Multipolar Plasmon Modes Research Articles

Routing the Exciton Emissions of WS2 Monolayer with the High-Order Plasmon Modes of Ag Nanorods.

Locally routing the exciton emissions in two-dimensional (2D) transition-metal dichalcogenides along different directions at the nanophotonic interface is of great interest in exploiting the promising 2D excitonic systems for functional nano-optical components. However, such control has remained elusive. Herein we report on a facile plasmonic approach for electrically controlled spatial modulation of the exciton emissions in a WS2 monolayer. The emission routing is enabled by the resonance coupling between the WS2 excitons and the multipole plasmon modes in individual silver nanorods placed on a WS2 monolayer. Different from prior demonstrations, the routing effect can be modulated by the doping level of the WS2 monolayer, enabling electrical control. Our work takes advantage of the high-quality plasmon modes supported by simple rod-shaped metal nanocrystals for the angularly resolved manipulation of 2D exciton emissions. Active control is achieved, which offers great opportunities for the development of nanoscale light sources and nanophotonic devices.

Magnetic Circular Dichroism Responses with High Sensitivity and Enhanced Spectral Resolution in Multipolar Plasmonic Modes of Silver Nanoparticles with Dimensions between 90 and 200 nm.

Characteristic features of magnetoplasmonic responses in higher-order multipolar (quadrupolar and octupolar) modes of Ag nanoparticles (from 90 to 200 nm in diameter) are demonstrated for the first time using magnetic circular dichroism (MCD) spectroscopy. In optical extinction spectra, with an increase in the size of the nanoparticles, the red shift of dipolar plasmon peaks and the appearance of higher-order multipolar resonances can reasonably be observed. Aside from the dipolar and quadrupolar modes, the octupolar plasmonic extinction is very weak and almost unresolved. In contrast, strikingly, MCD shows a very sharp and intense peak (or valley) for the octupolar resonance, meaning its unique properties with high sensitivity and enhanced spectral resolution. MCD responses assignable to the quadrupolar mode have a distinct derivative-like shape, which is different from those observed for Ag nanocubes and nanodecahedra in our previous studies. We then discuss this behavior from the viewpoint of size and/or polyhedral shape inhomogeneity.

A rational design of multimodal asymmetric nanoshells as efficient tunable absorbers within the biological optical window

In this work, the optical properties of asymmetric nanoshells with different geometries are comprehensively investigated in the quasi-static regime by applying the dipolar model and effective medium theory. The plasmonic behaviors of these nanostructures are explained by the plasmon hybridization model. Asymmetric hybrid nanoshells, composed of off-center core or nanorod core surrounded by a spherical metallic shell layer possess highly geometrically tunable optical resonances in the near-infrared regime. The plasmon modes of this nanostructures arise from the hybridization of the cavity and solid plasmon modes at the inner and outer surfaces of the shell. The results reveal that the symmetry breaking drastically affects the strength of hybridization between plasmon modes, which ultimately affects the absorption spectrum by altering the number of resonance modes, their wavelengths and absorption efficiencies. Therefore, offsetting the spherical core as well as changing the internal geometry of the nanoparticle to nanorod not only shift the resonance frequencies but can also strongly modify the relative magnitudes of the absorption efficiencies. Furthermore, higher order multipolar plasmon modes can appear in the spectrum of asymmetric nanoshell, especially in nanoegg configuration. The results also indicate that the strength of hybridization strongly depends on the metal of shell, material of core and the filling factor. Using Au-Ag alloy as a material of the shell can provide red-shifted narrow resonance peak in the near-infrared regime by combining the specific features of gold and silver. Moreover, inserting a high permittivity core in a nanoshell corresponds to a red-shift, while a core with small dielectric constant results in a blue-shift of spectrum. We envision that this research offers a novel perspective and provides a practical guideline in the fabrication of efficient tunable absorbers in the nanoscale regime.

Ultrasensitive nanoplasmonic biosensor based on interferometric excitation of multipolar plasmonic modes.

We propose a nanoplasmonic interferometric biosensor, which exploits the selective excitation of multipolar plasmonic modes in a nanoslit to provide a novel scheme for highly-sensitive biosensing. In this design, two counter-propagating surface plasmon polaritons interfere at the location of the nanoslit, selectively exciting the dipolar and quadrupolar modes of the structure depending on the phase relationship induced by the analyte. The contrasting radiation patterns produced by these modes result in large changes in the angular distribution of the transmitted light that depends on the analyte concentration. The resultant far-field is numerically modeled and the sensing performance of the structure is assessed, resulting in maximum bulk and surface sensitivities of SB = 1.12 × 105 deg/RIU and SS = 302 deg/RIU, respectively, and a bulk-sensing resolution of the order of 10-8 RIU. The design allows ample control over the trade-off between operating range and resolution through the slit's width, making this platform suitable for a broad range of sensing requirements.

