Normal Incidence Excitation of Out-of-Plane Lattice Resonances in Bipartite Arrays of Metallic Nanostructures.

As a result of their coherent interaction, two-dimensional periodic arrays of metallic nanostructures support collective modes commonly known as lattice resonances. Among them, out-of-plane lattice resonances, for which the nanostructures are polarized in the direction perpendicular to the array, are particularly interesting since their unique configuration minimizes radiative losses. Consequently, these modes present extremely high quality factors and field enhancements that make them ideal for a wide range of applications. However, for the same reasons, their excitation is very challenging and has only been achieved at oblique incidence, which adds a layer of complexity to experiments and poses some limitations on their usage. Here, we present an approach to excite out-of-plane lattice resonances in bipartite arrays under normal incidence. Our method is based on exploiting the electric-magnetic coupling between the nanostructures, which has been traditionally neglected in the characterization of arrays made of metallic nanostructures. Using a rigorous coupled dipole model, we demonstrate that this coupling provides a general mechanism to excite out-of-plane lattice resonances under normal incidence conditions. We complete our study with a comprehensive analysis of a potential implementation of our results using an array of nanodisks with the inclusion of a substrate and a coating. This work provides an efficient approach for the excitation of out-of-plane lattice resonances at normal incidence, thus paving the way for the leverage of the extraordinary properties of these optical modes in a wide range of applications.

Chiral Lattice Resonances in 2.5-Dimensional Periodic Arrays with Achiral Unit Cells.

Lattice resonances are collective electromagnetic modes supported by periodic arrays of metallic nanostructures. These excitations arise from the coherent multiple scattering between the elements of the array and, thanks to their collective origin, produce very strong and spectrally narrow optical responses. In recent years, there has been significant effort dedicated to characterizing the lattice resonances supported by arrays built from complex unit cells containing multiple nanostructures. Simultaneously, periodic arrays with chiral unit cells, made of either an individual nanostructure with a chiral morphology or a group of nanostructures placed in a chiral arrangement, have been shown to exhibit lattice resonances with different responses to right- and left-handed circularly polarized light. Motivated by this, here, we investigate the lattice resonances supported by square bipartite arrays in which the relative positions of the nanostructures can vary in all three spatial dimensions, effectively functioning as 2.5-dimensional arrays. We find that these systems can support lattice resonances with almost perfect chiral responses and very large quality factors, despite the achirality of the unit cell. Furthermore, we show that the chiral response of the lattice resonances originates from the constructive and destructive interference between the electric and magnetic dipoles induced in the two nanostructures of the unit cell. Our results serve to establish a theoretical framework to describe the optical response of 2.5-dimensional arrays and provide an approach to obtain chiral lattice resonances in periodic arrays with achiral unit cells.

Control of the Radiative Heat Transfer in a Pair of Rotating Nanostructures.

The fluctuations of the electromagnetic field are at the origin of the near-field radiative heat transfer between nanostructures, as well as the Casimir forces and torques that they exert on each other. Here, working within the formalism of fluctuational electrodynamics, we investigate the simultaneous transfer of energy and angular momentum in a pair of rotating nanostructures. We demonstrate that, due to the rotation of the nanostructures, the radiative heat transfer between them can be increased, decreased, or even reversed with respect to the transfer that occurs in the absence of rotation, which is solely determined by the difference in the temperature of the nanostructures. This work unravels the unintuitive phenomena arising from the simultaneous transfer of energy and angular momentum in pairs of rotating nanostructures.

Lattice Resonances Excited by Finite-Width Light Beams.

Periodic arrays of metallic nanostructures support collective lattice resonances, which give rise to optical responses that are, at the same time, stronger and more spectrally narrow than those of the localized plasmons of the individual nanostructures. Despite the extensive research effort devoted to investigating the optical properties of lattice resonances, the majority of theoretical studies have analyzed them under plane-wave excitation conditions. Such analysis not only constitutes an approximation to realistic experimental conditions, which require the use of finite-width light beams, but also misses a rich variety of interesting behaviors. Here, we provide a comprehensive study of the response of periodic arrays of metallic nanostructures when excited by finite-width light beams under both paraxial and nonparaxial conditions. We show how as the width of the light beam increases, the response of the array becomes more collective and converges to the plane-wave limit. Furthermore, we analyze the spatial extent of the lattice resonance and identify the optimum values of the light beam width to achieve the strongest optical responses. We also investigate the impact that the combination of finite-size effects in the array and the finite width of the light beam has on the response of the system. Our results provide a solid theoretical framework to understand the excitation of lattice resonances by finite-width light beams and uncover a set of behaviors that do not take place under plane-wave excitation.

