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Plasmonic nanoantennas focus light below the diffraction limit, creating strong field enhancements, typically within a nanoscale junction. Placing a nanostructure within the junction can greatly enhance the nanostructure's innate optical absorption, resulting in intense photothermal heating that could ultimately compromise both the nanostructure and the nanoantenna. Here, we demonstrate a three-dimensional "antenna-reactor" geometry that results in large nanoscale thermal gradients, inducing large local temperature increases in the confined nanostructure reactor while minimizing the temperature increase of the surrounding antenna. The nanostructure is supported on an insulating substrate within the antenna gap, while the antenna maintains direct contact with an underlying thermal conductor. Elevated local temperatures are quantified, and high local temperature gradients that thermally reshape only the internal reactor element within each antenna-reactor structure are observed. We also show that high local temperature increases of nominally 200 °C are achievable within antenna-reactors patterned into large extended arrays. This simple strategy can facilitate standoff optical generation of high-temperature hotspots, which may be useful in applications such as small-volume, high-throughput chemical processes, where reaction efficiencies depend exponentially on local temperature.

Plasmonic materials have optical cross sections that exceed by 10-fold their geometric sizes, making them uniquely suitable to convert light into electrical charges. Harvesting plasmon-generated hot carriers is of interest for the broad fields of photovoltaics and photocatalysis; however, their direct utilization is limited by their ultrafast thermalization in metals. To prolong the lifetime of hot carriers, one can place acceptor materials, such as semiconductors, in direct contact with the plasmonic system. Herein, we report the effect of operating temperature on hot electron generation and transfer to a suitable semiconductor. We found that an increase in the operation temperature improves hot electron harvesting in a plasmonic semiconductor hybrid system, contrasting what is observed on photodriven processes in nonplasmonic systems. The effect appears to be related to an enhancement in hot carrier generation due to phonon coupling. This discovery provides a new strategy for optimization of photodriven energy production and chemical synthesis.

Hot-electron dynamics taking place in nanostructured materials upon irradiation with fs-laser pulses has been the subject of intensive research, leading to the emerging field of ultrafast nanophotonics. However, the most common description of nonlinear interaction with ultrashort laser pulses assumes a homogeneous spatial distribution for the photogenerated carriers. Here we theoretically show that the inhomogeneous evolution of the hot carriers at the nanoscale can disclose unprecedented opportunities for ultrafast diffraction management. In particular, we design a highly symmetric plasmonic metagrating capable of a transient symmetry breaking driven by hot electrons. The subsequent power imbalance between symmetrical diffraction orders is calculated to exceed 20% under moderate (∼2 mJ/cm2) laser fluence. Our theoretical investigation also indicates that the recovery time of the symmetric configuration can be controlled by tuning the geometry of the metaatom, and can be as fast as 2 ps for electrically connected configurations.

The deep-level traps induced by charged defects at the grain boundaries (GBs) of polycrystalline organic–inorganic halide perovskite (OIHP) films serve as major recombination centres, which limit the device performance. Herein, we incorporate specially designed poly(3-aminothiophenol)-coated gold (Au@PAT) nanoparticles into the perovskite absorber, in order to examine the influence of plasmonic resonance on carrier dynamics in perovskite solar cells. Local changes in the photophysical properties of the OIHP films reveal that plasmon excitation could fill trap sites at the GB region through photo-brightening, whereas transient absorption spectroscopy and density functional theory calculations correlate this photo-brightening of trap states with plasmon-induced interfacial processes. As a result, the device achieved the best efficiency of 22.0% with robust operational stability. Our work provides unambiguous evidence for plasmon-induced trap occupation in OIHP and reveals that plasmonic nanostructures may be one type of efficient additives to overcome the recombination losses in perovskite solar cells and thin-film solar cells in general., The incorporation of plasmonic core-shell nanostructures at the grain boundaries of perovskite films reduces the charge recombination loss through photo-brightening of trap states.