Multipolar Plasmonic Resonances of Aluminum Nanoantenna Tuned by Graphene.

We numerically investigate the multipolar plasmonic resonances of Aluminum nanoantenna tuned by a monolayer graphene from ultraviolet (UV) to visible regime. It is shown that the absorbance of the plasmonic odd modes (l = 1 and l = 3) of graphene–Al nanoribbon structure is enhanced while the absorption at the plasmonic even modes (l = 2) is suppressed, compared to the pure Al nanoribbon structure. With the presence of the monolayer graphene, a change in the resonance strength of the multipolar plasmonic modes results from the near field interactions of the monolayer graphene with the electric fields of the multipolar plasmonic resonances of the Al resonator. In particular, a clear absorption peak with a high quality (Q)-factor of 27 of the plasmonic third-order mode (l = 3) is realized in the graphene–Al nanoribbon structure. The sensitivity and figure of merit of the plasmonic third-order mode of the proposed Graphene–Al nanoribbon structure can reach 25 nm/RIU and 3, respectively, providing potential applications in optical refractive-index sensing.

Spatio-Spectral Characterization of Multipolar Plasmonic Modes of Au Nanorods via Tip-Enhanced Raman Scattering.

Tip-enhanced Raman (TER) spectral images of 4-thiobenzonitrile-coated Au nanorods map the spatial profiles and trace the resonances of dipolar and multipolar plasmonic modes that are characteristic of the imaged particles. For any particular rod, we observe sequential transitions between high-order modes at low frequency shifts and lower-order modes at higher frequencies. We also notice that higher-order modes (up to m = 4) are generally observed for long rods as compared to their shorter analogues, where longitudinal dipolar resonances (m = 1) are observable. In effect, this work adds a new dimension to local optical field mapping via TERS, which we have previously explored. Not only can the magnitudes, vector components, local/nonlocal characters of local optical fields be imaged through molecular TERS, but spatially varying local optical resonances are also direct observables.

Interaction between spoof localized surface plasmon and terahertz vortex beam

We theoretically and experimentally investigate a method of exciting multipole plasmons, including terahertz dark spoof localized surface plasmon (Spoof-LSP) modes, by using normally incident terahertz vortex beam. The vortex beam with angular intensity profile and phase singularities, has well-defined angular momentum which can be decomposed into the polarization-state-related spin angular momentum (SAM) for characterizing the spin feature of photon, and the helical-wavefront-related orbital angular momentum (OAM) that is characterized by an integer <inline-formula><tex-math id="Z-20200915102424-1">\begin{document}$ (l) $\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="18-20200695_Z-20200915102424-1.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="18-20200695_Z-20200915102424-1.png"/></alternatives></inline-formula>, called the topological charge. By illuminating terahertz vortex beam on the metallic disk with periodic subwavelength grooves normally, we find that the terahertz dark multipole plasmons can be excited by the terahertz vortex beam carrying different OAM and SAM. We analyze the correspondence between the spin and orbital angular momentum of vortex beam and the excited dark multipolar plasmon modes. In the experiment, a terahertz stepped spiral phase plate (SPP) with high transmission and low dispersion based on the Tsurupica olefin polymer is developed and the stepped SPP can generate a terahertz vortex beam having a topological charge of 1. Then, we further study the excitation of dark multipolar Spoof-LSPs by utilizing the stepped SPP in combination with the near-field scanning terahertz microscopy. The collimated terahertz wave, which is radiated from a 100 fs (<i>λ</i> = 780 nm) laser pulse pumped photoconductive antenna emitter, is converted into terahertz circular polarized light (CPL) which can carry SAM by the combination of the quarter wave plate and the polarizer, and then terahertz CPL impinges on the stepped SPP, producing the terahertz vortex beam which can carry OAM. The spatial two-dimensional electric field distribution is collected in steps of 0.02 mm along the <i>x</i>-direction and <i>y</i>-direction by a commercial terahertz near-field probe which is located close (≈ 10 μm) to the one side of polyimide film by three-dimensional electric translation stage and a microscope (FORTUNE TECHPLOGY FT-FH1080). The experimental results are in good agreement with simulations. We believe that our method will open the way for detailed research on the terahertz physics, plasma and imaging fields.

Aluminum Metasurface with Hybrid Multipolar Plasmons for 1000-Fold Broadband Visible Fluorescence Enhancement and Multiplexed Biosensing.

