Search

Strain relaxation mechanisms during epitaxial growth of core-shell nanostructures play a key role in determining their morphologies, crystal structure and properties. To unveil those mechanisms, we perform atomic-scale aberration-corrected scanning transmission electron microscopy studies on planar core-shell ZnSe@ZnTe nanowires on α-Al 2 O 3 substrates. The core morphology affects the shell structure involving plane bending and the formation of low-angle polar boundaries. The origin of this phenomenon and its consequences on the electronic band structure are discussed. We further use monochromated valence electron energy-loss spectroscopy to obtain spatially resolved band-gap maps of the heterostructure with sub-nanometer spatial resolution. A decrease in band-gap energy at highly strained core-shell interfacial regions is found, along with a switch from direct to indirect band-gap. These findings represent an advance in the sub-nanometer-scale understanding of the interplay between structure and electronic properties associated with highly mismatched semiconductor heterostructures, especially with those related to the planar growth of heterostructured nanowire networks., (© 2022. The Author(s).)

Manipulation of the propagation and energy-transport characteristics of subwavelength infrared (IR) light fields is critical for the application of nanophotonic devices in photocatalysis, biosensing, and thermal management. In this context, metamaterials are useful composite materials, although traditional metal-based structures are constrained by their weak mid-IR response, while their associated capabilities for optical propagation and focusing are limited by the size of attainable artificial optical structures and the poor performance of the available active means of control. Herein, a tunable planar focusing device operating in the mid-IR region is reported by exploiting highly oriented in-plane hyperbolic phonon polaritons in α-MoO 3 . Specifically, an unprecedented change of effective focal length of polariton waves from 0.7 to 7.4 μm is demonstrated by the following three different means of control: the dimension of the device, the employed light frequency, and engineering of phonon-plasmon hybridization. The high confinement characteristics of phonon polaritons in α-MoO 3 permit the focal length and focal spot size to be reduced to 1/15 and 1/33 of the incident wavelength, respectively. In particular, the anisotropic phonon polaritons supported in α-MoO 3 are combined with tunable surface-plasmon polaritons in graphene to realize in situ and dynamical control of the focusing performance, thus paving the way for phonon-polariton-based planar nanophotonic applications., (© 2022 Wiley-VCH GmbH.)

We use a novel scanning electron Mach-Zehnder interferometer constructed in a conventional transmission electron microscope to perform inelastic interferometric imaging with free electrons. An electron wave function is prepared in two paths that pass on opposite sides of a gold nanoparticle, where plasmons are excited before the paths are recombined to produce electron interference. We show that the measured spectra are consistent with theoretical predictions, specifically that the interference signal formed by inelastically scattered electrons is π out of phase with respect to that formed by elastically scattered electrons. This technique is sensitive to the phase of localized optical modes, because the interference signal amounts to a substantial fraction of the transmitted electrons. Thus, we argue that inelastic interferometric imaging with our scanning electron Mach-Zehnder interferometer provides a new platform for controlling the transverse momentum of free electrons and studying coherent electron-matter interactions at the nanoscale.

BaSnO 3 exhibits the highest carrier mobility among perovskite oxides, making it ideal for oxide electronics. Collective charge carrier oscillations known as plasmons are expected to arise in this material, thus providing a tool to control the nanoscale optical field for optoelectronics applications. Here, the existence of relatively long-lived plasmons supported by high-mobility charge carriers in La-doped BaSnO 3 (BLSO) is demonstrated. By exploiting the high spatial and energy resolution of electron energy-loss spectroscopy with a focused beam in a scanning transmission electron microscope, the dispersion, confinement ratio, and damping of infrared localized surface plasmons (LSPs) in BLSO nanoparticles are systematically investigated. It is found that LSPs in BLSO exhibit a high degree of spatial confinement compared to those sustained by noble metals and have relatively low losses and high quality factors with respect to other doped oxides. Further analysis clarifies the relation between plasmon damping and carrier mobility in BLSO. The results support the use of nanostructured degenerate semiconductors for plasmonic applications in the infrared region and establish a solid alternative to more traditional plasmonic materials., (© 2022 The Authors. Small published by Wiley-VCH GmbH.)

