-)sensing. Here the photostability of this interface is shown to be sensitive even to room light levels for specific molecules and metals. Optical spectroscopy is used to track photoinduced migration of gold atoms when functionalised with different thiolated molecules that form uniform monolayers on Au.

Multi-faceted plasmonic nanocavities.

Plasmonic nanocavities form very robust sub-nanometer gaps between nanometallic structures and confine light within deep subwavelength volumes to enable unprecedented control of light-matter interactions. However, spherical nanoparticles acquire various polyhedral shapes during their synthesis, which has a significant impact in controlling many light-matter interactions, such as photocatalytic reactions. Here, we focus on nanoparticle-on-mirror nanocavities built from three polyhedral nanoparticles (cuboctahedron, rhombicuboctahedron, decahedron) that commonly occur during the synthesis.

Boosting Optical Nanocavity Coupling by Retardation Matching to Dark Modes.

Plasmonic nanoantennas can focus light at nanometer length scales providing intense field enhancements. For the tightest optical confinements (0.5-5 nm) achieved in plasmonic gaps, the gap spacing, refractive index, and facet width play a dominant role in determining the optical properties making tuning through antenna shape challenging.

Full Control of Plasmonic Nanocavities Using Gold Decahedra-on-Mirror Constructs with Monodisperse Facets.

Bottom-up assembly of nanoparticle-on-mirror (NPoM) nanocavities enables precise inter-metal gap control down to ≈ 0.4 nm for confining light to sub-nanometer scales, thereby opening opportunities for developing innovative nanophotonic devices. However limited understanding, prediction, and optimization of light coupling and the difficulty of controlling nanoparticle facet shapes restricts the use of such building blocks.

Fingerprinting the Hidden Facets of Plasmonic Nanocavities.

The optical properties of nanogap plasmonic cavities formed by a NanoParticle-on-Mirror (NPoM, or patch antenna) are determined here, across a wide range of geometric parameters including the nanoparticle diameter, gap refractive index, gap thickness, facet size and shape. Full understanding of the confined optical modes allows these nanocavities to be utilized in a wide range of experiments across many fields. We show that the gap thickness and refractive index are spectroscopically indistinguishable, accounted for by a single gap parameter = / .

Optical suppression of energy barriers in single molecule-metal binding.

Transient bonds between molecules and metal surfaces underpin catalysis, bio/molecular sensing, molecular electronics, and electrochemistry. Techniques aiming to characterize these bonds often yield conflicting conclusions, while single-molecule probes are scarce. A promising prospect confines light inside metal nanogaps to elicit in operando vibrational signatures through surface-enhanced Raman scattering.