Plasmon-exciton polaritons provide exciting possibilities to control light-matter interactions at the nanoscale by enabling closer investigation of quantum optical effects and facilitating novel technologies based, for instance, on Bose-Einstein condensation and polaritonic lasing. Nevertheless, observing and visualising polaritons is challenging, and traditional optical microscopy techniques often lead to ambiguities regarding the emergence and strength of the plasmon-exciton coupling. Electron microscopy offers a more robust means to study and verify the nature of plexcitons, but is still hindered by instrument limitations and resolution. A simple theoretical description of electron beam-excited plexcitons is therefore vital to complement ongoing experimental efforts. Here we apply analytic solutions for the electron-loss and photon-emission probabilities to evaluate plasmon-exciton coupling studied either with the recently adopted technique of electron energy-loss spectroscopy, or with the so-far unexplored in this context cathodoluminescence spectroscopy. Foreseeing the necessity to account for quantum corrections in the plasmonic response, we extend these solutions within the framework of general nonlocal hydrodynamic descriptions. As a specific example we study core-shell spherical emitter-molecule hybrids, going beyond the standard local-response approximation through the hydrodynamic Drude model for screening and the generalised nonlocal optical response theory for nonlocal damping. We show that electron microscopies are extremely powerful in describing the interaction of emitters with the otherwise weakly excited by optical means higher-order plasmonic multipoles, a response that survives when quantum-informed models are considered.
Plasmonic nanopatch antennas that incorporate dielectric gaps hundreds of picometers to several nanometers thick have drawn increasing attention over the past decade because they confine electromagnetic fields to grossly sub-diffraction limited volumes. Substantial control over the optical properties of excitons and color centers confined within these plasmonic cavities has already been demonstrated with far-field optical spectroscopies, but near-field optical spectroscopies are essential to an improved understanding of the plasmon-emitter interaction at the nanoscale. Here, we characterize th…
Nonlocal effects have been shown to be responsible for a variety of non-trivial optical effects in small-size plasmonic nanoparticles, beyond classical electrodynamics. However, it is not clear whether optical mode descriptions can be applied to such extreme confinement regimes. Here, we present a powerful and intuitive quasinormal mode description of the nonlocal optical response for three-dimensional plasmonic nanoresonators. The nonlocal hydrodynamical model and a generalized nonlocal optical response model for plasmonic nanoresonators are used to construct an intuitive modal theory and to …
We present a novel wave equation for linearized plasmonic response, obtained by combining the coupled real-space differential equations for the electric field and current density. Nonlocal dynamics are fully accounted for, and the formulation is very well suited for numerical implementation, allowing us to study waveguides with subnanometer cross-sections exhibiting extreme light confinement. We show that groove and wedge waveguides have a fundamental lower limit in their mode confinement, only captured by the nonlocal theory. The limitation translates into an upper limit for the corresponding…
We develop a nonlocal-response generalization to the Green-function surface-integral method (GSIM), also known as the boundary-element method (BEM). This numerically light method can accurately describe the linear hydrodynamic nonlocal response of arbitrarily shaped plasmonic nanowires in arbitrary dielectric backgrounds. All previous general-purpose methods for nonlocal response are bulk methods. We also expand the possible geometries to which the usual local-response GSIM can be applied, by showing how to regularize singularities that occur in the surface integrals when the nanoparticles tou…
As science progresses at the nanoscopic level, it becomes more and more important to comprehend the interactions taking place at the nanoscale, where optical near-fields play a key role. Their phenomenology differs significantly from the propagative light we experience at the macroscopic level. This is particularly important in applications such as surface-enhanced spectroscopies for single-molecule detection, where often the optimization of the plasmonic structures and surfaces relies on far-field characterizations. The processes dominating in the far-field picture, though, are not the same d…
The optical response of a coupled nanowire dimer is studied using a fully quantum mechanical approach. The translational invariance of the system allows to apply the time--dependent density functional theory for the plasmonic dimer with the largest size considered so far in quantum calculations. Detailed comparisons with results from classical electromagnetic calculations based on local and non local hydrodynamic response, as well as with results of the recently developed quantum corrected model is performed. We show that electron tunneling and dynamical screening are the major nonlocal quantu…
Nonlocal and nonlinear plasmonics in atomically thin heterostructures
University of Southern Denmark（南丹麦大学）；POLIMA—Center for Polariton-driven Light–Matter Interactions, University of Southern Denmark（极化激元驱动光-物质相互作用中心，南丹麦大学）；Danish Institute for Advanced Study, University of Southern Denmark（丹麦高级研究院，南丹麦大学）
Investigating Analyte Co-Localization at Electromagnetic Gap Hot-Spots For Highly Sensitive (Bio)molecular Detection by Plasmon Enhanced Spectroscopies
A local model of the dielectric response of a metal predicts that singular surfaces, such as sharp-edged structures, have a continuous absorption spectrum and extreme concentration of energy at the singularity. Here we show that nonlocality drastically alters this picture: the spectrum is now discrete and energy concentration, though still substantial, is greatly reduced.