Due to the two-dimensional character of graphene, the plasmons sustained by this material have been invariably studied in supported samples so far. The substrate provides stability for graphene but often causes undesired interactions (such as dielectric losses, phonon hybridization, and impurity scattering) that compromise the quality and limit the intrinsic flexibility of graphene plasmons. Here, we demonstrate the visualization of plasmons in suspended graphene at room temperature, exhibiting high-quality factor Q~33 and long propagation length > 3 μm. We introduce the graphene suspension height as an effective plasmonic tuning knob that enables in situ change of the dielectric environment and substantially modulates the plasmon wavelength, propagation length, and group velocity. Such active control of micrometer plasmon propagation facilitates near-unity-order modulation of nanoscale energy flow that serves as a plasmonic switch with an on-off ratio above 14. The suspended graphene plasmons possess long propagation length, high tunability, and controllable energy transmission simultaneously, opening up broad horizons for application in nano-photonic devices., (© 2022. The Author(s).)

Entangled photons are pivotal elements in emerging quantum information technologies. While several schemes are available for the production of entangled photons, they typically require the assistance of cumbersome optical elements to couple them to other components involved in logic operations. Here, we introduce a scheme by which entangled photon pairs are directly generated as guided mode states in optical waveguides. The scheme relies on the intrinsic nonlinearity of the waveguide material, circumventing the use of bulky optical components and their associated phase-matching constraints. Specifically, we consider an optical waveguide under normal illumination, so that photon down-conversion can take place to excite waveguide states with opposite momentum in a spectral region populated by only two accessible modes. By additionally configuring the external illumination to interfere different incident directions, we can produce maximally entangled photon-pair states, directly generated as waveguide modes with conversion efficiencies that are competitive with respect to existing macroscopic schemes. These results should find application in the design of more efficient and compact quantum optics devices., (© 2022 Álvaro Rodríguez Echarri et al., published by De Gruyter, Berlin/Boston.)

Electronic states and their dynamics are of critical importance for electronic and optoelectronic applications. Here, various relevant electronic states in monolayer MoS 2 , such as multiple excitonic Rydberg states and free-particle energy bands are probed with a high relative contrast of up to ≥200 via broadband (from ≈1.79 to 3.10 eV) static third-harmonic spectroscopy (THS), which is further supported by theoretical calculations. Moreover, transient THS is introduced to demonstrate that third-harmonic generation can be all-optically modulated with a modulation depth exceeding ≈94% at ≈2.18 eV, providing direct evidence of dominant carrier relaxation processes associated with carrier-exciton and carrier-phonon interactions. The results indicate that static and transient THS are not only promising techniques for the characterization of monolayer semiconductors and their heterostructures, but also a potential platform for disruptive photonic and optoelectronic applications, including all-optical modulation and imaging., (© 2021 Wiley-VCH GmbH.)

Nanoscale nonlinear optics is limited by the inherently weak nonlinear response of conventional materials and the small light-matter interaction volumes available in nanostructures. Plasmonic excitations can alleviate these limitations through subwavelength light focusing, boosting optical near fields that drive the nonlinear response, but also suffering from large inelastic losses that are further aggravated by fabrication imperfections. Here, we theoretically explore the enhanced nonlinear response arising from extremely confined plasmon polaritons in few-atom-thick crystalline noble metal films. Our results are based on quantum-mechanical simulations of the nonlinear optical response in atomically thin metal films that incorporate crucial electronic band structure features associated with vertical quantum confinement, electron spill-out, and surface states. We predict an overall enhancement in plasmon-mediated nonlinear optical phenomena with decreasing film thickness, underscoring the importance of surface and electronic structure in the response of ultrathin metal films., (© 2021 Álvaro Rodríguez Echarri et al., published by De Gruyter, Berlin/Boston.)