Near-Field Radiative Heat Transfer Eigenmodes.

The near-field electromagnetic interaction between nanoscale objects produces enhanced radiative heat transfer that can greatly surpass the limits established by far-field blackbody radiation. Here, we present a theoretical framework to describe the temporal dynamics of the radiative heat transfer in ensembles of nanostructures, which is based on the use of an eigenmode expansion of the equations that govern this process. Using this formalism, we identify the fundamental principles that determine the thermalization of collections of nanostructures, revealing general but often unintuitive dynamics. Our results provide an elegant and precise approach to efficiently analyze the temporal dynamics of the near-field radiative heat transfer in systems containing a large number of nanoparticles.

Tuning Electrogenerated Chemiluminescence Intensity Enhancement Using Hexagonal Lattice Arrays of Gold Nanodisks.

Electrogenerated chemiluminescence (ECL) microscopy shows promise as a technique for mapping chemical reactions on single nanoparticles. The technique's spatial resolution is limited by the quantum yield of the emission and the diffusive nature of the ECL process. To improve signal intensity, ECL dyes have been coupled with plasmonic nanoparticles, which act as nanoantennas. Here, we characterize the optical properties of hexagonal arrays of gold nanodisks and how they impact the enhancement of ECL from the coreaction of tris(2,2'-bipyridyl)dichlororuthenium(II) hexahydrate and tripropylamine. We find that varying the lattice spacing results in a 23-fold enhancement of ECL intensity because of increased dye-array near-field coupling as modeled using finite element method simulations.

Super- and Subradiant Lattice Resonances in Bipartite Nanoparticle Arrays.

Lattice resonances, the collective modes supported by periodic arrays of metallic nanoparticles, give rise to very strong and spectrally narrow optical responses. Thanks to these properties, which emerge from the coherent multiple scattering enabled by the periodic ordering of the array, lattice resonances are used in a variety of applications such as nanoscale lasing and biosensing. Here, we investigate the lattice resonances supported by bipartite nanoparticle arrays. We find that, depending on the relative position of the two particles within the unit cell, these arrays can support lattice resonances with a super- or subradiant character. While the former result in large values of reflectance with broad lineshapes due to the increased radiative losses, the latter give rise to very small linewidths and maximum absorbance, consistent with a reduction of the radiative losses. Furthermore, by analyzing the response of arrays with finite dimensions, we demonstrate that the subradiant lattice resonances of bipartite arrays require a much smaller number of elements to reach a given quality factor than the lattice resonances of arrays with single-particle unit cells. The results of this work, in addition to advancing our knowledge of the optical response of periodic arrays of nanostructures, provide an efficient approach to obtain narrow lattice resonances that are robust to fabrication imperfections.

Analysis of the Limits of the Near-Field Produced by Nanoparticle Arrays.

Periodic arrays are an exceptionally interesting arrangement for metallic nanostructures because of their ability to support collective lattice resonances. These modes, which arise from the coherent multiple scattering enabled by the lattice periodicity, give rise to very strong and spectrally narrow optical responses. Here, we investigate the enhancement of the near-field produced by the lattice resonances of arrays of metallic nanoparticles when illuminated with a plane wave. We find that, for infinite arrays, this enhancement can be made arbitrarily large by appropriately designing the geometrical characteristics of the array. On the other hand, in the case of finite arrays, the near-field enhancement is limited by the number of elements of the array that interact coherently. Furthermore, we show that, as the near-field enhancement increases, the length scale over which it extends above and below the array becomes larger and its spectral linewidth narrows. We also analyze the impact that material losses have on these behaviors. As a direct application of our results, we investigate the interaction between a nanoparticle array and a dielectric slab placed a certain distance above it and show that the extraordinary near-field enhancement produced by the lattice resonance can lead to very strong interactions, even at significantly large separations. This work provides a detailed characterization of the limits of the near-field produced by lattice resonances and, therefore, advances our knowledge of the optical response of periodic arrays of nanostructures, which can be used to design and develop applications exploiting the extraordinary properties of these systems.

