Plasmonic tunnel junctions for single-molecule redox chemistry.

Nanoparticles attached just above a flat metallic surface can trap optical fields in the nanoscale gap. This enables local spectroscopy of a few molecules within each coupled plasmonic hotspot, with near thousand-fold enhancement of the incident fields. As a result of non-radiative relaxation pathways, the plasmons in such sub-nanometre cavities generate hot charge carriers, which can catalyse chemical reactions or induce redox processes in molecules located within the plasmonic hotspots.

Generalized circuit model for coupled plasmonic systems.

We develop an analytic circuit model for coupled plasmonic dimers separated by small gaps that provides a complete account of the optical resonance wavelength. Using a suitable equivalent circuit, it shows how partially conducting links can be treated and provides quantitative agreement with both experiment and full electromagnetic simulations. The model highlights how in the conducting regime, the kinetic inductance of the linkers set the spectral blue-shifts of the coupled plasmon.

Observing Single Molecules Complexing with Cucurbit[7]uril through Nanogap Surface-Enhanced Raman Spectroscopy.

In recent years, single-molecule sensitivity achievable by surface-enhanced Raman spectroscopy (SERS) has been widely reported. We use this to investigate supramolecular host-guest chemistry with the macrocyclic host cucurbit[7]uril, on a few-to-single-molecule level. A nanogap geometry, comprising individual gold nanoparticles on a planar gold surface spaced by a single layer of molecules, gives intense SERS signals.

Capillary-Force-Assisted Optical Tuning of Coupled Plasmons.

An ultrathin (few nanometer) polymer spacer layer is softened by local optical heating and restructured by strong capillary forces, which increase the gap between the plasmonic metal components. This results in a continuous blue-shift of the coupled plasmon from near infrared to visible with a tuning range of >150 nm that can be tightly controlled by adjusting either irradiation time or power.

Controllable Tuning Plasmonic Coupling with Nanoscale Oxidation.

The nanoparticle on mirror (NPoM) construct is ideal for the strong coupling of localized plasmons because of its simple fabrication and the nanometer-scale gaps it offers. Both of these are much harder to control in nanoparticle dimers. Even so, realizing controllable gap sizes in a NPoM remains difficult and continuous tunability is limited.

Ultrathin CdSe in Plasmonic Nanogaps for Enhanced Photocatalytic Water Splitting.

Enhanced plasmonic fields are a promising way to increase the efficiency of photocatalytic water splitting. The availability of atomically thin materials opens up completely new opportunities. We report photocatalytic water splitting on ultrathin CdSe nanoplatelets placed in plasmonic nanogaps formed by a flat gold surface and a gold nanoparticle.

Unfolding the contents of sub-nm plasmonic gaps using normalising plasmon resonance spectroscopy.

Plasmonic coupling of gold nanoparticles to a gold surface creates intense plasmonic hot spots with large electromagnetic field-enhancements within the cavity formed by the two metallic surfaces. The localised field in such structures is extremely sensitive to morphological fluctuations and subtle changes in the dielectric properties of the cavity contents. Here, we present an optical method that pins down the properties of the gap contents with high sensitivity, termed normalising plasmon resonance (NPR) spectroscopy.

Monitoring morphological changes in 2D monolayer semiconductors using atom-thick plasmonic nanocavities.

Nanometer-sized gaps between plasmonically coupled adjacent metal nanoparticles enclose extremely localized optical fields, which are strongly enhanced. This enables the dynamic investigation of nanoscopic amounts of material in the gap using optical interrogation. Here we use impinging light to directly tune the optical resonances inside the plasmonic nanocavity formed between single gold nanoparticles and a gold surface, filled with only yoctograms of semiconductor.

Nanooptics of molecular-shunted plasmonic nanojunctions.

Gold nanoparticles are separated above a planar gold film by 1.1 nm thick self-assembled molecular monolayers of different conductivities. Incremental replacement of the nonconductive molecules with a chemically equivalent conductive version differing by only one atom produces a strong 50 nm blue-shift of the coupled plasmon.

Nanoimprint lithography of Al nanovoids for deep-UV SERS.

Deep-ultraviolet surface-enhanced Raman scattering (UV-SERS) is a promising technique for bioimaging and detection because many biological molecules possess UV absorption lines leading to strongly resonant Raman scattering. Here, Al nanovoid substrates are developed by combining nanoimprint lithography of etched polymer/silica opal films with electron beam evaporation, to give a high-performance sensing platform for UV-SERS. Enhancement by more than 3 orders of magnitude in the UV-SERS performance was obtained from the DNA base adenine, matching well the UV plasmonic optical signatures and simulations, demonstrating its suitability for biodetection.

Probing confined phonon modes in individual CdSe nanoplatelets using surface-enhanced Raman scattering.

The phonon modes of individual ultrathin CdSe nanoplatelets are investigated using surface-enhanced Raman scattering in a tightly confined plasmonic geometry. The surface-enhanced Raman scattering spectra, taken on single nanoplatelets sandwiched between a gold nanoparticle and a gold surface, reveal a phonon doublet arising from oscillations perpendicular to and within the platelet plane. The out-of-plane mode cannot be observed with conventional Raman spectroscopy.

Watching individual molecules flex within lipid membranes using SERS.

Interrogating individual molecules within bio-membranes is key to deepening our understanding of biological processes essential for life. Using Raman spectroscopy to map molecular vibrations is ideal to non-destructively 'fingerprint' biomolecules for dynamic information on their molecular structure, composition and conformation. Such tag-free tracking of molecules within lipid bio-membranes can directly connect structure and function.

DNA origami based assembly of gold nanoparticle dimers for surface-enhanced Raman scattering.

Plasmonic sensors are extremely promising candidates for label-free single-molecule analysis but require exquisite control over the physical arrangement of metallic nanostructures. Here we employ self-assembly based on the DNA origami technique for accurate positioning of individual gold nanoparticles. Our innovative design leads to strong plasmonic coupling between two 40 nm gold nanoparticles reproducibly held with gaps of 3.

Controlling subnanometer gaps in plasmonic dimers using graphene.

Graphene is used as the thinnest possible spacer between gold nanoparticles and a gold substrate. This creates a robust, repeatable, and stable subnanometer gap for massive plasmonic field enhancements. White light spectroscopy of single 80 nm gold nanoparticles reveals plasmonic coupling between the particle and its image within the gold substrate.

Reproducible Deep-UV SERRS on Aluminum Nanovoids.

Surface-enhanced Raman scattering (SERS) with deep-UV excitation is of particular interest because a large variety of biomolecules such as amino acids exhibit electronic transitions in the UV spectral range and resonant excitation dramatically increases the cross section of the associated vibrational modes. Despite its potential, UV-SERS is still little-explored. We present a novel straightforward scalable route to fabricate aluminum nanovoids for reproducible SERS in the deep-UV without the need of expensive lithographic techniques.