Aluminum (Al)-based nanoantennae traditionally suffer from weak plasmonic performance in the visible range, necessitating the application of more expensive noble metal substrates for rapidly expanding biosensing opportunities. We introduce a metasurface comprising Al nanoantennae of nanodisks-in-cavities that generate hybrid multipolar lossless plasmonic modes to strongly enhance local electromagnetic fields and increase the coupled emitter's local density of states throughout the visible regime. This results in highly efficient electromagnetic field confinement in visible wavelengths by these nanoantennae, favoring real-world plasmonic applications of Al over other noble metals. Additionally, we demonstrate spontaneous localization and concentration of target molecules at metasurface hotspots, leading to further improved on-chip detection sensitivity and a broadband fluorescence-enhancement factor above 1000 for visible wavelengths with respect to glass chips commonly used in bioassays. Using the metasurface and a multiplexing technique involving three visible wavelengths, we successfully detected three biomarkers, insulin, vascular endothelial growth factor, and thrombin relevant to diabetes, ocular and cardiovascular diseases, respectively, in a single 10 μL droplet containing only 1 fmol of each biomarker.

Tip-Enhanced Raman Excitation Spectroscopy (TERES): Direct Spectral Characterization of the Gap-Mode Plasmon.

The plasmonic properties of tip-substrate composite systems are of vital importance to near-field optical spectroscopy, in particular tip-enhanced Raman spectroscopy (TERS), which enables operando studies of nanoscale chemistry at a single molecule level. The nanocavities formed in the tip-substrate junction also offer a highly tunable platform for studying field-matter interactions at the nanoscale. While the coupled nanoparticle dimer model offers a correct qualitative description of gap-mode plasmon effects, it ignores the full spectrum of multipolar tip plasmon modes and their interaction with surface plasmon polariton (SPP) excitation in the substrate. Herein, we perform the first tip-enhanced Raman excitation spectroscopy (TERES) experiment and use the results, both in ambient and aqueous media, in combination with electrodynamics simulations, to explore the plasmonic response of a Au tip-Au substrate composite system. The gap-mode plasmon features a wide spectral window corresponding to a host of tip plasmon modes interacting with the plasmonic substrate. Simulations of the electric field confinement demonstrate that optimal spatial resolution is achieved when a hybrid plasmon mode that combines a multipolar tip plasmon and a substrate SPP is excited. Nevertheless, a wide spectral window over 1000 nm is available for exciting the tip plasmon with high spatial resolution, which enables the simultaneous resonant detection of different molecular species. This window is robust as a function of tip-substrate distance and tip radius of curvature, indicating that many choices of tips will work, but it is restricted to wavelengths longer than ∼600 nm for the Au tip-Au substrate combination. Other combinations, such as Ag tip-Ag substrate, can access wavelengths as low as 350 nm.

Colour routing with single silver nanorods

Elongated plasmonic nanoparticles have been extensively explored over the past two decades. However, in comparison with the dipolar plasmon mode that has attracted the most interest, much less attention has been paid to multipolar plasmon modes because they are usually thought to be “dark modes”, which are unable to interact with far-field light efficiently. Herein, we report on an intriguing far-field scattering phenomenon, colour routing, based on longitudinal multipolar plasmon modes supported by high-aspect-ratio single Ag nanorods. Taking advantage of the distinct far-field behaviours of the odd and even multipolar plasmon modes, we demonstrate two types of colour routing, where the incident white light can be scattered into several beams with different colours as well as different propagation directions. Because of the narrow linewidths of the longitudinal multipolar plasmon modes, there is little spectral overlap between the adjacent peaks, giving rise to outstanding colour selectivity. Our experimental results and theoretical model provide a simple yet effective picture for understanding the far-field behaviour of the longitudinal multipolar plasmon modes and the resultant colour routing phenomenon. Moreover, the outstanding colour routing capability of the high-aspect-ratio Ag nanorods enables nanoscale optical components with simple geometries for controlling the propagation of light below the diffraction limit of light.

Coupling of Surface Plasmon Modes and Refractive Index Sensitivity of Hollow Silver Nanoprism

Localized surface plasmon (LSP) modes depend strongly on the morphology of nanoparticle and the surrounding dielectric medium. The hollow nanostructure provides a new way to modulate the surface plasmon modes due to the additional cavity surface. In this work, we study systematically the multipolar surface plasmon modes of hollow silver nanoprism (HSN) by simulation of electron energy loss spectroscopy (EELS) spectra based on the boundary element method (BEM). Herein the effects of the cavity size and position are taken into account. The LSP modes of HSNs are compared with those of perfect silver nanoprism (SN). The red-shift behaviors of multipolar modes can be found as increasing the cavity size. Modes A and C have similar red-shift tendency and obey the plasmon ruler equation, which can be explained by dipole-dipole coupling mode. Meanwhile, the degenerate modes will be split by changing the cavity position, and opposite shift tendencies of split degenerate states are observed. These are caused by different coupling nature of degenerate modes. Moreover, high refractive index sensitivity (RIS) can be obtained for HSN by changing the cavity size and position.