Nineteenth-century nanotechnology: The plasmonic properties of daguerreotypes.

Plasmons, the collective oscillations of mobile electrons in metallic nanostructures, interact strongly with light and produce vivid colors, thus offering a new route to develop color printing technologies with improved durability and material simplicity compared with conventional pigments. Over the last decades, researchers in plasmonics have been devoted to manipulating the characteristics of metallic nanostructures to achieve unique and controlled optical effects. However, before plasmonic nanostructures became a science, they were an art. The invention of the daguerreotype was publicly announced in 1839 and is recognized as the earliest photographic technology that successfully captured an image from a camera, with resolution and clarity that remain impressive even by today's standards. Here, using a unique combination of daguerreotype artistry and expertise, experimental nanoscale surface analysis, and electromagnetic simulations, we perform a comprehensive analysis of the plasmonic properties of these early photographs, which can be recognized as an example of plasmonic color printing. Despite the large variability in size, morphology, and material composition of the nanostructures on the surface of a daguerreotype, we are able to identify and characterize the general mechanisms that give rise to the optical response of daguerreotypes. Therefore, our results provide valuable knowledge to develop preservation protocols and color printing technologies inspired by past ones.

Hybridization of Lattice Resonances.

Plasmon hybridization, the electromagnetic analog of molecular orbital theory, provides a simple and intuitive method to describe the plasmonic response of complex nanostructures from the combination of the responses of their individual constituents. Here, we follow this approach to investigate the optical properties of periodic arrays of plasmonic nanoparticles with multiparticle unit cells. These systems support strong collective lattice resonances, arising from the coherent multiple scattering enabled by the lattice periodicity. Due to the extended nature of these modes, the interaction between them is very different from that among localized surface plasmons supported by individual nanoparticles. This leads to a much richer hybridization scenario, which we exploit here to design periodic arrays with engineered properties. These include arrays with two-particle unit cells, in which the interaction between the individual lattice resonances can be canceled or maximized by controlling the relative position of the particles within the unit cell, as well as arrays whose response can be made either invariant to the polarization of the incident light or strongly dependent on it. Moreover, we explore systems with three- and four-particle unit cells and show that they can be designed to support lattice resonances with complex hybridization patterns in which different groups of particles in the unit cell can be selectively excited. The results of this work serve to advance our understanding of periodic arrays of nanostructures and provide a methodology to design periodic structures with engineered properties for applications in nanophotonics.

Flat top surface plasmon polariton beams.

Surface plasmon polaritons (SPPs) have emerged as powerful tools for guiding and manipulating light below the diffraction limit. In this context, the availability of flat top SPP beams displaying a constant transversal profile can allow for uniform excitation and coupling scenarios, thus opening the door to developing novel applications that cannot be achieved using conventional Gaussian SPP beams. Here, we present a rigorous theoretical description of flat top SPP beams propagating along flat metal-dielectric interfaces. This is accomplished through the use of Hermite-Gaussian SPP modes that constitute a complete basis set for the solutions of Maxwell's equations for a metal-dielectric interface in the paraxial approximation. We provide a comprehensive analysis of the evolution of the transversal profiles of these beams as they propagate, which is complemented with the study of the width and kurtosis parameters. Our results serve to enlarge the capabilities of surface plasmon polaritons to control and manipulate light below the diffraction limit.

Controlling the Heat Dissipation in Temperature-Matched Plasmonic Nanostructures.