Nonlinear light-matter interactions in structured materials are the source of exciting properties and enable vanguard applications in photonics. However, the magnitude of nonlinear effects is generally small, thus requiring high optical intensities for their manifestation at the nanoscale. Here, we reveal a large nonlinear response of monolayer hexagonal boron nitride (hBN) in the mid-infrared phonon-polariton region, triggered by the strongly anharmonic potential associated with atomic vibrations in this material. We present robust first-principles theory predicting a threshold light field ∼24 MV/m to produce order-unity effects in Kerr nonlinearities and harmonic generation, which are made possible by a combination of the long lifetimes exhibited by optical phonons and the strongly asymmetric landscape of the configuration energy in hBN. We further foresee polariton blockade at the few-quanta level in nanometer-sized structures. In addition, by mixing static and optical fields, the strong nonlinear response of monolayer hBN gives rise to substantial frequency shifts of optical phonon modes, exceeding their spectral width for in-plane DC fields that are attainable using lateral gating technology. We therefore predict a practical scheme for electrical tunability of the vibrational modes with potential interest in mid-infrared optoelectronics. The strong nonlinear response, low damping, and robustness of hBN polaritons set the stage for the development of applications in light modulation, sensing, and metrology, while triggering the search for an intense vibrational nonlinear response in other ionic materials.

All-optical control of nonlinear photonic processes in nanomaterials is of significant interest from a fundamental viewpoint and with regard to applications ranging from ultrafast data processing to spectroscopy and quantum technology. However, these applications rely on a high degree of control over the nonlinear response, which still remains elusive. Here, we demonstrate giant and broadband all-optical ultrafast modulation of second-harmonic generation (SHG) in monolayer transition-metal dichalcogenides mediated by the modified excitonic oscillation strength produced upon optical pumping. We reveal a dominant role of dark excitons to enhance SHG by up to a factor of ∼386 at room temperature, 2 orders of magnitude larger than the current state-of-the-art all-optical modulation results. The amplitude and sign of the observed SHG modulation can be adjusted over a broad spectral range spanning a few electronvolts with ultrafast response down to the sub-picosecond scale via different carrier dynamics. Our results not only introduce an efficient method to study intriguing exciton dynamics, but also reveal a new mechanism involving dark excitons to regulate all-optical nonlinear photonics., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Nonlinear nanophotonics leverages engineered nanostructures to funnel light into small volumes and intensify nonlinear optical processes with spectral and spatial control. Owing to its intrinsically large and electrically tunable nonlinear optical response, graphene is an especially promising nanomaterial for nonlinear optoelectronic applications. Here we report on exceptionally strong optical nonlinearities in graphene-insulator-metal heterostructures, which demonstrate an enhancement by three orders of magnitude in the third-harmonic signal compared with that of bare graphene. Furthermore, by increasing the graphene Fermi energy through an external gate voltage, we find that graphene plasmons mediate the optical nonlinearity and modify the third-harmonic signal. Our findings show that graphene-insulator-metal is a promising heterostructure for optically controlled and electrically tunable nano-optoelectronic components.

Phonon polaritons enable light confinement at deep subwavelength scales, with potential technological applications, such as subdiffraction imaging, sensing and engineering of spontaneous emission. However, the trade-off between the degree of confinement and the excitation efficiency of phonon polaritons prevents direct observation of these modes in monolayer hexagonal boron nitride (h-BN), where they are expected to reach ultrahigh confinement. Here, we use monochromatic electron energy-loss spectroscopy (about 7.5 meV energy resolution) in a scanning transmission electron microscope to measure phonon polaritons in monolayer h-BN, directly demonstrating the existence of these modes as the phonon Reststrahlen band (RS) disappears. We find phonon polaritons in monolayer h-BN to exhibit high confinement (>487 times smaller wavelength than that of light in free space) and ultraslow group velocity down to about 10 -5 c. The large momentum compensation provided by electron beams additionally allows us to excite phonon polaritons over nearly the entire RS band of multilayer h-BN. These results open up a broad range of opportunities for the engineering of metasurfaces and strongly enhanced light-matter interactions.

Semimetals are being explored for their unique advantages in low-energy high-speed photodetection, although they suffer from serious drawbacks such as an intrinsically high dark current. In this Perspective, we envision the exploitation of topological effects in the photoresponse of these materials as a promising route to circumvent these problems. We overview recent studies on photodetection based on graphene and other semimetals, and further discuss the opportunities created by topological effects, along with the additional challenges that they impose on photodetector designs.

