Plasmonic waveguide modes of film-coupled metallic nanocubes.

A metallic nanoparticle positioned over a metal film offers great advantages as a highly controllable system relevant for probing field-enhancement and other plasmonic effects. Because the size and shape of the gap between the nanoparticle and film can be controlled to subnanometer precision using relatively simple, bottom-up fabrication approaches, the film-coupled nanoparticle geometry has recently been applied to enhancing optical fields, accessing the quantum regime of plasmonics, and the design of surfaces with controlled reflectance. In the present work, we examine the plasmon modes associated with a silver nanocube positioned above a silver or gold film, separated by an organic, dielectric spacer layer. The film-coupled nanocube is of particular interest due to the formation of waveguide cavity-like modes between the nanocube and film. These modes impart distinctive scattering characteristics to the system that can be used in the creation of controlled reflectance surfaces and other applications. We perform both experimental spectroscopy and numerical simulations of individual nanocubes positioned over a metal film, finding excellent agreement between experiment and simulation. The waveguide mode description serves as a starting point to explain the optical properties observed.

Hot electrons do the impossible: plasmon-induced dissociation of H2 on Au.

Heterogeneous catalysis is of paramount importance in chemistry and energy applications. Catalysts that couple light energy into chemical reactions in a directed, orbital-specific manner would greatly reduce the energy input requirements of chemical transformations, revolutionizing catalysis-driven chemistry. Here we report the room temperature dissociation of H(2) on gold nanoparticles using visible light. Surface plasmons excited in the Au nanoparticle decay into hot electrons with energies between the vacuum level and the work function of the metal. In this transient state, hot electrons can transfer into a Feshbach resonance of an H(2) molecule adsorbed on the Au nanoparticle surface, triggering dissociation. We probe this process by detecting the formation of HD molecules from the dissociations of H(2) and D(2) and investigate the effect of Au nanoparticle size and wavelength of incident light on the rate of HD formation. This work opens a new pathway for controlling chemical reactions on metallic catalysts.

A plasmonic Fano switch.

Plasmonic clusters can support Fano resonances, where the line shape characteristics are controlled by cluster geometry. Here we show that clusters with a hemicircular central disk surrounded by a circular ring of closely spaced, coupled nanodisks yield Fano-like and non-Fano-like spectra for orthogonal incident polarization orientations. When this structure is incorporated into an uniquely broadband, liquid crystal device geometry, the entire Fano resonance spectrum can be switched on and off in a voltage-dependent manner. A reversible transition between the Fano-like and non-Fano-like spectra is induced by relatively low (∼6 V) applied voltages, resulting in a complete on/off switching of the transparency window.

Near-normal incidence dark-field microscopy: applications to nanoplasmonic spectroscopy.

The spectroscopic characterization of individual nanostructures is of fundamental importance to understanding a broad range of physical and chemical processes. One general and powerful technique that addresses this aim is dark-field microscopy, with which the scattered light from an individual structure can be analyzed with minimal background noise. We present the spectroscopic analysis of individual plasmonic nanostructures using dark-field illumination with incidence nearly normal to the substrate. We show that, compared to large incidence angle approaches, the near-normal incidence approach provides significantly higher signal-to-background ratios and reduced retardation field effects. To demonstrate the utility of this technique, we characterize an individual chemically synthesized gold nanoshell and a lithographically defined heptamer exhibiting a pronounced Fano-like resonance. We show that the line shape of the latter strongly depends on the incidence angle. Near-normal incidence dark-field microscopy can be used to characterize a broad range of molecules and nanostructures and can be adapted to most microscopy setups.

Plasmonic nanoclusters: near field properties of the Fano resonance interrogated with SERS.