Substantial effort has been invested in generating narrow bandwidth visible colors from metasurfaces using a wide variety of geometries and materials. In this work we continue these explorations and demonstrate how a combination of a plasmonic Fano resonance and a Bragg reflector can contribute to the generation of narrowband visible colors. We demonstrate active tuning of these colors by stretching the array in the x- and y- directions and the reflector in z- to shift the colorimetric response of both elements. The combination of these two types of photonic structures allows for substantially increased flexibility in design and color-space tuning. Additionally, by fabricating these structures at scale, this methodology could prove useful towards the manufacture of agile metasurface color pixels

Dielectric metasurfaces have recently been shown to provide an excellent platform for the harmonic generation of light due to their low optical absorption and to the strong electromagnetic field en...

The ever-increasing global need for potable water requires practical, sustainable approaches for purifying abundant alternative sources such as seawater, high-salinity processed water, or underground reservoirs. Evaporation-based solutions are of particular interest for treating high salinity water, since conventional methods such as reverse osmosis have increasing energy requirements for higher concentrations of dissolved minerals. Demonstration of efficient water evaporation with heat localization in nanoparticle solutions under solar illumination has led to the recent rapid development of sustainable, solar-driven distillation methods. Given the amount of solar energy available per square meter at the Earth’s surface, however, it is important to utilize these incident photons as efficiently as possible to maximize clean water output. Here we show that merely focusing incident sunlight into small “hot spots” on a photothermally active desalination membrane dramatically increases––by more than 50%––the flux of distilled water. This large boost in efficiency results from the nearly exponential dependence of water vapor saturation pressure on temperature, and therefore on incident light intensity. Exploiting this inherent but previously unrecognized optical nonlinearity should enable the design of substantially higher-throughput solar thermal desalination methods. This property provides a mechanism capable of enhancing a far wider range of photothermally driven processes with supralinear intensity dependence, such as light-driven chemical reactions and separation methods.

Surface plasmon enhanced processes and hot-carrier dynamics in plasmonic nanostructures are of great fundamental interest to reveal light-matter interactions at the nanoscale. Using plasmonic tunnel junctions as a platform supporting both electrically- and optically excited localized surface plasmons, we report a much greater (over 1000x) plasmonic light emission at upconverted photon energies under combined electro-optical excitation, compared with electrical or optical excitation separately. Two mechanisms compatible with the form of the observed spectra are interactions of plasmon-induced hot carriers and electronic anti-Stokes Raman scattering. Our measurement results are in excellent agreement with a theoretical model combining electro-optical generation of hot carriers through non-radiative plasmon excitation and hot-carrier relaxation. We also discuss the challenge of distinguishing relative contributions of hot carrier emission and the anti-Stokes electronic Raman process. This observed increase in above-threshold emission in plasmonic systems may open avenues in on-chip nanophotonic switching and hot carrier photocatalysis., 21 pages, 4 figures, plus 27 pages Supporting Info with 7 figures

Plasmonic metal nanoparticles exhibit large dipole moments upon photoexcitation and have the potential to induce electronic transitions in nearby materials, but fast internal relaxation has to date limited the spatial range and efficiency of plasmonic mediated processes. In this work, we use photo-electrochemistry to synthesize hybrid nanoantennas comprised of plasmonic nanoparticles with photoconductive polymer coatings. We demonstrate that the formation of the conductive polymer is selective to the nanoparticles and that polymerization is enhanced by photoexcitation. In situ spectroscopy and simulations support a mechanism in which up to 50% efficiency of nonradiative energy transfer is achieved. These hybrid nanoantennas combine the unmatched light-harvesting properties of a plasmonic antenna with the similarly unmatched device processability of a polymer shell.