We study the effect of nonlocal optical response on the optical properties of metallic nanowires, by numerically implementing the hydrodynamical Drude model for arbitrary nanowire geometries. We first demonstrate the accuracy of our frequency-domain finite-element implementation by benchmarking it in a wide frequency range against analytical results for the extinction cross section of a cylindrical plasmonic nanowire. Our main results concern more complex geometries, namely cylindrical and bow-tie nanowire dimers that can strongly enhance optical fields. For both types of dimers we find that n…
Inelastic electron tunneling and surface-enhanced optical spectroscopies at the molecular scale require cryogenic local temperatures even under illumination - conditions that are challenging to achieve with plasmonically resonant metallic nanostructures. We report a detailed study of the laser heating of plasmonically active nanowires at substrate temperatures from 5 to 60 K. The increase of the local temperature of the nanowire is quantified by a bolometric approach and could be as large as 100 K for a substrate temperature of 5 K and typical values of laser intensity. We also demonstrate tha…
Classical nonlocality in conducting nanostructures has been shown to dramatically alter the linear optical response, by placing a fundamental limit on the maximum field enhancement that can be achieved. This limit directly extends to all nonlinear processes, which depend on field amplitudes. A study of third-harmonic generation in metal film-coupled nanowires reveals that for sub-nanometer vacuum gaps the nonlocality enhances the effective nonlinearity by four orders of magnitude as the field penetrates deeper inside the metal than that predicted assuming a purely local electronic response.
Contrary to classical predictions, the optical response of few-nm plasmonic particles depends on particle size due to effects such as nonlocality and electron spill-out. Ensembles of such nanoparticles (NPs) are therefore expected to exhibit a nonclassical inhomogeneous spectral broadening due to size distribution. For a normal distribution of free-electron NPs, and within the simple nonlocal Hydrodynamic Drude Model (HDM), both the nonlocal blueshift and the plasmon linewidth are shown to be considerably affected by ensemble averaging. Size-variance effects tend however to conceal nonlocality…
Localized surface plasmons (LSP) in semiconductor particles are expected to exhibit spatial nonlocal response effects as the geometry enters the nanometer scale. To investigate these nonlocal effects, we apply the hydrodynamic model to nanospheres of two different semiconductor materials: intrinsic InSb and $n$-doped GaAs. Our results show that the semiconductors indeed display nonlocal effects, and that these effects are even more pronounced than in metals. In a $150\mathrm{\,nm}$ InSb particle at $300\mathrm{\,K}$, the LSP frequency is blueshifted 35%, which is orders of magnitude larger tha…
We theoretically study hot electron generation through the emission of a dipole source coupled to a nanoresonator on a metal surface. In our hybrid approach, we solve the time-harmonic Maxwell's equations numerically and apply a quantum model to predict the efficiency of hot electron generation. Strongly confined electromagnetic fields and the strong enhancement of hot electron generation at the metal surface are predicted and are further interpreted with the theory of quasinormal modes. In the investigated nanoresonator setup, both the emitting source and the acceptor resonator are localized …
Geometrical singularities in plasmonic metasurfaces have recently been proposed for the enhancement of light-matter interactions, owing to their broadband light-harvesting properties and extreme plasmon confinement. However, the large plasmon momenta thus achieved lead to failure of local descriptions of the optical response of metals. Here we study a class of metasurfaces consisting of a periodic metal slab with a smooth modulation of its thickness. When the thinnest part shrinks, the two surfaces almost touch, forming a near-singular point. Using transformation optics, we show analytically h…