While the far field properties of Fano resonances are well-known, clusters of plasmonic nanoparticles also possess Fano resonances with unique and spatially complex near field properties. Here we examine the near field properties of individual Fano resonant plasmonic clusters using surface-enhanced Raman scattering (SERS) both from molecules distributed randomly on the structure and from dielectric nanoparticles deposited at specific locations within the cluster. Cluster size, geometry, and interparticle spacing all modify the near field properties of the Fano resonance. For molecules, the spatially dependent SERS response obtained from near field calculations correlates well with the relative SERS intensities observed for individual clusters and for specific Stokes modes of a para-mercaptoaniline adsorbate. In all cases, the largest SERS enhancement is found when both the excitation and the Stokes shifted wavelengths overlap the Fano resonances. In contrast, for SERS from carbon nanoparticles we find that the dielectric screening introduced by the nanoparticle can drastically redistribute the field enhancement associated with the Fano resonance and lead to a significantly modified SERS response compared to what would be anticipated from the bare nanocluster.

Designing and deconstructing the Fano lineshape in plasmonic nanoclusters.

By varying the relative dimensions of the central and peripheral disks of a plasmonic nanocluster, the depth of its Fano resonance can be systematically modified; spectral windows where the scattering cross section of the nanocluster is negligible can be obtained. In contrast, electron-beam excitation of the plasmon modes at specific locations within the nanocluster yields cathodoluminescence spectra with no Fano resonance. By examining the selection rules for plasmon excitation in the context of a coupled oscillator picture, we provide an intuitive explanation of this behavior based on the plasmon modes observed for optical and electron-beam excitation in this family of nanostructures.

Orientation-preserving transfer and directional light scattering from individual light-bending nanoparticles.

A nanocup, or semishell, is an asymmetric plasmonic "Janus" nanoparticle with electric and magnetic plasmon modes; the latter scatters light in a direction controlled by nanoparticle orientation, making it the nanoscale analog of a parabolic antenna. Here we report a method for transferring nanocups from their growth substrate to oxide-terminated substrates that precisely preserves their three-dimensional orientation, enabling their use as nanophotonic components. This enables us to selectively excite and probe the electric and magnetic plasmon modes of individual nanocups, showing how the scattered light depends on the direction of incoming light and the orientation of this nanoparticle antenna.

Fano resonances in plasmonic nanoclusters: geometrical and chemical tunability.

Clusters of plasmonic nanoparticles and nanostructures support Fano resonances. Here we show that this spectral feature, produced by the interference between bright and dark modes of the nanoparticle cluster, is strongly dependent upon both geometry and local dielectric environment. This permits a highly sensitive tunability of the Fano dip in both wavelength and amplitude by varying cluster dimensions, geometry, and relative size of the individual nanocluster components. Plasmonic nanoclusters show an unprecedented sensitivity to dielectric environment with a local surface plasmon resonance figure of merit of 5.7, the highest yet reported for localized surface plasmon resonance sensing in a finite nanostructure.

Fanoshells: nanoparticles with built-in Fano resonances.

A nanoparticle consisting of a dielectric (SiO(2)) and metallic (Au) shell layer surrounding a solid Au nanoparticle core can be designed with its superradiant and subradiant plasmon modes overlapping in energy, resulting in a Fano resonance in its optical response. Synthesis of this nanoparticle around an asymmetric core yields a structure that possesses additional Fano resonances as revealed by single particle dark field microspectroscopy. A mass-and-spring coupled oscillator model provides an excellent description of the plasmon interactions and resultant optical response of this nanoparticle.

Heterodimers: plasmonic properties of mismatched nanoparticle pairs.

Heterodimers-two closely adjacent metallic nanoparticles differing in size or shape-exemplify a simple nanoscale geometry that gives rise to a remarkably rich set of properties. These include Fano resonances, avoided crossing behavior, and a surprising dependence of the scattering spectrum on the direction of excitation, known as the "optical nanodiode" effect. In a series of studies, we experimentally probe and theoretically analyze these properties in heterodimer nanostructures, where nanoparticle size and plasmon resonance frequency are varied systematically. Polarization-dependent dark-field microspectroscopy on individual heterodimer structures fabricated using a novel electromigration assembly method allows us to examine these properties in detail. These studies expand our understanding of the range of physical effects that can be observed in adjacent metallic nanoparticle pairs.

