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.

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.

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.

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.

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.

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.

Vivid, full-color aluminum plasmonic pixels.

Aluminum is abundant, low in cost, compatible with complementary metal-oxide semiconductor manufacturing methods, and capable of supporting tunable plasmon resonance structures that span the entire visible spectrum. However, the use of Al for color displays has been limited by its intrinsically broad spectral features. Here we show that vivid, highly polarized, and broadly tunable color pixels can be produced from periodic patterns of oriented Al nanorods. Whereas the nanorod longitudinal plasmon resonance is largely responsible for pixel color, far-field diffractive coupling is used to narrow the plasmon linewidth, enabling monochromatic coloration and significantly enhancing the far-field scattering intensity of the individual nanorod elements. The bright coloration can be observed with p-polarized white light excitation, consistent with the use of this approach in display devices. The resulting color pixels are constructed with a simple design, are compatible with scalable fabrication methods, and provide contrast ratios exceeding 100:1.

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.

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.

Molecular Plasmonics.

Graphene supports surface plasmons that have been observed to be both electrically and geometrically tunable in the mid- to far-infrared spectral regions. In particular, it has been demonstrated that graphene plasmons can be tuned across a wide spectral range spanning from the mid-infrared to the terahertz. The identification of a general class of plasmonic excitations in systems containing only a few dozen atoms permits us to extend this versatility into the visible and ultraviolet. As appealing as this extension might be for active nanoscale manipulation of visible light, its realization constitutes a formidable technical challenge. We experimentally demonstrate the existence of molecular plasmon resonances in the visible for ionized polycyclic aromatic hydrocarbons (PAHs), which we reversibly switch by adding, then removing, a single electron from the molecule. The charged PAHs display intense absorption in the visible regime with electrical and geometrical tunability analogous to the plasmonic resonances of much larger nanographene systems. Finally, we also use the switchable molecular plasmon in anthracene to demonstrate a proof-of-concept low-voltage electrochromic device.

Pronounced Linewidth Narrowing of an Aluminum Nanoparticle Plasmon Resonance by Interaction with an Aluminum Metallic Film.

Aluminum nanocrystals and fabricated nanostructures are emerging as highly promising building blocks for plasmonics in the visible region of the spectrum. Even at the individual nanocrystal level, however, the localized plasmons supported by Al nanostructures possess a surprisingly broad spectral response. We have observed that when an Al nanocrystal is coupled to an underlying Al film, its dipolar plasmon resonance linewidth narrows remarkably and shows an enhanced scattering efficiency. This behavior is observable in other plasmonic metals, such as gold; however, it is far more dramatic in the aluminum nanoparticle-film system, reducing the dipolar plasmon linewidth by more than half. A substrate-mediated hybridization of the dipolar and quadrupolar plasmons of the nanoparticle reduces the radiative losses of the dipolar plasmon. While this is a general effect that applies to all metallic nanoparticle-film systems, this finding specifically provides a new mechanism for narrowing plasmon resonances in aluminum-based systems, quite possibly expanding the potential of Al-based plasmonics in real-world applications.

Aluminum nanocrystals.

We demonstrate the facile synthesis of high purity aluminum nanocrystals over a range of controlled sizes from 70 to 220 nm diameter with size control achieved through a simple modification of solvent ratios in the reaction solution. The monodisperse, icosahedral, and trigonal bipyramidal nanocrystals are air-stable for weeks, due to the formation of a 2-4 nm thick passivating oxide layer on their surfaces. We show that the nanocrystals support size-dependent ultraviolet and visible plasmon modes, providing a far more sustainable alternative to gold and silver nanoparticles currently in widespread use.

Parametric characterization of surface plasmon polaritons at a lossy interface.

Using exact solutions of Maxwell's equations, we investigate the evolution of the transversal profile of a surface plasmon polariton (SPP) packet propagating along a planar interface between a dielectric and a lossy metal. We introduce a parameter to measure the propagation length of the SPP packet and analyze its behavior with respect to the shape of the packet and the dielectric characteristics of the interface. Furthermore, we study the polarization properties of the SPP packet and define two parameters to quantify the fraction of the irradiance contained in the s- and p-polarization components of the associated field. Our results help to advance in the understanding of the SPP optics beyond the single-mode description.

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.

Interacting plasmon and phonon polaritons in aligned nano- and microwires.

The availability of macroscopic, nearly periodic structures known as eutectics opens a new path for controlling light at wavelength scales determined by the geometrical parameters of these materials and the intrinsic properties of their component phases. Here, we analyze the optical waveguiding properties of eutectic mixtures of alkali halides, formed by close-packed arrangements of aligned cylindrical inclusions. The wavelengths of phonon polaritons in these constituents are conveniently situated in the infrared and are slightly larger than the diameter and separation of the inclusions, typically consisting on single-crystal wires down to submicrometer diameter. We first discuss the gap mode and the guiding properties of metallic cylindrical waveguides in the visible and near-infrared, and in particular we investigate the transition between cylinder touching and non-touching regimes. Then, we demonstrate that these properties can be extended to the mid infrared by means of phonon polaritons. Finally, we analyze the guiding properties of an actual eutectic. For typical eutectic dimensions, we conclude that crosstalk between neighboring cylindrical wires is small, thus providing a promising platform for signal propagation and image analysis in the mid infrared.

Rotational quantum friction.

We investigate the frictional forces due to quantum fluctuations acting on a small sphere rotating near a surface. At zero temperature, we find the frictional force near a surface to be several orders of magnitude larger than that for the sphere rotating in vacuum. For metallic materials with typical conductivity, quantum friction is maximized by matching the frequency of rotation with the conductivity. Materials with poor conductivity are favored to obtain large quantum frictions. For semiconductor materials that are able to support surface plasmon polaritons, quantum friction can be further enhanced by several orders of magnitude due to the excitation of surface plasmon polaritons.

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.

Stimulated light emission and inelastic scattering by a classical linear system of rotating particles.

The rotational dynamics of particles subject to external illumination is found to produce light amplification and inelastic scattering at high rotation velocities. Light emission at frequencies shifted with respect to the incident light by twice the rotation frequency dominates over elastic scattering within a wide range of light and rotation frequencies. Remarkably, net amplification of the incident light is produced in this classical linear system via stimulated emission. Large optically induced acceleration rates are predicted in vacuum accompanied by moderate heating of the particle, thus supporting the possibility of observing these effects under extreme rotation conditions.