High-Q Tamm plasmon-like resonance in spherical Bragg microcavity resonators.

This work proposes what we believe to be a novel Tamm plasmon-like resonance supporting structure consisting of an Au/SiO2 core-shell metal nanosphere structure surrounded by a TiO2/SiO2 spherical Bragg resonator (SBR). The cavity formed between the core metal particle and the SBR supports a localized mode similar to Tamm plasmons in planar dielectric multilayers. Theoretical simulations reveal a sharp absorption peak in the SBR bandgap region, associated with this mode, together with strong local field enhancement. We studied the modification of a dipolar electric emitter's radiative and non-radiative decay rates in this resonant structure, resulting in a quantum efficiency of ∼90% for a dipole at a distance of r=60n m from the Au nanosphere surface. A 30-layer metal-SBR Tamm plasmon-like resonant supporting structure results in a Q up to ∼103. The Tamm plasmon-like mode is affected by the Bragg wavelength and the number of layers of the SBR, and the thickness of the spacer cavity layer. These results will open a new avenue for generating high-Q Tamm plasmon-like modes for switches, optical logic computing devices, and nonlinear applications.

Enhancement Factors: A Central Concept during 50 Years of Surface-Enhanced Raman Spectroscopy.

In this Perspective, we provide an overview of the core concepts around surface-enhanced Raman spectroscopy (SERS) enhancement factors (EFs), including both theoretical and experimental considerations: EF definitions, the distinction between maximum and average EFs, EF distribution and hot-spot localization, EF measurement and its order of magnitude. We then highlight some of the current challenges in this field, focusing on a selection of topics that we feel are both topical and important: analyte-capture onto a SERS substrate, surface-enhanced resonant Raman scattering, orientation/tensorial effects, and nonradiative effects. We hope this Perspective can provide a platform to reflect on the past 50 years of SERS and its future.

Generalised coupled-dipole model for core-satellite nanostructures.

Plasmonic core-satellite nanostructures have recently attracted interest in photocatalytic applications. The core plasmonic nanoparticle acts like an antenna, funnelling incident light into the near-field region, where it excites the smaller satellite nanoparticles with resonantly enhanced absorption. Computer simulations of the optical absorption by such structures can prove challenging, even with state-of-the-art numerical methods, due to the large difference in size between core and satellite particles. We present a generalised coupled-dipole model that enables efficient computations of light absorption in such nanostructures, including those with many satellites. The method accurately predicts the local absorption in each satellite despite being two orders of magnitude weaker than the absorption in the core particle. We assess the range of applicability of this model by comparing the results against the superposition T-matrix method, a rigorous solution of Maxwell's equations that is much more resource-intensive and becomes impractical as the number of satellite particles increases.

Interface-Dependent Selectivity in Plasmon-Driven Chemical Reactions.

Plasmonic nanoparticles can drive chemical reactions powered by sunlight. These processes involve the excitation of surface plasmon resonances (SPR) and the subsequent charge transfer to adsorbed molecular orbitals. Nonetheless, controlling the flow of energy and charge from SPR to adsorbed molecules is still difficult to predict or tune. Here, we show the crucial role of halide ions in modifying the energy landscape of a plasmon-driven chemical reaction by carefully engineering the nanoparticle-molecule interface. By doing so, the selectivity of plasmon-driven chemical reactions can be controlled, either enhancing or inhibiting the metal-molecule charge and energy transfer or by regulating the vibrational pumping rate. These results provide an elegant method for controlling the energy flow from plasmonic nanoparticles to adsorbed molecules, in situ, and selectively targeting chemical bonds by changing the chemical nature of the metal-molecule interface.

Comparison of dynamic corrections to the quasistatic polarizability and optical properties of small spheroidal particles.