The recent generalised nonlocal optical response (GNOR) theory for plasmonics is analysed, and its main input parameter, namely the complex hydrodynamic convection-diffusion constant, is quantified in terms of enhanced Landau damping due to diffusive surface scattering of electrons at the surface of the metal. GNOR has been successful in describing plasmon damping effects, in addition to the frequency shifts originating from induced-charge screening, through a phenomenological electron diffusion term implemented into the traditional hydrodynamic Drude model of nonlocal plasmonics. Nevertheless…
Quantum effects of plasmonic phenomena have been explored through ab-initio studies, but only for exceedingly small metallic nanostructures, leaving most experimentally relevant structures too large to handle. We propose instead an effective description with the computationally appealing features of classical electrodynamics, while quantum properties are described accurately through an infinitely thin layer of dipoles oriented normally to the metal surface. The nonlocal polarizability of the dipole layer is mapped from the free-electron distribution near the metal surface as obtained with 1D q…
Nanomaterials capable of confining light are desirable for enhancing spectroscopies such as Raman scattering, infrared absorption, and nonlinear optical processes. Plasmonic superlattices have shown the ability to host collective resonances in the mid-infrared, but require stringent fabrication processes to create well-ordered structures. Here, we demonstrate how short-range-ordered Au nanoparticle multilayers on a mirror, self-assembled by a sub-nm molecular spacer, support collective plasmon-polariton resonances in the visible and infrared, continuously tunable beyond 11 $μ$m by simply varyi…
We investigate unusual surface plasmons polariton (SPP) propagation and light-matter interactions in ultrathin black phosphorus (BP) films, a 2D material that exhibits exotic electrical and physical properties due to its extremely anisotropic crystal structure. Recently, it has been speculated that the ultra-confined surface plasmons supported by BP may present various topologies of wave propagation bands, ranging from anisotropic elliptic to hyperbolic, across the mid- and near-infrared regions of the electromagnetic spectrum. By carefully analyzing the natural nonlocal anisotropic optical co…
Nonreciprocal plasmonic response of drift-biased two-dimensional metals
Istituto Italiano di Tecnologia（意大利理工大学）；University of Southern Denmark（南丹麦大学）；Danish Institute for Advanced Study, University of Southern Denmark（南丹麦大学丹麦高等研究院）
It is commonly assumed that photocurrent in two-dimensional systems with centrosymmetric lattice is generated at structural inhomogenities, such as p-n junctions. Here, we study an alternative mechanism of photocurrent generation associated with inhomogenity of the driving electromagnetic field, termed as 'plasmonic drag'. It is associated with direct momentum transfer from field to conduction electrons, and can be characterized by a non-local non-linear conductivity $σ^{(2)}({\bf q},ω)$. By constructing a classical kinetic model of non-linear conductivity with full account of non-locality, we…
Metallic nanostructures exhibit a multitude of optical resonances associated with localized surface plasmon excitations. Recent observations of plasmonic phenomena at the sub-nanometer to atomic scale have stimulated the development of various sophisticated theoretical approaches for their description. Here instead we present a comparatively simple semiclassical generalized nonlocal optical response (GNOR) theory that unifies quantum-pressure convection effects and induced-charge diffusion kinetics, with a concomitant complex-valued GNOR parameter. Our theory explains surprisingly well both th…
The nonclassical modification of plasmon-assisted fluorescence enhancement is theoretically explored by placing two-level dipole emitters at the narrow gaps encountered in canonical plasmonic architectures, namely dimers and trimers of different metallic nanoparticles. Through detailed simulations, in comparison with appropriate analytical modelling, it is shown that within classical electrodynamics, and for the reduced separations explored here, fluorescence enhancement factors of the order of $10^{5}$ can be achieved, with a divergent behaviour as the particle touching regime is approached. …