Heat dissipation in a plasmonic nanostructure is generally assumed to be ruled only by its own optical response even though also the temperature should be considered for determining the actual energy-to-heat conversion. Indeed, temperature influences the optical response of the nanostructure by affecting its absorption efficiency. Here, we show both theoretically and experimentally how, by properly nanopatterning a metallic surface, it is possible to increase or decrease the light-to-heat conversion rate depending on the temperature of the system. In particular, by borrowing the concept of matching condition from the classical antenna theory, we first analytically demonstrate how the temperature sets a maximum value for the absorption efficiency and how this quantity can be tuned, thus leading to a temperature-controlled optical heat dissipation. In fact, we show how the nonlinear dependence of the absorption on the electron-phonon damping can be maximized at a specific temperature, depending on the system geometry. In this regard, experimental results supported by numerical calculations are presented, showing how geometrically different nanostructures can lead to opposite dependence of the heat dissipation on the temperature, hence suggesting the fascinating possibility of employing plasmonic nanostructures to tailor the light-to-heat conversion rate of the system.

How To Identify Plasmons from the Optical Response of Nanostructures.

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 techniques for a wide variety of physical systems, we describe how an optical resonance of a nanostructure can be classified as either plasmonic or nonplasmonic. More precisely, we define a universal metric for such classification, the generalized plasmonicity index (GPI), which can be straightforwardly implemented in any computational electronic-structure method or classical electromagnetic approach to discriminate plasmons from single-particle excitations and photonic modes. Using the GPI, we investigate the plasmonicity of optical resonances in a wide range of systems including: the emergence of plasmonic behavior in small jellium spheres as the size and the number of electrons increase; atomic-scale metallic clusters as a function of the number of atoms; and nanostructured graphene as a function of size and doping down to the molecular plasmons in polycyclic aromatic hydrocarbons. Our study provides a rigorous foundation for the further development of ultrasmall nanostructures based on molecular plasmonics.

Lateral Casimir Force on a Rotating Particle near a Planar Surface.

We study the lateral Casimir force experienced by a particle that rotates near a planar surface. The origin of this force lies in the symmetry breaking induced by the particle rotation in the vacuum and thermal fluctuations of its dipole moment, and therefore, in contrast to lateral Casimir forces previously described in the literature for corrugated surfaces, it exists despite the translational invariance of the planar surface. Working within the framework of fluctuational electrodynamics, we derive analytical expressions for the lateral force and analyze its dependence on the geometrical and material properties of the system. In particular, we show that the direction of the force can be controlled by adjusting the particle-surface distance, which may be exploited as a new mechanism to manipulate nanoscale objects.

Hot Hole Photoelectrochemistry on Au@SiO2@Au Nanoparticles.

There is currently a worldwide need to develop efficient photocatalytic materials that can reduce the high-energy cost of common industrial chemical processes. One possible solution focuses on metallic nanoparticles (NPs) that can act as efficient absorbers of light due to their surface plasmon resonance. Recent work indicates that small NPs, when photoexcited, may allow for efficient electron or hole transfer necessary for photocatalysis. Here we investigate the mechanisms behind hot hole carrier dynamics by studying the photodriven oxidation of citrate ions on Au@SiO2@Au core-shell NPs. We find that charge transfer to adsorbed molecules is most efficient at higher photon energies but still present with lower plasmon energy. On the basis of these experimental results, we develop a simple theoretical model for the probability of hot carrier-adsorbate interactions across the NP surface. These results provide a foundation for understanding charge transfer in plasmonic photocatalytic materials, which could allow for further design and optimization of photocatalytic processes.

Ultrafast radiative heat transfer.

Light absorption in conducting materials produces heating of their conduction electrons, followed by relaxation into phonons within picoseconds, and subsequent diffusion into the surrounding media over longer timescales. This conventional picture of optical heating is supplemented by radiative cooling, which typically takes place at an even lower pace, only becoming relevant for structures held in vacuum or under extreme thermal isolation. Here, we reveal an ultrafast radiative cooling regime between neighboring plasmon-supporting graphene nanostructures in which noncontact heat transfer becomes a dominant channel. We predict that more than 50% of the electronic heat energy deposited on a graphene disk can be transferred to a neighboring nanoisland within a femtosecond timescale. This phenomenon is facilitated by the combination of low electronic heat capacity and large plasmonic field concentration in doped graphene. Similar effects should occur in other van der Waals materials, thus opening an unexplored avenue toward efficient heat management.Electron relaxation, which is the dominant release channel of electronic heat in nanostructures, occurs with characteristic times of several picoseconds. Here, the authors predict that an ultrafast (femtosecond) radiative cooling regime takes place in plasmonically active neighboring graphene nanodisks prior to electron relaxation.

