Universal scaling of plasmon coupling in metal nanostructures: extension from particle pairs to nanoshells

It has been recently shown that the strength of plasmon coupling between a pair of plasmonic metal nanoparticles falls as a function of the interparticle gap scaled by the particle size with a near-exponential decay trend that is universally independent of nanoparticle size, shape, metal type, or medium dielectric constant. In this letter, we extend this universal scaling behavior to the dielectric core-metal shell nanostructure. By using extended Mie theory simulations of silica core-metal nanoshells, we show that when the shift of the nanoshell plasmon resonance wavelength scaled by the solid nanosphere resonance wavelength is plotted against the shell thickness scaled by the core radius, nanoshells with different dimensions (radii) exhibit the same near-exponential decay. Thus, the nanoshell system becomes physically analogous to the particle-pair system, i.e., the nanoshell plasmon resonance results from the coupling of the inner shell surface (cavity) and the outer shell surface (sphere) plasmons over a separation distance essentially given by the metal shell thickness, which is consistent with the plasmon hybridization model of Prodan, Halas, and Nordlander. By using the universal scaling behavior in the nanoshell system, we propose a simple expression for predicting the dipolar plasmon resonance of a silica-gold nanoshell of given dimensions.     

Influence of the interaction between two Ag nanoparticles on optical properties of Ag/PGMEA nanocomposite materials

We report local electric field calculations in Ag/PGMEA nanocomposite materials using the dipole discrete approximation. We employ calculation and simulation to show that the nanoparticle radius and the interparticle distance could control and tune the surface plasmon resonances, which influence the extinction spectra and the near-field enhancement of Ag/PGMEA nanostructures. With decreasing interparticle distance, the near-field coupling between particles will induce the shift of surface plasmon resonance peak and improve the near-field intensity. With increasing radius (r), the resonance wavelength peak is red-shifted because of the interaction between two Ag nanoparticles. At 449 nm, the highest near-field enhancement factor obtained in the center of the gap was 30.5 for two interacting Ag nanoparticles of r = 11 nm with a gap of 5 nm.     

Hot‐Electron‐Assisted Femtosecond All‐Optical Modulation in Plasmonics

The optical Kerr nonlinearity of plasmonic metals provides enticing prospects for developing reconfigurable and ultracompact all‐optical modulators. In nanostructured metals, the coherent coupling of light energy to plasmon resonances creates a nonequilibrium electron distribution at an elevated electron temperature that gives rise to significant Kerr optical nonlinearities. Although enhanced nonlinear responses of metals facilitate the realization of efficient modulation devices, the intrinsically slow relaxation dynamics of the photoexcited carriers, primarily governed by electron–phonon interactions, impedes ultrafast all‐optical modulation. Here, femtosecond (≈190 fs) all‐optical modulation in plasmonic systems via the activation of relaxation pathways for hot electrons at the interface of metals and electron acceptor materials, following an on‐resonance excitation of subradiant lattice plasmon modes, is demonstrated. Both the relaxation kinetics and the optical nonlinearity can be actively tuned by leveraging the spectral response of the plasmonic design in the linear regime. The findings offer an opportunity to exploit hot‐electron‐induced nonlinearities for design of self‐contained, ultrafast, and low‐power all‐optical modulators based on plasmonic platforms.     

DNA‐Directed Gold Nanodimers with Tunable Sizes and Interparticle Distances and Their Surface Plasmonic Properties