Nanoscale photothermal effects enable important applications in cancer therapy, imaging and catalysis. These effects also induce substantial changes in the optical response experienced by the probing light, thus suggesting their application in all-optical modulation. Here, we demonstrate the ability of graphene, thin metal films, and graphene/metal hybrid systems to undergo photothermal optical modulation with depths as large as >70% over a wide spectral range extending from the visible to the terahertz frequency domains. We envision the use of ultrafast pump laser pulses to raise the electron temperature of graphene during a picosecond timescale in which its mid-infrared plasmon resonances undergo dramatic shifts and broadenings, while visible and near-infrared plasmons in the neighboring metal films are severely attenuated by the presence of hot graphene electrons. Our study opens a promising avenue toward the active photothermal manipulation of the optical response in atomically thin materials with potential applications in ultrafast light modulation., Competing Interests: Conflict of interestThe authors declare that they have no conflict of interest., (© The Author(s) 2020.)

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.

Topological optical states exhibit unique immunity to defects, rendering them ideal for photonic applications. A powerful class of such states is based on time-reversal symmetry breaking of the optical response. However, existing proposals either involve sophisticated and bulky structural designs or can only operate in the microwave regime. Here we show a theoretical demonstration for highly confined topologically protected optical states to be realized at infrared frequencies in a simple two-dimensional (2D) material structure-a periodically patterned graphene monolayer-subject to a magnetic field of only 2 tesla. In our graphene honeycomb superlattice structures, plasmons exhibit substantial nonreciprocal behavior at the superlattice junctions under moderate static magnetic fields, leading to the emergence of topologically protected edge states and localized bulk modes. This approach is simple and robust for realizing topologically nontrivial optical states in 2D atomic layers, and could pave the way for building fast, nanoscale, defect-immune photonic devices.

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.

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.

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.

Surface-enhanced Raman scattering (SERS) has become a widely used spectroscopic technique for chemical identification, providing unbeaten sensitivity down to the single-molecule level. The amplification of the optical near field produced by collective electron excitations -plasmons- in nanostructured metal surfaces gives rise to a dramatic increase by many orders of magnitude in the Raman scattering intensities from neighboring molecules. This effect strongly depends on the detailed geometry and composition of the plasmon-supporting metallic structures. However, the search for optimized SERS substrates has largely relied on empirical data, due in part to the complexity of the structures, whose simulation becomes prohibitively demanding. In this work, we use state-of-the-art electromagnetic computation techniques to produce predictive simulations for a wide range of nanoparticle-based SERS substrates, including realistic configurations consisting of random arrangements of hundreds of nanoparticles with various morphologies. This allows us to derive rules of thumb for the influence of particle anisotropy and substrate coverage on the obtained SERS enhancement and optimum spectral ranges of operation. Our results provide a solid background to understand and design optimized SERS substrates.

Capturing and controlling plasmons at buried interfaces with nanometre and femtosecond resolution has yet to be achieved and is critical for next generation plasmonic devices. Here we use light to excite plasmonic interference patterns at a buried metal-dielectric interface in a nanostructured thin film. Plasmons are launched from a photoexcited array of nanocavities and their propagation is followed via photon-induced near-field electron microscopy (PINEM). The resulting movie directly captures the plasmon dynamics, allowing quantification of their group velocity at ∼0.3 times the speed of light, consistent with our theoretical predictions. Furthermore, we show that the light polarization and nanocavity design can be tailored to shape transient plasmonic gratings at the nanoscale. This work, demonstrating dynamical imaging with PINEM, paves the way for the femtosecond and nanometre visualization and control of plasmonic fields in advanced heterostructures based on novel two-dimensional materials such as graphene, MoS 2 , and ultrathin metal films.

Electro-optical modulation of visible and near-infrared light is important for a wide variety of applications, ranging from communications to sensing and smart windows. However, currently available approaches result in rather bulky devices, suffer from low integrability, and can hardly operate at the low power consumption levels and fast switching rates required by microelectronic drivers. Here we show that planar nanostructures patterned in ultrathin metal-graphene hybrid films sustain highly tunable plasmons in the visible and near-infrared spectral regions. Strong variations in the reflection and absorption of incident light take place when the plasmons are tuned on- and off-resonance with respect to externally incident light. As a result, a remarkable modulation depth (i.e., the maximum relative variation with/without graphene doping) exceeding 90% in transmission and even more dramatic in reflection (>600%) is predicted for graphene-loaded silver films of 1-5 nm thickness and currently attainable lateral dimensions. These new structures hold great potential for fast low-power electro-optical modulation.