We discuss the optical response peculiarities for ultrathin plasmonic films of finite lateral size. Due to their plasma frequency spatial dispersion caused by the spatial confinement of the electron motion, the film dielectric permittivity tensor is spatially dispersive as well and so nonlocal. Such a confinement induced nonlocality can result in peculiar magneto-optical effects. For example, the frequency dependence of the magnetic permeability of the film exhibits a sharp resonance structure shifting to the red as the film aspect ratio increases. The properly tuned ultrathin plasmonic films …
We study the nonlocal response of a confined electron gas within the hydrodynamical Drude model. We address the question whether plasmonic nanostructures exhibit nonlocal resonances that have no counterpart in the local-response Drude model. Avoiding the usual quasi-static approximation, we find that such resonances do indeed occur, but only above the plasma frequency. Thus the recently found nonlocal resonances at optical frequencies for very small structures, obtained within quasi-static approximation, are unphysical. As a specific example we consider nanosized metallic cylinders, for which …
Plasmonic nanoparticles provide an ideal environment for the enhancement of fluorescent emission. On the one hand, they locally amplify the electromagnetic fields, increasing the emitter excitation rate, and on the other hand, they provide a high local density of states that accelerates spontaneous emission. However, when the emitter is placed in close proximity to a single metal nanoparticle, the number of nonradiative states increases dramatically, causing the fluorescence to quench. It has been predicted theoretically that, through a judicious placing of the emitter, fluorescence in plasmon…
Surface plasmons on metals can concentrate light into sub-nanometric volumes and on these near atomic length scales the electronic response at the metal interface is smeared out over a Thomas-Fermi screening length. This nonlocality is a barrier to a good understanding of atomic scale response to light and complicates the practical matter of computing the fields. In this letter, we present a local analogue model and show that spatial nonlocality can be represented by replacing the nonlocal metal with a composite material, comprising a thin dielectric layer on top of a local metal. This method …
The nonlocal response of plasmonic materials and nanostructures is usually described within a hydrodynamic approach which is based on the Euler-Drude equation. In this work, we reconsider this approach within linear response theory and employ Halevi's extension to this standard hydrodynamic model. After discussing the impact of this improved model, which we term the Halevi model, on the propagation of longitudinal volume modes, we accordingly extend the Mie-Ruppin theory. Specifically, we derive the dispersion relation of cylindrical surface plasmons. This reveals a nonlocal, collisional dampi…
Sub-wavelength confinement of mid-infrared light can be achieved exploiting the metal-like optical response of polar dielectric crystals in their Reststrahlen spectral region, where they support evanescent modes termed surface phonon polaritons. In the past few years the investigation of phonon polaritons localised in nanoresonators and layered heterostructures has enjoyed remarkable success, highlighting them as a promising platform for mid-infrared nanophotonic applications. Here we prove that the standard local dielectric description of phonon polaritons in nanometric objects fails due to t…
Recent results have shown unprecedented control over separation distances between two metallic elements hundreds of nanometers in size, underlying the effects of free-electron nonlocal response also at mid-infrared wavelengths. Most of metallic systems however, still suffer from some degree of inhomogeneity due to fabrication-induced surface roughness. Nanoscale roughness in such systems might hinder the understanding of the role of microscopic interactions. Here we investigate the effect of surface roughness in coaxial nanoapertures resonating at mid-infrared frequencies. We show that althoug…
The plasmon response of metallic nanostructures is anticipated to exhibit nonlocal dynamics of the electron gas when exploring the true nanoscale. We extend the local-response approximation (based on Ohm's law) to account for a general short-range nonlocal response of the homogeneous electron gas. Without specifying further details of the underlying physical mechanism we show how this leads to a Laplacian correction term in the electromagnetic wave equation. Within the hydrodynamic model we demonstrate this explicitly and we identify the characteristic nonlocal range to be vF/omega where vF is…