A quantitative understanding of the localized surface plasmon resonances (LSPRs) of metallic nanostructures has received tremendous interest. However, most of the current studies are concentrated on theoretical calculation due to the difficulty in experimentally obtaining monodisperse discrete metallic nanostructures with high purity. In this work, endeavors to assemble symmetric and asymmetric gold nanoparticle (AuNP) dimer structures with exceptional purity are reported using a DNA self‐assembly strategy through a one‐step gel electrophoresis, which greatly facilitates the preparation process and improves the final purity. In the obtained Au nanodimers, the sizes of AuNPs (13, 20, and 40 nm) and the interparticle distances (5, 10, and 15 nm) are tunable. The size‐ and distance‐dependent plasmon coupling of ensembles of single, isolated dimers in solution are subsequently investigated. The experimental measurements are correlated with the modeled plasmon optical properties of Au nanodimers, showing an expected resonance shift with changing particle sizes and interparticle distances. This new strategy of constructing monodisperse metallic nanodimers will be helpful for building more complicated nanostructures, and our theoretical and experimental understanding of the intrinsic dependence of plasmon property of metallic nanodimer on the sizes and interparticle distances will benefit the future investigation and exploitation of near‐field plasmonic properties.     

Optothermal escape of plasmonically coupled silver nanoparticles from a three-dimensional optical trap

We demonstrate that optical trapping of multiple silver nanoparticles is strongly influenced by plasmonic coupling of the nanoparticles. Employing dark-field Rayleigh scattering imaging and spectroscopy on multiple silver nanoparticles optically trapped in three dimensions, we experimentally investigate the time-evolution of the coupled plasmon resonance and its influence on the trapping stability. With time the coupling strengthens, which is observed as a gradual red shift of the coupled plasmon scattering. When the coupled plasmon becomes resonant with the trapping laser wavelength, the trap is destabilized and nanoparticles are released from the trap. Modeling of the trapping potential and its comparison to the plasmonic heating efficiency at various nanoparticle separation distances suggests a thermal mechanism of the trap destabilization. Our findings provide insight into the specificity of three-dimensional optical manipulation of plasmonic nanostructures suitable for field enhancement, for example for surface-enhanced Raman scattering.     

Surface plasmon near-field resonance characteristics of silver shell nanocylinders arranged in triangular geometry

The optical near-field surface plasmon effects of a triangular system of silver nanoshell cylinders are numerically studied using the two-dimensional finite difference time domain method. The dependence of interparticle distance, shell thickness of the cylinder, dielectric constant of shell core as well as embedding medium, and orientation of the optical source plane on the plasmonic resonances of the nanocylinder shells is studied. The plasmonic resonances are found to have strong dependence on the interparticle distance. As the size of the particle is increased, the field intensity peak shows a redshift. The resonance condition varies with the dielectric constant of the environment as well as the core. In addition, the orientation of the incident source plane has a significant role in the near-field intensity distribution. Since the near-field intensity has the same trend as that of the scattering cross section, the results can be used in the design of various applications like sensing, antennas, and waveguides.     

Plasmon-induced long-lived hot electrons in degenerately doped molybdenum oxides for visible-light-driven photochemical reactions

Plasmon-induced hot electrons offer unique advantages in solar-light-driven chemical reactions. Noble metal nanostructures have been the most studied plasmonic materials, but the hot electron lifetime is extremely short. Here, we have discovered extraordinarily long-lived hot electrons in degenerately doped molybdenum oxides with surface plasmon resonance in the visible and near-infrared region. Their lifetime is nanosecond-scale, which is enhanced by 4 orders of magnitude compared to their noble metal counterparts. Such a property is ascribed to the quasi-metallic feature of molybdenum oxides driven by hydrogen dopant-induced bandgap trap states, in which the electron–phonon scattering is dominant over the ultrafast electron–electron scattering in the decay dynamics of hot electrons. The plasmonic dye oxidation and hydrogen evolution are explored without the coupling of semiconductors, providing a viable way towards expanding the candidates for direct plasmonic photocatalysis.     

Chiral Surface Lattice Resonances

Collective excitation of periodic arrays of metallic nanoparticles by coupling localized surface plasmon resonances to grazing diffraction orders leads to surface lattice resonances with narrow line width. These resonances may find numerous applications in optical sensing and information processing. Here, a new degree of freedom of surface lattice resonances is experimentally investigated by demonstrating handedness-dependent excitation of surface lattice resonances in arrays of chiral plasmonic crescents. The self-assembly of particles used as mask and modified colloidal lithography is applied to produce arrays of planar and 3D gold crescents over large areas. The excitation of surface lattice resonances as a function of the interparticle distance and the degree of order within the arrays is investigated. The chirality of the individual 3D crescents leads to the formation of chiral lattice modes, that is, surface lattice resonances that exhibit optical activity.     