Plasmons-the collective oscillations of electrons in conducting materials-play a pivotal role in nanophotonics because of their ability to couple electronic and photonic degrees of freedom. In particular, plasmons in graphene-the atomically thin carbon material-offer strong spatial confinement and long lifetimes, accompanied by extraordinary optoelectronic properties derived from its peculiar electronic band structure. Understandably, this material has generated great expectations for its application to enhanced integrated devices. However, an efficient scheme for detecting graphene plasmons remains a challenge. Here we show that extremely compact graphene nanostructures are capable of realizing on-chip electrical detection of single plasmons. Specifically, we predict a 2-fold increase in the electrical current across a graphene nanostructure junction caused by the excitation of a single plasmon. This effect, which is due to the increase in electron temperature following plasmon decay, should persist during a picosecond time interval characteristic of electron-gas relaxation. We further show that a broad spectral detection range is accessible either by electrically doping the junction or by varying the size of the nanostructure. The proposed graphene plasmometer could find application as a basic component of future optics-free integrated nanoplasmonic devices.

Efficient treatments in bacterial infections require the fast and accurate recognition of pathogens, with concentrations as low as one per milliliter in the case of septicemia. Detecting and quantifying bacteria in such low concentrations is challenging and typically demands cultures of large samples of blood (~1 milliliter) extending over 24-72 hours. This delay seriously compromises the health of patients. Here we demonstrate a fast microorganism optical detection system for the exhaustive identification and quantification of pathogens in volumes of biofluids with clinical relevance (~1 milliliter) in minutes. We drive each type of bacteria to accumulate antibody functionalized SERS-labelled silver nanoparticles. Particle aggregation on the bacteria membranes renders dense arrays of inter-particle gaps in which the Raman signal is exponentially amplified by several orders of magnitude relative to the dispersed particles. This enables a multiplex identification of the microorganisms through the molecule-specific spectral fingerprints.

The ability of graphene to support long-lived, electrically tunable plasmons that interact strongly with light, combined with its highly nonlinear optical response, has generated great expectations for application of the atomically thin material to nanophotonic devices. These expectations are mainly reinforced by classical analyses performed using the response derived from extended graphene, neglecting finite-size and nonlocal effects that become important when the carbon layer is structured on the nanometer scale in actual device designs. Here we show that finite-size effects produce large contributions that increase the nonlinear response of nanostructured graphene to significantly higher levels than those predicted by classical theories. We base our analysis on a quantum-mechanical description of graphene using tight-binding electronic states combined with the random-phase approximation. While classical and quantum descriptions agree well for the linear response when either the plasmon energy is below the Fermi energy or the size of the structure exceeds a few tens of nanometers, this is not always the case for the nonlinear response, and in particular, third-order Kerr-type nonlinearities are generally underestimated by the classical theory. Our results reveal the complex quantum nature of the optical response in nanostructured graphene, while further supporting the exceptional potential of this material for nonlinear nanophotonic devices.

Nanophotonic structures make it possible to precisely engineer the optical response at deep subwavelength scales. However, a fundamental understanding of the general performance limits remains a challenge. Here we use extensive electrodynamics simulations to demonstrate that the so-called f-sum rule sets a strict upper bound to the light extinction by nanostructures regardless their internal interactions and retardation effects. In particular, we show that the f-sum rule applies to arbitrarily complex plasmonic metal structures that exhibit an extraordinary spectral sensitivity to size, shape, near-field coupling effects, and incident polarization. The results may be used for benchmarking light scattering and absorption efficiencies, thus imposing fundamental limits on solar light harvesting, biomedical photonics, and optical communications.

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.

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.

Inspired by the concept of living polymerization reaction, we are able to produce silver-gold-silver nanowires with a precise control over their total length and plasmonic properties by establishing a constant silver deposition rate on the tips of penta-twinned gold nanorods used as seed cores. Consequently, the length of the wires increases linearly in time. Starting with ∼210 nm × 32 nm gold cores, we produce nanowire lengths up to several microns in a highly controlled manner, with a small self-limited increase in thickness of ∼4 nm, corresponding to aspect ratios above 100, whereas the low polydispersity of the product allows us to detect up to nine distinguishable plasmonic resonances in a single colloidal solution. We analyze the spatial distribution and the nature of the plasmons by electron energy loss spectroscopy and obtain excellent agreement between measurements and electromagnetic simulations, clearly demonstrating that the presence of the gold core plays a marginal role, except for relatively short wires or high-energy modes.