The optical properties of small spheroidal metallic nanoparticles can be simply studied within the quasistatic/electrostatic approximation, but this is limited to particles much smaller than the wavelength. A number of approaches have been proposed to extend the range of validity of this simple approximation to a range of sizes more relevant to applications in plasmonics, where resonances play a key role. The most common approach, called the modified long-wavelength approximation, is based on physical considerations of the dynamic depolarization field inside the spheroid, but alternative empirical expressions have also been proposed, presenting better accuracy. Recently, an exact Taylor expansion of the full electromagnetic solution has been derived [Majic et al., Phys. Rev. A 99, 013853 (2019)], which should arguably provide the best approximation for a given order. We here compare the merits of these approximations to predict orientation-averaged extinction/scattering/absorption spectra of metallic spheroidal nanoparticles. The Taylor expansion is shown to provide more accurate predictions over a wider range of parameters (aspect ratio and prolate/oblate shape). It also allows us to consider quadrupole and octupole resonances. This simple approximation can therefore be used for small and intermediate-size nanoparticles in situations where computing the full electromagnetic solution is not practical.

Present and Future of Surface-Enhanced Raman Scattering.

The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article.

Combined Extinction and Absorption UV-Visible Spectroscopy as a Method for Revealing Shape Imperfections of Metallic Nanoparticles.

Metallic nanoparticle solutions are routinely characterized by measuring their extinction spectrum (with UV-vis spectroscopy). Theoretical predictions such as Mie theory for spheres can then be used to infer important properties, such as particle size and concentration. Here we highlight the benefits of measuring not only the extinction (the sum of absorption and scattering) but also the absorption spectrum (which excludes scattering) for routine characterization of metallic nanoparticles. We use an integrating sphere-based method to measure the combined extinction-absorption spectra of silver nanospheres and nanocubes. Using a suite of electromagnetic modeling tools (Mie theory, T-matrix, surface integral equation methods), we show that the absorption spectrum, in contrast to extinction, is particularly sensitive to shape imperfections such as roughness, faceting, or edge rounding. We study in detail the canonical case of silver nanospheres, where small discrepancies between experimental and calculated extinction spectra are still common and often overlooked. We show that this mismatch between theory and experiment becomes much more important when considering the absorption spectrum and can no longer be dismissed as experimental imperfections. We focus in particular on the quadrupolar localized plasmon resonance of silver nanospheres, which is predicted to be very prominent in the absorption spectrum but is not observed in our experiments. We consider and discuss a number of possible explanations to account for this discrepancy, including changes in the dielectric function of Ag, size polydispersity, and shape imperfections such as elongation, faceting, and roughness. We are able to pinpoint faceting and roughness as the likely causes for the observed discrepancy. A similar analysis is carried out on silver nanocubes to demonstrate the generality of this conclusion. We conclude that the absorption spectrum is in general much more sensitive to the fine details of a nanoparticle geometry, compared to the extinction spectrum. The ratio of extinction to absorption also provides a sensitive indicator of size for many types of nanoparticles, much more reliably than any observed plasmon resonance shifts. Overall, this work demonstrates that combined absorption-extinction measurements provide a much richer characterization tool for metallic nanoparticles.

Electromagnetic interactions of dye molecules surrounding a nanosphere.

Enhanced interaction between light and molecules adsorbed on metallic nanoparticles is a cornerstone of plasmonics and surface-enhanced spectroscopies. Recent experimental access to the electronic absorption spectrum of dye molecules on silver colloids at low molecular coverage has revealed subtle changes in the spectral shape that may be attributed to a combination of factors, from a chemical modification of the molecule in contact with a metal surface to electromagnetic dye-dye and dye-metal interactions. Here we develop an original model to rigorously address the electromagnetic effects. The dye molecules are described as coupled anisotropic polarisable dipoles and their interaction with the core metal particle is described using a generalised Mie theory. The theory is readily amenable to numerical implementation and yields far-field optical cross-sections that can be compared to experimental results. We apply this model to specific adsorption geometries of practical interest to highlight the effect of molecular orientation on predicted spectral shifts and enhancement factors, as a function of surface coverage. These are compared to experimental results and reproduce the measured spectral changes as a function of concentration. These results have direct implications for the interpretation of surface selection rules and enhancement factors in surface-enhanced spectroscopies, and of orientation and coverage effects in molecular/plasmonic resonance coupling experiments.