Substrate Phonon‐Mediated Plasmon Hybridization in Coplanar Graphene Nanostructures for Broadband Plasmonic Circuits

The mode hybridization between adjacent graphene nanoribbons determines the integration density of graphene‐based plasmonic devices. Here, plasmon hybridization in graphene nanostructures is demonstrated through the characterization of the coupling strength of plasmons in graphene nanoribbons as a function of charge density and inter‐ribbon spacing using Fourier transform infrared microscopy. In combination with numerical simulations, it is shown that the plasmon coupling is strongly mediated by the substrate phonons. For polar substrates, the plasmon coupling strength is limited by the plasmon–phonon interactions. In contrast, a nonpolar substrate affects neither the energy distribution of the original plasmon modes in graphene nanostructures nor their plasmon interactions, which increases exponentially as the inter‐ribbon spacing decreases. To further explore the potential of graphene broadband plasmonics on nonpolar substrates, a scheme is proposed that uses a metal–dielectric heterostructure to prevent the overlap of plasmons between neighboring graphene nanoribbons. The device structures retain the plasmon resonance frequency of the graphene ribbons and maximally isolate the plasmonic components from the surrounding electromagnetic environment, allowing modular design in integrated plasmonic circuits.     

Reconfigurable core-satellite nanoassemblies as molecularly-driven plasmonic switches

Molecular control of plasmon coupling is investigated in sub-100 nm assemblies composed of 13 nm gold "satellite" particles tethered by reconfigurable DNA nanostructures to a 50 nm gold "core" particle. Reconfiguration of the DNA nanostructures from a compact to an extended state results in blue shifting of the assembly plasmon resonance, indicating reduced interparticle coupling and lengthening of the core-satellite tether. Scattering spectra of the core-satellite assemblies before and after reconfiguration are compared with spectra calculated using a structural model that incorporates the core/satellite ratio determined by TEM imaging and estimates of tether length based upon prior measurements of interparticle separation in DNA linked nanoparticle networks. A strong correspondence between measured and simulated difference spectra validates the structural models that link the observed plasmon modulation with DNA nanostructure reconfiguration.     

Gold Nanorods: From Synthesis and Properties to Biological and Biomedical Applications

Noble metal nanoparticles are capable of confining resonant photons in such a manner as to induce coherent surface plasmon oscillation of their conduction band electrons, a phenomenon leading to two important properties. Firstly, the confinement of the photon to the nanoparticle's dimensions leads to a large increase in its electromagnetic field and consequently great enhancement of all the nanoparticle's radiative properties, such as absorption and scattering. Moreover, by confining the photon's wavelength to the nanoparticle's small dimensions, there exists enhanced imaging resolving powers, which extend well below the diffraction limit, a property of considerable importance in potential device applications. Secondly, the strongly absorbed light by the nanoparticles is followed by a rapid dephasing of the coherent electron motion in tandem with an equally rapid energy transfer to the lattice, a process integral to the technologically relevant photothermal properties of plasmonic nanoparticles. Of all the possible nanoparticle shapes, gold nanorods are especially intriguing as they offer strong plasmonic fields while exhibiting excellent tunability and biocompatibility. We begin this review of gold nanorods by summarizing their radiative and nonradiative properties. Their various synthetic methods are then outlined with an emphasis on the seed‐mediated chemical growth. In particular, we describe nanorod spontaneous self‐assembly, chemically driven assembly, and polymer‐based alignment. The final section details current studies aimed at applications in the biological and biomedical fields.     