Unveiling and Imaging Degenerate States in Plasmonic Nanoparticles with Nanometer Resolution.

Metal nanoparticles host localized plasmon excitations that allow the manipulation of optical fields at the nanoscale. Despite the availability of several techniques for imaging plasmons, direct access into the symmetries of these excitations remains elusive, thus hindering progress in the development of applications. Here, we present a combination of angle-, polarization-, and space-resolved cathodoluminescence spectroscopy methods to selectively access the symmetry and degeneracy of plasmonic states in lithographically fabricated gold nanoprisms. We experimentally reveal and spatially map degenerate states of multipole plasmon modes with nanometer spatial resolution and further provide recipes for resolving optically dark and out-of-plane modes. Full-wave simulations in conjunction with a simple tight-binding model explain the complex plasmon structure in these particles and reveal intriguing mode-symmetry phenomena. Our approach introduces systematics for a comprehensive symmetry characterization of plasmonic states in high-symmetry nanostructures.

Dynamics of the Optically Directed Assembly and Disassembly of Gold Nanoplatelet Arrays.

The tremendous progress in nanoscience now allows the creation of static nanostructured materials for a broad range of applications. A further goal is to achieve dynamic and reconfigurable nanostructures. One approach involves nanoparticle-based optical matter, but so far, studies have only considered spherical constituents. A nontrivial issue is that nanoparticles with other shapes are expected to have different local electromagnetic field distributions and interactions with neighbors in optical-matter arrays. Therefore, one would expect their dynamics to be different as well. This paper reports the directed assembly of ordered arrays of gold nanoplatelets in optical line traps, demonstrating the reconfigurability of the array by altering the phase gradient via holographic-beam shaping. The weaker gradient forces and resultant slower motion of the nanoplatelets, as compared with plasmonic (Ag and Au) nanospheres, allow the precise study of their assembly and disassembly dynamics. Both temporal and spatial correlations are detected between particles separated by distances of hundreds of nanometers to several microns. Electrodynamics simulations reveal the presence of multipolar plasmon modes that induce short-range (near-field) and longer-range electrodynamic (e.g., optical binding) interactions. These interactions and the interferences between mutipolar plamon modes cause both the strong correlations and the nonuniform dynamics observed. Our study demonstrates new opportunities for the generation of complex addressable optical matter and the creation of novel active optical technology.

Tunability of Multipolar Plasmon Resonances and Fano Resonances in Bimetallic Nanoshells

We study the multipolar surface plasmon modes and its link to Fano resonances in bimetallic nanoparticles. General expressions for the multipolar surface plasmon frequencies and damping rates are analytically derived by long-wave approximation. The results are in agreement with that from plasmon hybridization model for nanoshell system. Numerical results show that the surface plasmon resonances and damping rates for Au/Ag and Ag/Au nanoshells exhibit quite different behavior with the increase of shell thickness. In addition, both the near-field diagram and the far-field quantity are theoretically investigated. Fano resonances of scattering efficiency by Ag/Au core-shell nanoparticles occur due to the dipole-dipole coupling. The asymmetry of Fano profiles can be tuned by adjusting the size ratio of the core and the shell. Our results may found some potential applications in optical devices and biomedicine.

Collective modes in multipolar plasmonic lattices: control of interparticle-gap upward/downward energy streams

We numerically study the collective resonances and field profiles of two-dimensional arrays of large metallic nanodisks supporting multipolar plasmonic modes in nearly homogeneous environments. We show that, depending on the wavelength, these arrays can support two distinct collective modes with orthogonal field intensity distributions. In one of these modes (scattering mode), the optical scattering between the nanodisks forms a sharp optical feature with significant sensitivity to the refractive index of the environment. In the second mode (optical-band mode), the nanodisks are mainly coupled via an optical band with a field intensity profile perpendicular to the incident light polarization. This mode is associated with a subtle optical peak with much less sensitivity to the environment. We demonstrate that around this peak, the nanodisks support a unique asymmetrical field dispersion and energy flow paths. For a given wavelength range, the plasmon fields in this mode deeply penetrate into the substrate while energy moves up from the substrate between the gaps of the nanodisks, forming energy whirlpools in the superstrate. With a slight wavelength change, these fields switch to the superstrate, and the direction of the gap energy path is inverted. We investigate how such features can be tuned by adding a thin layer of silicon between the substrate and superstrate and discuss the applicability of the scattering mode for sensitive sensors.