Infrared spectroscopy is the technique of choice for chemical identification of biomolecules through their vibrational fingerprints. However, infrared light interacts poorly with nanometric-size molecules. We exploit the unique electro-optical properties of graphene to demonstrate a high-sensitivity tunable plasmonic biosensor for chemically specific label-free detection of protein monolayers. The plasmon resonance of nanostructured graphene is dynamically tuned to selectively probe the protein at different frequencies and extract its complex refractive index. Additionally, the extreme spatial light confinement in graphene—up to two orders of magnitude higher than in metals—produces an unprecedentedly high overlap with nanometric biomolecules, enabling superior sensitivity in the detection of their refractive index and vibrational fingerprints. The combination of tunable spectral selectivity and enhanced sensitivity of graphene opens exciting prospects for biosensing., (Copyright © 2015, American Association for the Advancement of Science.)

Plasmon modes of the exact same individual gold nanoprisms are investigated through combined nanometer-resolved electron energy-loss spectroscopy (EELS) and cathodoluminescence (CL) measurements. We show that CL only probes the radiative modes, in contrast to EELS, which additionally reveals dark modes. The combination of both techniques on the same particles thus provides complementary information and also demonstrates that although the radiative modes give rise to very similar spatial distributions when probed by EELS or CL, their resonant energies appear to be different. We trace this phenomenon back to plasmon dissipation, which affects in different ways the plasmon signatures probed by these techniques. Our experiments are in agreement with electromagnetic numerical simulations and can be further interpreted within the framework of a quasistatic analytical model. We therefore demonstrate that CL and EELS are closely related to optical scattering and extinction, respectively, with the addition of nanometer spatial resolution.

The observation and electrical manipulation of infrared surface plasmons in graphene have triggered a search for similar photonic capabilities in other atomically thin materials that enable electrical modulation of light at visible and near-infrared frequencies, as well as strong interaction with optical quantum emitters. Here, we present a simple analytical description of the optical response of such kinds of structures, which we exploit to investigate their application to light modulation and quantum optics. Specifically, we show that plasmons in one-atom-thick noble-metal layers can be used both to produce complete tunable optical absorption and to reach the strong-coupling regime in the interaction with neighboring quantum emitters. Our methods are applicable to any plasmon-supporting thin materials, and in particular, we provide parameters that allow us to readily calculate the response of silver, gold, and graphene islands. Besides their interest for nanoscale electro-optics, the present study emphasizes the great potential of these structures for the design of quantum nanophotonics devices.

We use an extension of the hydrodynamic model to study nonlocal effects in the collective plasmon excitations at metal surfaces and narrow gaps between metals, including the surface spill-out of conduction band electrons. In particular, we simulate metal surfaces consisting of a smooth conduction-electron density profile and an abrupt jellium edge. We focus on aluminum and gold as prototypical examples of simple and noble metals, respectively. Our calculations agree with the dispersion relations measured from planar surfaces for these materials. Systems involving small gaps display a regime of tunnelling electrons, which is partially captured by the overlap of electron densities. This extension of the hydrodynamic model to cope with inhomogeneous density profiles provides a relatively fast and accurate way of describing the optical response of metal surfaces at subnanometer distances.

Advances in the field of nanoplasmonics are hindered by the limited capabilities of simulation tools in dealing with realistic systems comprising regions that extend over many light wavelengths. We show that the optical response of unprecedentedly large systems can be accurately calculated by using a combination of surface integral equation (SIE) method of moments (MoM) formulation and an expansion of the electromagnetic fields in a suitable set of spatial wave functions via fast multipole methods. We start with a critical review of volume versus surface integral methods, followed by a short tutorial on the key features that render plasmons useful for sensing (field enhancement and confinement). We then use the SIE-MoM to examine the plasmonic and sensing capabilities of various systems with increasing degrees of complexity, including both individual and interacting gold nanorods and nanostars, as well as large random and periodic arrangements of ∼1000 gold nanorods. We believe that the present results and methodology raise the standard of numerical electromagnetic simulations in the field of nanoplasmonics to a new level, which can be beneficial for the design of advanced nanophotonic devices and optical sensing structures.

Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg(2+) and the more toxicologically relevant methylmercury (CH₃Hg(+)) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg(2+) and CH₃Hg(+) to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms.