Correct Spectral Conversion between Surface‐Enhanced Raman and Plasmon Resonance Scattering from Nanoparticle Dimers for Single‐Molecule Detection

Simultaneous measurement of surface‐enhanced Raman scattering (SERS) and localized surface plasmon resonance (LSPR) in nanoparticle dimers presents outstanding opportunities in molecular identification and in the elucidation of physical properties, such as the size, distance, and deformation of target species. SERS–LSPR instrumentation exists and has been used under limited conditions, but the extraction of SERS and LSPR readouts from a single measurement is still a challenge. Herein, the extraction of LSPR spectra from SERS signals is reported and a tool for measuring the interparticle distance from Raman enhancement data by the standardization of the SERS signal is proposed. The SERS nanoruler mechanism incorporates two important aspects (the LSPR scattering peak shift and the Raman shift for measuring interparticle distance), and signifies their exact one‐to‐one correspondence after spectral correction. The developed methodology is applied to calculate the interparticle distance between nanoparticle dimers from SERS signals, to detect and quantify DNA at the single‐molecule level in a base‐pair‐specific manner. It is also shown that the SERS nanoruler concept can be used in structural analysis for the specific detection of the interaction of immunoglobulin G (IgG) with its target from bianalyte Raman signals with identical shaping at single‐molecule resolution. The SERS profile shaping approach not only offers a new detection mechanism for single molecules, but also has excellent potential for studying protein interactions and the intracellular detection of mRNA.     

Plasmon transmutation: inducing new modes in nanoclusters by adding dielectric nanoparticles

Planar clusters of coupled plasmonic nanoparticles support nanoscale electromagnetic "hot spots" and coherent effects, such as Fano resonances, with unique near and far field signatures, currently of prime interest for sensing applications. Here we show that plasmonic cluster properties can be substantially modified by the addition of individual, discrete dielectric nanoparticles at specific locations on the cluster, introducing new plasmon modes, or transmuting existing plasmon modes to new ones, in the resulting metallodielectric nanocomplex. Depositing a single carbon nanoparticle in the junction between a pair of adjacent nanodisks induces a metal-dielectric-metal quadrupolar plasmon mode. In a ten-membered cluster, placement of several carbon nanoparticles in junctions between multiple adjacent nanoparticles introduces a collective magnetic plasmon mode into the Fano dip, giving rise to an additional subradiant mode in the metallodielectric nanocluster response. These examples illustrate that adding dielectric nanoparticles to metallic nanoclusters expands the number and types of plasmon modes supported by these new mixed-media nanoscale assemblies.     

Resolving sub-diffraction limit encounters in nanoparticle tracking using live cell plasmon coupling microscopy

We use plasmon coupling between individual gold nanoparticle labels to monitor subdiffraction limit distances in live cell nanoparticle tracking experiments. While the resolving power of our optical microscope is limited to approximately 500 nm, we improve this by more than an order of magnitude by detecting plasmon coupling between individual gold nanoparticle labels using a ratiometric detection scheme. We apply this plasmon coupling microscopy to resolve the interparticle separations during individual encounters of gold nanoparticle labeled fibronectin-integrin complexes in living HeLa cells.     

Classical analog of electromagnetically induced absorption in plasmonics

The ability to manipulate the phase shift between two resonantly coupled plasmonic oscillators in a controlled fashion has been unavailable up to now. Here we present a strategy to overcome this limitation by employing the benefits of near-field coupling on the one hand and retardation effects due to far-field coupling on the other hand. We theoretically and experimentally demonstrate that in the intermediate regime the coupling of a broad dipolar to a narrow dark quadrupolar plasmon resonance is possible while simultaneously allowing for a retardation-induced phase shift. This leads to constructive interference and enhanced absorption. The observed phenomenon can thus be termed a classical analog of electromagnetically induced absorption.     