Molecular Plasmon-Phonon Coupling.

Charged polycyclic aromatic hydrocarbons (PAHs), ultrasmall analogs of hydrogen-terminated graphene consisting of only a few fused aromatic carbon rings, have been shown to possess molecular plasmon resonances in the visible region of the spectrum. Unlike larger nanostructures, the PAH absorption spectra reveal rich, highly structured spectral features due to the coupling of the molecular plasmons with the vibrations of the molecule. Here, we examine this molecular plasmon-phonon interaction using a quantum mechanical approach based on the Franck-Condon approximation. We show that an independent boson model can be used to describe the complex features of the PAH absorption spectra, yielding an analytical and semiquantitative description of their spectral features. This investigation provides an initial insight into the coupling of fundamental excitations-plasmons and phonons-in molecules.

Extraordinary Light-Induced Local Angular Momentum near Metallic Nanoparticles.

The intense local field induced near metallic nanostructures provides strong enhancements for surface-enhanced spectroscopies, a major focus of plasmonics research over the past decade. Here we consider that plasmonic nanoparticles can also induce remarkably large electromagnetic field gradients near their surfaces. Sizeable field gradients can excite dipole-forbidden transitions in nearby atoms or molecules and provide unique spectroscopic fingerprinting for chemical and bimolecular sensing. Specifically, we investigate how the local field gradients near metallic nanostructures depend on geometry, polarization, and wavelength. We introduce the concept of the local angular momentum (LAM) vector as a useful figure of merit for the design of nanostructures that provide large field gradients. This quantity, based on integrated fields rather than field gradients, is particularly well-suited for optimization using numerical grid-based full wave electromagnetic simulations. The LAM vector has a more compact structure than the gradient matrix and can be straightforwardly associated with the angular momentum of the electromagnetic field incident on the plasmonic structures.

Toward Surface Plasmon-Enhanced Optical Parametric Amplification (SPOPA) with Engineered Nanoparticles: A Nanoscale Tunable Infrared Source.

Active optical processes such as amplification and stimulated emission promise to play just as important a role in nanoscale optics as they have in mainstream modern optics. The ability of metallic nanostructures to enhance optical nonlinearities at the nanoscale has been shown for a number of nonlinear and active processes; however, one important process yet to be seen is optical parametric amplification. Here, we report the demonstration of surface plasmon-enhanced difference frequency generation by integration of a nonlinear optical medium, BaTiO3, in nanocrystalline form within a plasmonic nanocavity. These nanoengineered composite structures support resonances at pump, signal, and idler frequencies, providing large enhancements of the confined fields and efficient coupling of the wavelength-converted idler radiation to the far-field. This nanocomplex works as a nanoscale tunable infrared light source and paves the way for the design and fabrication of a surface plasmon-enhanced optical parametric amplifier.

Aluminum Nanocrystals as a Plasmonic Photocatalyst for Hydrogen Dissociation.

Hydrogen dissociation is a critical step in many hydrogenation reactions central to industrial chemical production and pollutant removal. This step typically utilizes the favorable band structure of precious metal catalysts like platinum and palladium to achieve high efficiency under mild conditions. Here we demonstrate that aluminum nanocrystals (Al NCs), when illuminated, can be used as a photocatalyst for hydrogen dissociation at room temperature and atmospheric pressure, despite the high activation barrier toward hydrogen adsorption and dissociation. We show that hot electron transfer from Al NCs to the antibonding orbitals of hydrogen molecules facilitates their dissociation. Hot electrons generated from surface plasmon decay and from direct photoexcitation of the interband transitions of Al both contribute to this process. Our results pave the way for the use of aluminum, an earth-abundant, nonprecious metal, for photocatalysis.