We experimentally and theoretically explore near-field nanopatterning obtained by irradiation of hexagonal monolayers of micron-sized polystyrene spheres on photosensitive Ge(2)Sb(5)Te(5) (GST) films. The imprinted patterns are strongly sensitive to the illumination conditions, as well as the size of the spheres and the orientation of the monolayer, which we change to demonstrate control over the resulting structures. We show that the presence of multiple scattering effects cannot be neglected to describe the resulting pattern. The experimental patterns imprinted are shown to be robust to small displacements and structural defects of the monolayer. Our method enables the design and experimental verification of patterns with multiple focii per particle and complex shapes, which can be directly implemented for large scale fabrication on different substrates.

Nanopositioning of single quantum emitters to control their coupling to integrated photonic structures is a crucial step in the fabrication of solid-state quantum optics devices. We use the optical near-field enhancement produced by nanofabricated gold antennas subject to near-infrared illumination to deterministically trap and position single nanodiamonds (NDs) hosting nitrogen-vacancy (NV) centers. The positioning of the NDs at the antenna regions of maximum field intensity is first characterized using both fluorescence and electron microscopy imaging. We further study the interaction between the nanoantenna and the delivered NV center by analyzing its change in fluorescence lifetime, which is driven by the increase in the local density of optical states at the trapping positions. Additionally, the plasmonic enhancement of the near-field intensity allows us to optically control the NV excited lifetime using relatively low NIR illumination intensities, some 20 times lower than in the absence of the antennas.

We theoretically study absorption by an undoped graphene layer decorated with arrays of small particles. We discuss periodic and random arrays within a common formalism, which predicts a maximum absorption of 50% for suspended graphene in both cases. The limits of weak and strong scatterers are investigated, and an unusual dependence on particle-graphene separation is found and explained in terms of the effective number of contributing evanescent diffraction orders of the array. Our results can be important to boost absorption by single-layer graphene due to its simple setup with potential applications to light harvesting and photodetection based on energy (Förster) rather than charge transfer.

Molecular chemistry offers a unique toolkit to draw inspiration for the design of artificial metamolecules. For a long time, optical circular dichroism has been exclusively the terrain of natural chiral molecules, which exhibit optical activity mainly in the UV spectral range, thus greatly hindering their significance for a broad range of applications. Here we demonstrate that circular dichroism can be generated with artificial plasmonic chiral nanostructures composed of the minimum number of spherical gold nanoparticles required for three-dimensional (3D) chirality. We utilize a rigid addressable DNA origami template to precisely organize four nominally identical gold nanoparticles into a three-dimensional asymmetric tetramer. Because of the chiral structural symmetry and the strong plasmonic resonant coupling between the gold nanoparticles, the 3D plasmonic assemblies undergo different interactions with left and right circularly polarized light, leading to pronounced circular dichroism. Our experimental results agree well with theoretical predictions. The simplicity of our structure geometry and, most importantly, the concept of resorting on biology to produce artificial photonic functionalities open a new pathway to designing smart artificial plasmonic nanostructures for large-scale production of optically active metamaterials.

The ability of plasmons to enhance the electromagnetic field intensity in the gap between metallic nanoparticles derives from their strong optical confinement relative to the light wavelength. The spatial extension of plasmons in doped graphene has recently been shown to be boldly reduced with respect to conventional plasmonic metals. Here, we show that graphene nanostructures are capable of capitalizing such strong confinement to yield unprecedented levels of field enhancement, well beyond what is found in noble metals of similar dimensions (~ tens of nanometers). We perform realistic, quantum-mechanical calculations of the optical response of graphene dimers formed by nanodisks and nanotriangles, showing a strong sensitivity of the level of enhancement to the type of carbon edges near the gap region, with armchair edges favoring stronger interactions than zigzag edges. Our quantum-mechanical description automatically incorporates nonlocal effects that are absent in classical electromagnetic theory, leading to over an order of magnitude higher enhancement in armchair structures. The classical limit is recovered for large structures. We predict giant levels of light concentration for dimers ~200 nm, leading to infrared-absorption enhancement factors ~10(8). This extreme light enhancement and confinement in nanostructured graphene has great potential for optical sensing and nonlinear devices.