Understanding the shape effect on the plasmonic response of small ligand coated nanoparticles

The plasmonic properties of metallic nanoparticles typically depend strongly on their shapes and local environment. However, not much is known about the shape effects on the plasmonic response in small metallic nanoparticles when quantum size effects become important. In this work, we use atomistic electrodynamics models incorporated with quantum size effects to study the optical properties of both bare and ligand coated Ag nanoparticles in different shapes. Using classical electrodynamics, we find that the plasmonic response of bare metallic nanoparticles depends strongly on the morphology of the nanoparticles due to the presence of higher-order plasmon modes. By including quantum size effects in the simulations, we find a significant blue-shift of the dipole plasmon as well as the smearing-out of the multipole plasmon modes, and both lead to a weak shape dependence. The ligand effects on the nanoparticles cause a significant red-shift of the plasmon resonance arising from the reduction of the conductivity of the Ag atoms where the ligands bind. In contrast to the bare nanoparticles, we find several higher-order plasmon modes in the ligand coated nanoparticles, that are likely caused by the weak electron spill-out effect and the symmetry breaking at the surface in the presence of the ligands. Furthermore, we show that the ligand layer strongly modify the near-field distribution due to the screening of the ligands. This work highlights the importance of quantum size and ligand effects on the optical properties of small metallic nanoparticles.

Tunable Lattice Coupling of Multipole Plasmon Modes and Near-Field Enhancement in Closely Spaced Gold Nanorod Arrays.

Considering the nanogap and lattice effects, there is an attractive structure in plasmonics: closely spaced metallic nanoarrays. In this work, we demonstrate experimentally and theoretically the lattice coupling of multipole plasmon modes for closely spaced gold nanorod arrays, offering a new insight into the higher order cavity modes coupled with each other in the lattice. The resonances can be greatly tuned by changes in inter-rod gaps and nanorod heights while the influence of the nanorod diameter is relatively insignificant. Experimentally, pronounced suppressions of the reflectance are observed. Meanwhile, the near-field enhancement can be further enhanced, as demonstrated through surface enhanced Raman scattering (SERS). We then confirm the correlation between the near-field and far-field plasmonic responses, which is significantly important for maximizing the near-field enhancement at a specific excitation wavelength. This lattice coupling of multipole plasmon modes is of broad interest not only for SERS but also for other plasmonic applications, such as subwavelength imaging or metamaterials.

Localized plasmons on a metal surface

This paper considers collective oscillations of electron density localized near a metal surface. Its description involves the wave equation of plasma oscillations. Assuming the axial symmetry of the problem, separation of variables in the equation is carried out and a set of analytical functions providing the variety of solutions is obtained. The solutions provide natural multipole quantization of surface plasmon states. Expressions are obtained for local potential fields formed by multipole plasmon modes at the interface. Their role in physical implementation of mechanisms of localization of excess electrons on the metal surface is discussed.

Nanoscale Color Sorting of Surface Plasmons in a Double-Nanogap Structure with Multipolar Plasmon Excitation.

We demonstrated a new plasmonic nanodevice that spatially sorts photons according to their colors on the nanoscale while maintaining their nanoconcentration. The properties of this nanoscale color sorting based on constructive and destructive interferences between different multipolar plasmon modes are controlled by tuning the incidence angle of the incoming photons. The added ability of color sorting and its manipulation could significantly influence the development of possible photonic applications, including nanoscale spectroscopy and sensing.

Probing Plasmonic Gap Resonances between Gold Nanorods and a Metallic Surface

The plasmonic resonances in individual gold nanorods nanoscopically coupled to a gold film with different gap spacing have been experimentally and theoretically investigated. The spectral widths, wavelengths, and optical polarizabilities of the maxima in measured single-nanoparticle scattering spectra are significantly modified as the gap distance changes in the sub-20 nm domain. Comparing the experimental data with numerical simulations reveals that these modifications arise from the complex hybridization of several dipolar and multipolar plasmon modes that are strongly localized at the gap. These plasmon gap modes have distinct resonant and spatial characteristics as a result of near-field interaction between the elongated nanorods and the gold film. Additionally, the excitation of these gap modes is highly dependent on the gap spacing. Finally, we also discuss influences of these plasmonic modes on absorption properties of the system and propose a potential application of the studied structures in facilitating photothermal conversion.