Reshaping the plasmonic properties of an individual nanoparticle.

When symmetry is broken in plasmonic nanostructures, new optical properties emerge. Here we controllably reshape an individual Au nanoshell into a reduced-symmetry nanoegg, then a semishell or nanocup by a novel electron-beam-induced ablation method, transforming its plasmonic properties. We follow the changes in the plasmonic response at the single nanostructure level throughout this reshaping process, observing the splitting of plasmon modes and the onset of electroinductive plasmons upon controlled, incremental opening of the outer metallic layer of the nanoparticle.

Substrates matter: influence of an adjacent dielectric on an individual plasmonic nanoparticle.

Studying the plasmonic properties of metallic nanoparticles at the individual nanostructure level is critical to our understanding of nanoscale metallic systems. Here we show how the presence of a nearby dielectric substrate modifies the energies of the plasmon modes of a metallic nanoparticle. The adjacent dielectric lifts the degeneracy of the dipole plasmon modes oriented parallel and perpendicular to the substrate, introducing a significant energy splitting that depends strongly on the permittivity of the substrate. This energy splitting can easily be misinterpreted as an anomalously broadened plasmon line shape for excitation of an individual nanoparticle with unpolarized light.

Tailoring plasmonic substrates for surface enhanced spectroscopies.

Our understanding of how the geometry of metallic nanostructures controls the properties of their surface plasmons, based on plasmon hybridization, is useful for developing high-performance substrates for surface enhanced spectroscopies. In this tutorial review, we outline the design of metallic nanostructures tailored specifically for providing electromagnetic enhancements for surface enhanced Raman scattering (SERS). The concepts developed for nanoshell-based substrates can be generalized to other nanoparticle geometries and scaled to other spectroscopies, such as surface enhanced infrared absorption spectroscopy (SEIRA).

Close encounters between two nanoshells.

Plasmonic nanoparticle pairs known as "dimers" embody a simple system for generating intense nanoscale fields for surface enhanced spectroscopies and for developing an understanding of coupled plasmons. Individual nanoshell dimers in directly adjacent pairs and touching geometries show dramatically different plasmonic properties. At close distances, hybridized plasmon modes appear whose energies depend extremely sensitively on the presence of a small number of molecules in the interparticle junction. When touching, a new plasmon mode arising from charge transfer oscillations emerges. The extreme modification of the overall optical response due to minute changes in very reduced volumes opens up new approaches for ultrasensitive molecular sensing and spectroscopy.

Optical properties of a nanosized hole in a thin metallic film.

Subwavelength holes are one of the most important structures in nanophotonics, providing a useful geometry for nanosensing and giving rise to extraordinary transmission when patterned in arrays. Here we theoretically and experimentally examine the optical properties of an individual nanohole in a thin metallic film. In contrast to localized plasmonic nanostructures with their own characteristic resonances, nanoholes provide a site for excitation of the underlying thin film surface plasmons. We show that both hole diameter and film thickness determine the energy of the optical resonance. A theoretical dispersion curve was obtained and verified using spectral measurements of individual nanoholes.

Nanoshells made easy: improving Au layer growth on nanoparticle surfaces.

The growth of a continuous, uniform Au layer on a dielectric nanoparticle is the critical step in the synthesis of nanoparticles such as nanoshells or nanorice, giving rise to their unique geometry-dependent plasmon resonant properties. Here, we report a novel, streamlined method for Au layer metallization on prepared nanoparticle surfaces using carbon monoxide as the reducing agent. This approach consistently yields plasmonic nanoparticles with highly regular shell layers and is immune to variations in precursor or reagent preparation. Single particle spectroscopy combined with scanning electron microscopy reveal that thinner, more uniform shell layers with correspondingly red-shifted optical resonances are achievable with this approach.