Thin wire shortening of plasmonic nanoparticle dimers: the reason for red shifts

We studied experimentally and theoretically resonance characteristics of plasmonic nanoparticle dimers connected by a narrow metal wire. The "conductive" coupling between the particles results in complete redistribution of the surface charge yielding abrupt red shift of the plasmon resonance: detuning >900 nm and order of magnitude improvement in intensity enhancement. The resonance in the conductive coupling regime is determined completely by the characteristics of the unified particle and significantly different from that of capacitive coupling.     

Coherent molecular resonances in quantum dot-metallic nanoparticle systems: coherent self-renormalization and structural effects

It is known that surface-plasmon resonances of metallic nanoparticles can significantly enhance the field experienced by semiconductor quantum dots. In this paper we show that, when quantum dots are in the vicinity of metallic nanoparticles and interact with coherent light sources (laser fields), coherent exciton-plasmon coupling (quantum coherence effects) can increase the amount of the plasmonic field enhancement significantly. We also study how the coherent molecular resonances generated by such a coupling process are influenced by the self-renormalization of the plasmonic fields and the structural parameters of the systems, particularly the size and shape of the metallic nanoparticle. The renormalization process happens via mutual impacts of the radiative decay rate of excitons and the coherent exciton-plasmon coupling on each other. Our results highlight the conditions where the molecular resonances become very sharp, offering optical switching processes with high extinction ratio and wide ranging device applications.     

Near-Field Photothermal Heating with a Plasmonic Nanofocusing Probe

Noble metal nanostructures support plasmon resonances—collective oscillation of charge carriers at optical frequencies—and serve as effective tools to create bright light sources at the nanoscale. These sources are useful in broad application areas including, super-resolution imaging and spectroscopy, nanolithography, and near-field optomechanical transducers. The feasibility of these applications relies on efficient conversion of free-space propagating light to plasmons. Recently, we demonstrated a hybrid nanofocusing scheme for efficient coupling of light to plasmons at the apex of a scanning probe. In the approach, free-space light is coupled to propagating surface plasmon polaritons (SPPs) on the tapered shaft of the scanning probe. The SPPs propagate adiabatically towards the probe tip where they are coupled to localized plasmons (LSPs). The nanofocusing scheme was explored in a near-field scanning optical microscope for super-resolution imaging, near-field transduction of nanomechanical vibrations, and local detection of ultrasound. Owing to the strong concentration of light at the probe, significant heating of the tip and a sample positioned in the optical near-field is expected. This paper investigates the local heating produced by the plasmonic nanofocusing probe under steady-state conditions using the tip-enhanced Raman scattering approach. In addition, a finite element model is explored to study the coupling of free propagating light to LSPs, and to estimate the temperature rise expected in a halfspace heated by absorption of the LSPs. This study has implications for exploring the plasmonic nanofocusing probe in heat-assisted nanofabrication and fundamental studies of nanoscale heat transport in materials.     

Exciton-plasmon interactions in quantum dot-gold nanoparticle structures

We present a self-assembly method to construct CdSe/ZnS quantum dot-gold nanoparticle complexes. This method allows us to form complexes with relatively good control of the composition and structure that can be used for detailed study of the exciton-plasmon interactions. We determine the contribution of the polarization-dependent near-field enhancement, which may enhance the absorption by nearly two orders of magnitude and that of the exciton coupling to plasmon modes, which modifies the exciton decay rate.     

Distance-dependent plasmon resonant coupling between a gold nanoparticle and gold film

We present an experimental analysis of the plasmonic scattering properties of gold nanoparticles controllably placed nanometers away from a gold metal film. We show that the spectral response of this system results from the interplay between the localized plasmon resonance of the nanoparticle and the surface plasmon polaritons of the gold film, as previously predicted by theoretical studies. In addition, we report that the metal film induces a polarization to the single nanoparticle light scattering, resulting in a doughnut-shaped point spread function when imaged in the far-field. Both the spectral response and the polarization effects are highly sensitive to the nanoparticle-film separation distance. Such a system shows promise in potential biometrology and diagnostic devices.