Surface-enhanced infrared absorption using individual cross antennas tailored to chemical moieties.

The development of antenna structures for surface-enhanced infrared absorption spectroscopy (SEIRA) is a topic of intense and growing interest for extending IR spectroscopy to zeptomolar quantities and ultimately to the single-molecule level. Here we show that strong infrared spectroscopic enhancements can be obtained from individual gold nanoantennas using conventional IR spectrometric sources. The antenna structure dimensions can be tuned to enhance the IR modes of specific chemical moieties. Simulations of the electric field intensity in the antenna junction region reveal a maximum SEIRA enhancement factor of more than 12,000. These findings open new opportunities for analyzing IR vibrations of exceptionally small quantities of molecules using widely accessible light sources.

Geometric Dependence of the Line Width of Localized Surface Plasmon Resonances.

For the same number of electrons and plasmon frequencies, longitudinal plasmon resonances in metallic nanorods exhibit narrower line widths than plasmon modes in spherical particles. We show that this property is a general feature of high aspect ratio nanostructures and can be explained very simply by incorporating retardation effects into a harmonic oscillator model. The origin of the effect is dynamic depolarization, which renormalizes the mass of the electrons and the oscillating electron liquid. The scattering spectrum derived from our model agrees very well with FDTD simulations. Because plasmon damping determines many important features and applications of LSPR, such as the Q factor of plasmonics devices and the magnitude of the induced field enhancements, our study will play an important role for the design of nanostructures with narrow plasmon resonances.

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.

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.

Real-space mapping of Fano interference in plasmonic metamolecules.

An unprecedented control of the spectral response of plasmonic nanoantennas has recently been achieved by designing structures that exhibit Fano resonances. This new insight is paving the way for a variety of applications, such as biochemical sensing and surface-enhanced Raman spectroscopy. Here we use scattering-type near-field optical microscopy to map the spatial field distribution of Fano modes in infrared plasmonic systems. We observe in real space the interference of narrow (dark) and broad (bright) plasmonic resonances, yielding intensity and phase toggling between different portions of the plasmonic metamolecules when either their geometric sizes or the illumination wavelength is varied.

Photodetection with active optical antennas.

Nanoantennas are key optical components for light harvesting; photodiodes convert light into a current of electrons for photodetection. We show that these two distinct, independent functions can be combined into the same structure. Photons coupled into a metallic nanoantenna excite resonant plasmons, which decay into energetic, "hot" electrons injected over a potential barrier at the nanoantenna-semiconductor interface, resulting in a photocurrent. This dual-function structure is a highly compact, wavelength-resonant, and polarization-specific light detector, with a spectral response extending to energies well below the semiconductor band edge.

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.

Experimental realization of subradiant, superradiant, and fano resonances in ring/disk plasmonic nanocavities.

Subradiant and superradiant plasmon modes in concentric ring/disk nanocavities are experimentally observed. The subradiance is obtained through an overall reduction of the total dipole moment of the hybridized mode due to antisymmetric coupling of the dipole moments of the parent plasmons. Multiple Fano resonances appear within the superradiant continuum when structural symmetry is broken via a nanometric displacement of the disk, due to coupling with higher order ring modes. Both subradiant modes and Fano resonances exhibit substantial reductions in line width compared to the parent plasmon resonances, opening up possibilities in optical and near IR sensing via plasmon line shape design.

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.

Fano resonances in individual coherent plasmonic nanocavities.

We observe the appearance of Fano resonances in the optical response of plasmonic nanocavities due to the coherent coupling between their superradiant and subradiant plasmon modes. Two reduced-symmetry nanostructures probed via confocal spectroscopy, a dolmen-style slab arrangement and a ring/disk dimer, clearly exhibit the strong polarization and geometry dependence expected for this behavior at the individual nanostructure level, confirmed by full-field electrodynamic analysis of each structure. In each case, multiple Fano resonances occur as structure size is increased.