We show that chemically synthesized polycyclic aromatic hydrocarbons (PAHs) exhibit molecular plasmon resonances that are remarkably sensitive to the net charge state of the molecule and the atomic structure of the edges. These molecules can be regarded as nanometer-sized forms of graphene, from which they inherit their high electrical tunability. Specifically, the addition or removal of a single electron switches on/off these molecular plasmons. Our first-principles time-dependent density-functional theory (TDDFT) calculations are in good agreement with a simpler tight-binding approach that can be easily extended to much larger systems. These fundamental insights enable the development of novel plasmonic devices based upon chemically available molecules, which, unlike colloidal or lithographic nanostructures, are free from structural imperfections. We further show a strong interaction between plasmons in neighboring molecules, quantified in significant energy shifts and field enhancement, and enabling molecular-based plasmonic designs. Our findings suggest new paradigms for electro-optical modulation and switching, single-electron detection, and sensing using individual molecules.

When an Au nanoparticle in a liquid medium is illuminated with resonant light of sufficient intensity, a nanometer scale envelope of vapor-a "nanobubble"-surrounding the particle, is formed. This is the nanoscale onset of the well-known process of liquid boiling, occurring at a single nanoparticle nucleation site, resulting from the photothermal response of the nanoparticle. Here we examine bubble formation at an individual metallic nanoparticle in detail. Incipient nanobubble formation is observed by monitoring the plasmon resonance shift of an individual, illuminated Au nanoparticle, when its local environment changes from liquid to vapor. The temperature on the nanoparticle surface is monitored during this process, where a dramatic temperature jump is observed as the nanoscale vapor layer thermally decouples the nanoparticle from the surrounding liquid. By increasing the intensity of the incident light or decreasing the interparticle separation, we observe the formation of micrometer-sized bubbles resulting from the coalescence of nanoparticle-"bound" vapor envelopes. These studies provide the first direct and quantitative analysis of the evolution of light-induced steam generation by nanoparticles from the nanoscale to the macroscale, a process that is of fundamental interest for a growing number of applications.

Graphene has emerged as an outstanding material for optoelectronic applications due to its high electronic mobility and unique doping capabilities. Here we demonstrate electrical tunability and hybridization of plasmons in graphene nanodisks and nanorings down to 3.7 μm light wavelength. By electrically doping patterned graphene arrays with an applied gate voltage, we observe radical changes in the plasmon energy and strength, in excellent quantitative agreement with rigorous analytical theory. We further show evidence of an unexpected increase in plasmon lifetime with growing energy. Plasmon hybridization and electrical doping in nanorings of suitably chosen nanoscale dimensions are key elements for bringing the optical response of graphene closer to the near-infrared, where it can provide a robust, integrable platform for light modulation, switching, and sensing.

Organization of nanoparticles (NPs) of different materials into superstructures of higher complexity represents a key challenge in nanotechnology. Polymerase chain reaction (PCR) was used in this study to fabricate chains consisting of plasmonic NPs of different sizes, thus denoted heterochains. The NPs in such chains are connected by DNA oligomers, alternating in a sequence big-small-big-small-... and spanning lengths in the range of 40-300 nm by varying the number of PCR cycles. They display strong plasmonic chirality at 500-600 nm, the chiral activity revealing nonmonotonous dependence on the length of heterochains. We find the strength of surface-enhanced Raman scattering (SERS) to increase with chain length, while the chiral response initially increased and then decreased with the number of PCR cycles. The relationship between the optical properties of the heterochains and their structure/length is discussed. The length-dependent intense optical response of the plasmonic NP heterochains holds great potential for biosensing applications.

One of the simplest and most common structures used for directing light in macroscale applications is the parabolic reflector. Parabolic reflectors are ubiquitous in many technologies, from satellite dishes to hand-held flashlights. Today, there is a growing interest in the use of ultracompact metallic structures for manipulating light on the wavelength scale. Significant progress has been made in scaling radiowave antennas to the nanoscale for operation in the visible range, but similar scaling of parabolic reflectors employing ray-optics concepts has not yet been accomplished because of the difficulty in fabricating nanoscale three-dimensional surfaces. Here, we demonstrate that plasmon physics can be employed to realize a resonant elliptical cavity functioning as an essentially planar nanometallic structure that serves as a broadband unidirectional parabolic antenna at optical frequencies.