Realistic ports in integrating spheres: reflectance, transmittance, and angular redirection.

We use Monte Carlo ray-tracing modeling to follow the stochastic trajectories of rays entering a cylindrical port from inside an integrating sphere. This allows us to study and quantify properties of realistic ports of non-negligible length, as opposed to the common thin-port assumption used in most theoretical treatments, where the port is simply considered as a hole in the spherical wall. We show that most practical ports encountered in integrating sphere applications cannot be modeled as thin ports. Indeed, a substantial proportion of rays entering the port can be reflected back into the sphere, with port reflectances as high as 80% demonstrated on realistic examples. This can have significant consequences on estimates of the sphere multiplier and therefore pathlength inside the sphere, a critical parameter in many applications. Moreover, a nonzero port reflectance is inevitably associated with reduced transmittance through the port, with implications in terms of overall throughput. We also discuss angular redistribution effects in a realistic port and the consequences in terms of detected throughput within a fixed numerical aperture. Those results highlight the importance of real port effects for any quantitative predictions of optical systems using integrating spheres. We believe that those effects can be exploited to engineer ports for specific applications and improve the overall sphere performance in terms of pathlength or throughput. This work carries important implications in our theoretical understanding of integrating spheres and on the practical design of optical systems using them.

Spheroidal harmonic expansions for the solution of Laplace's equation for a point source near a sphere.

We propose a powerful approach to solve Laplace's equation for point sources near a spherical object. The central new idea is to use prolate spheroidal solid harmonics, which are separable solutions of Laplace's equation in spheroidal coordinates, instead of the more natural spherical solid harmonics. Using electrostatics as an example, we motivate this choice and show that the resulting series expansions converge much faster. This improvement is discussed in terms of the singularity of the solution and its analytic continuation. The benefits of this approach are further illustrated for a specific example: the calculation of modified decay rates of light emitters close to nanostructures in the quasistatic approximation. We expect the general approach to be applicable with similar benefits to the solution of Laplace's equation for other geometries and to other equations of mathematical physics.

Simple accurate approximations for the optical properties of metallic nanospheres and nanoshells.

This work aims to provide simple and accurate closed-form approximations to predict the scattering and absorption spectra of metallic nanospheres and nanoshells supporting localised surface plasmon resonances. Particular attention is given to the validity and accuracy of these expressions in the range of nanoparticle sizes relevant to plasmonics, typically limited to around 100 nm in diameter. Using recent results on the rigorous radiative correction of electrostatic solutions, we propose a new set of long-wavelength polarizability approximations for both nanospheres and nanoshells. The improvement offered by these expressions is demonstrated with direct comparisons to other approximations previously obtained in the literature, and their absolute accuracy is tested against the exact Mie theory.

Tiny peaks vs mega backgrounds: a general spectroscopic method with applications in resonant Raman scattering and atmospheric absorptions.

A simple method using standard spectrometers with charge-coupled device (CCD) detectors is described to routinely measure background-corrected spectra in situations where the signal is composed of weak spectral features (such as Raman peaks or absorption lines) engulfed in a much stronger (by as much as ∼10(5)) broad background. The principle of the method is to subtract the dominant fixed-structure noise and obtain a shot-noise limited spectrum. The final noise level can therefore be reduced as desired by sufficient integration time. The method requires multiple shifts of the diffraction gratings to extract the pixel-dependent noise structure, which is then used as a flat-field correction. An original peak-retrieval procedure is proposed, demonstrating accurate determination of peak lineshapes and linewidths and robustness on practical examples where conventional methods would not be applicable. Examples are discussed to illustrate the potential of the technique to perform routine resonant Raman measurements of fluorescent dyes with high quantum yield, using conventional Raman systems. The method can equally be applied to other situations where small features are masked by a broad overwhelming background. An explicit example is given with the measurement of weak absorption lines in atmospheric gases.