Giant field enhancement and field singularities are a natural consequence of the commonly employed local-response framework. We show that a more general nonlocal treatment of the plasmonic response leads to new and possibly fundamental limitations on field enhancement with important consequences for our understanding of SERS. The intrinsic length scale of the electron gas serves to smear out assumed field singularities, leaving the SERS enhancement factor finite even for geometries with infinitely sharp features. For silver nano-groove structures, mimicked by periodic arrays of half-cylinders …
Recent experiments have shown that spatial dispersion may have a conspicuous impact on the response of plasmonic structures. This suggests that in some cases the Drude model should be replaced by more advanced descriptions that take spatial dispersion into account, like the hydrodynamic model. Here we show that nonlocality in the metallic response affects surface plasmons propagating at the interface between a metal and a dielectric with high permittivity. As a direct consequence, any nanoparticle with a radius larger than 20 nm can be expected to be sensitive to spatial dispersion whatever it…
Historically, the field of plasmonics has been relying on the framework of classical electrodynamics, with the local-response approximation of material response being applied even when dealing with nanoscale metallic structures. However, when approaching the atomic-scale confinement of the electromagnetic radiation, mesoscopic effects are anticipated to become observable, e.g., those associated with the nonlocal electrodynamic surface response of the electron gas. We investigate nonlocal effects in propagating gap surface plasmon modes in ultrathin metal--dielectric--metal planar waveguides, e…
We use quantum electrodynamics and the confinement-induced nonlocal dielectric response model based on the Keldysh-Rytova electron interaction potential to study the epsilon-near-zero modes of metallic films in the transdimensional regime. New peculiar effects are revealed such as the plasmon mode degeneracy lifting and the dipole emitter coupling to the split epsilon-near-zero modes, leading to thickness-controlled spontaneous decay with up to three-orders-of-magnitude increased rates.
Plasmonics has attracted much attention not only because it has useful properties such as strong field enhancement, but also because it reveals the quantum nature of matter. To handle quantum plasmonics effects, ab initio packages or empirical Feibelman d-parameters have been used to explore the quantum correction of plasmonic resonances. However, most of these methods are formulated within the quasi-static framework. The self-consistent hydrodynamics model offers a reliable approach to study quantum plasmonics because it can incorporate the quantum effect of the electron gas into classical el…
Hybrid molecular-plasmonic nanostructures have demonstrated their potential for surface enhanced spectroscopies, sensing or quantum control at the nanoscale. In this work, we investigate the strong coupling regime and explicitly describe the hybridization between the localized plasmons of a metal nanoparticle and the excited state of a quantum emitter, offering a simple and precise understanding of the energy exchange in full analogy with cavity quantum electrodynamics treatment and dressed atom picture. Both near field emission and far field radiation are discussed, revealing the richness of …
Metal nanostructures act as powerful optical antennas[1, 2] because collective modes of the electron fluid in the metal are excited when light strikes the surface of the nanostructure. These excitations, known as plasmons, can have evanescent electromagnetic fields that are orders of magnitude larger than the incident electromagnetic field. The largest field enhancements often occur in nanogaps between plasmonically active nanostructures[3, 4], but it is extremely challenging to measure the fields in such gaps directly. These enhanced fields have applications in surface-enhanced spectroscopies…
We propose and illustrate a quantum hydrodynamic (QHD) model for the description of plasmonic oscillations in the $\rm C_{60}$ molecule. Although simpler than competing approaches such as time-dependent density functional theory (TDDFT), the model contains the key ingredients to characterize plasmonic modes, namely the Hartree, exchange and correlation potentials, as well as nonlocal, nonlinear and quantum effects to the lowest order. A variational technique is used to solve analytically the QHD model for the case of breathing (monopolar) plasmonic oscillations, revealing a bulk mode near the …
Edge states are ubiquitous for many condensed matter systems with multicomponent wave functions. For example, edge states play a crucial role in transport in zigzag graphene nanoribbons. Here, we report microscopic calculations of quantum plasmonics in doped graphene nanodisks with zigzag edges. We express the nanodisk conductivity $σ(ω)$ as a sum of the conventional bulk conductivity $σ_{\scriptscriptstyle\text{B}}(ω)$, and a novel term $σ_{\scriptscriptstyle\text{E}}(ω)$, corresponding to a coupling between the edge and bulk states. We show that the edge states give rise to a red-shift and b…
We present a proof of concept for a spectrally selective thermal mid-IR source based on nanopatterned graphene (NPG) with a typical mobility of CVD-grown graphene (up to $3000$ cm$^2$V$^{-1}$s$^{-1}$), ensuring scalability to large areas. For that, we solve the electrostatic problem of a conducting hyperboloid with an elliptical wormhole in the presence of an in-plane electric field. The localized surface plasmons (LSPs) on the NPG sheet allow for the control and tuning of the thermal emission spectrum in the wavelength regime from 3 $μ$m to 12 $μ$m. The LSPs along with an optical cavity incre…
Surface plasmons, which allow extreme confinement of light, suffer from high intrinsic electronic losses. It has been shown that stimulated emission of electrons can transfer energy to plasmons and compensate for the high intrinsic losses. To-date, these realizations have relied on introducing an external gain media coupled to the surface plasmon. Here, we propose that plasmons in two-dimensional materials with closely located electron and hole Fermi pockets can experience gain, when an electrical current bias is applied along the displaced electron-hole pockets, without the need for an extern…
As characteristic lengths in plasmonics rapidly approach the sub-nm regime, quantum-informed models that can capture those aspects of the quantum nature of the electron gas that are not accessible by the standard approximations of classical electrodynamics, or even go beyond the free-electron description, become increasingly more important. Here we propose a template for comparing and validating the predictions of such models, through the circular dichroism signal of a metallic nanoparticle helix. For illustration purposes, we compare three widely used models, each dominant at different nanopa…
We theoretically investigate the creation of a magnetic moment in gold nanoparticles by circularly polarized laser light. To this end, we describe the collective electron dynamics in gold nanoparticles using a semiclassical approach based on a quantum hydrodynamic model that incorporates the prin- cipal quantum many-body and nonlocal effects, such as the electron spill-out, the Hartree potential, and the exchange and correlation effects. We use a variational approach to investigate the breathing and the dipole dynamics induced by an external electric field. We show that gold nanoparticles can …
Crystalline metal flakes: Platforms for advanced plasmonics and hybrid 2D material architectures
Swiss Federal Institute of Technology Lausanne (EPFL)（洛桑联邦理工学院）；Universität Würzburg（维尔茨堡大学）；Leibniz Institute of Photonic Technology（莱布尼茨光子技术研究所）；University of Southern Denmark（南丹麦大学）
A promising trend in plasmonics involves shrinking the size of plasmon-supporting structures down to a few nanometers, thus enabling control over light-matter interaction at extreme-subwavelength scales. In this limit, quantum mechanical effects, such as nonlocal screening and size quantization, strongly affect the plasmonic response, rendering it substantially different from classical predictions. For very small clusters and molecules, collective plasmonic modes are hard to distinguish from other excitations such as single-electron transitions. Using rigorous quantum mechanical computational …