Combined SPR and SERS microscopy in the Kretschmann configuration.

A novel hybrid spectroscopic technique is proposed, combining surface plasmon resonance (SPR) with surface-enhanced Raman scattering (SERS) microscopy. A standard Raman microscope is modified to accommodate the excitation of surface plasmon-polaritons (SPPs) on flat metallic surfaces in the Kretschmann configuration, while retaining the capabilities of Raman microscopy. The excitation of SPPs is performed as in standard SPR-microscopy; namely, a beam with TM-polarization traverses off-axis a high numerical aperture oil immersion objective, illuminating at an angle the metallic film from the (glass) substrate side. The same objective is used to collect the full Kretschmann cone containing the SERS emission on the substrate side. The angular dispersion of the plasmon resonance is measured in reflectivity for different coupling conditions and, simultaneously, SERS spectra are recorded from Nile Blue (NB) molecules adsorbed onto the surface. A trade-off is identified between the conditions of optimum coupling to SPPs and the spot size (which is related to the spatial resolution). This technique opens new horizons for SERS microscopy with uniform enhancement on flat surfaces.

Simplified expressions of the T-matrix integrals for electromagnetic scattering.

The extended boundary condition method, also called the null-field method, provides a semianalytic solution to the problem of electromagnetic scattering by a particle by constructing a transition matrix (T-matrix) that links the scattered field to the incident field. This approach requires the computation of specific integrals over the particle surface, which are typically evaluated numerically. We introduce here a new set of simplified expressions for these integrals in the commonly studied case of axisymmetric particles. Simplifications are obtained using the differentiation properties of the radial functions (spherical Bessel) and angular functions (associated Legendre functions) and integrations by parts. The resulting simplified expressions not only lead to faster computations, but also reduce the risks of loss of precision and provide a simpler framework for further analytical work.

Fingers Crossed: Optical Activity of a Chiral Dimer of Plasmonic Nanorods.

We investigate theoretically the optical activity of a dimer of plasmonic nanoantennas, mimicking the geometry of a molecule with two isolated chromophores, a situation commonly described as exciton coupling in organic chemistry. As the scale of the system increases and approaches the wavelength of visible light, a rich variety of effects arise that are unique to the plasmonic case. Scattering of light by the particles, negligible in very small clusters, strongly perturbs, and eventually dominates, the optical activity. Additionally, retardation effects in dimers with an interparticle separation commensurate with the wavelength of the incident light affect the electromagnetic coupling between the particles and lead to an asymmetric circular dichroism spectrum. We identify conditions for efficient interaction and predict remarkably large anisotropy factors.

Diffractive coupling in gold nanoparticle arrays and the effect of disorder.

Two-dimensional arrays of gold nanoparticles with a periodicity commensurate with the wavelength of resonant excitation of localized plasmons have been shown to exhibit a strong long-range interaction between particles. We investigate experimentally the effect of varying the degree of disorder in the geometrical arrangement from a periodic to a disordered lattice with constant occupancy. We also investigate the effect of disorder arising from variations in particle size for a regular lattice, and the effect this has on the broadening of the spectral line shape is discussed. A coupled dipole model is used to describe the observed spectral features.

Collective resonances in gold nanoparticle arrays.

We present experimental evidence of sharp spectral features in the optical response of 2D arrays of gold nanorods. A simple coupled dipole model is used to describe the main features of the observed spectral line shape. The resonance involves an interplay between the excitation of plasmons localized on the particles and diffraction resulting from the scattering by the periodic arrangement of these particles. We investigate this interplay by varying the particle size, aspect ratio, and interparticle spacing, and observe the effect on the position, width, and intensity of the sharp spectral feature.