Ultrafast nanophotonics is an emerging research field aimed at the development of nanodevices capable of light modulation with unprecedented speed1–4. A promising approach exploits the optical nonlinearity of nanostructured materials (either metallic or dielectric) to modulate their effective permittivity via interaction with intense ultrashort laser pulses. Although the ultrafast temporal dynamics of such nanostructures following photoexcitation has been studied in depth5, sub-picosecond transient spatial inhomogeneities taking place at the nanoscale have been overlooked so far. Here, we demonstrate that the inhomogeneous spacetime distribution of photogenerated hot carriers induces a transient symmetry breaking in a highly symmetric plasmonic metasurface. The process is fully reversible and results in a broadband transient dichroism with a recovery of the initial isotropic state in less than 1 ps, overcoming the speed bottleneck caused by slower (electron–phonon and phonon–phonon) relaxation processes. Our results pave the way to ultrafast dichroic devices for high-speed modulation of light polarization. Inhomogeneity of the photogenerated carrier spacetime distribution enables transient symmetry breaking in a metasurface. As a result, broadband transient dichroism is demonstrated.

The photothermoelectric (PTE) effect enables efficient harvesting of the energy of photogenerated hot carriers and is a promising choice for high-efficiency photoelectric energy conversion and photodetection. Recently, the PTE effect was reported in low-dimensional nanomaterials, suggesting the possibility of optimizing their energy conversion efficiency. Unfortunately, the PTE effect becomes extremely inefficient in low-dimensional nanomaterials, owing to intrinsic disadvantages, such as low optical absorption and immature fabrication methods. In this study, a giant PTE effect was observed in lightly doped p-type silicon nanoribbons caused by photogenerated hot carriers. The open-circuit photovoltage responsivity of the device was 3-4 orders of magnitude higher than those of previously reported PTE devices. The measured photovoltage responses fit very well with the proposed photothermoelectric multiphysics models. This research proposes an application of the PTE effect and a possible method for utilizing hot carriers in semiconductors to significantly improve their photoelectric conversion efficiency., Light: Science & Applications photothermoelectric effect in silicon: a giant leap from light to electricity Silicon nanoribbons can achieve a three to four orders of magnitude increased photovoltage response by photothermoelectric effect, relative to previously developed low-dimensional materials, offering greatly improved photoresponse, and practical application for on-chip photodetectors or power supplies. In the photothermoelectric effect, photoelectric conversion is achieved by the optical-induced temperature difference in the carrier system. The photothermoelectric effect is expected to utilize the hot carrier energy which is wasted in the traditional photoelectric conversion. The past reported photothermoelectric effect was in low-dimensional materials, such as carbon nanotubes, III–V semiconductor nanowires, dichalcogenide materials, and graphene. Researchers in China and the USA, led by Zhiqiang Guan and Hongxing Xu at Wuhan University, China, extended this effect to silicon nanomaterials. The successful observation of photothermoelectric effect in silicon relies on the low doping concentrations and nanometer size of the silicon nanoribbon. Ohmic electrode contact is also important to reveal the photothermoelectric effect instead of photovoltaic effect. This innovation greatly expands the practical application by the photothermoelectric effect and utilizes the hot carrier energy thus improve the photoelectric conversion efficiency. It could lead to more efficient light-powered systems, ranging from photo-detecting devices to solar cells.

Dimers, two closely spaced metallic nanostructures, are one of the primary nanoscale geometries in plasmonics, supporting high local field enhancements in their interparticle junction under excitation of their hybridized "bonding" plasmon. However, when a dimer is fabricated on a metallic substrate, its characteristics are changed profoundly. Here we examine the properties of a Au dimer on a Au substrate. This structure supports a bright "bonding" dimer plasmon, screened by the metal, and a lower energy magnetic charge transfer plasmon. Changing the dielectric environment of the dimer-on-film structure reveals a broad family of higher-order hybrid plasmons in the visible region of the spectrum. Both of the localized surface plasmons resonances (LSPR) of the individual dimer-on-film structures as well as their collective surface lattice resonances (SLR) show a highly sensitive refractive index sensing response. Implementation of such all-metal magnetic-resonant nanostructures offers a promising route to achieve higher-performance LSPR- and SLR-based plasmonic sensors.

Nonlinear metasurface devices for generation and manipulation of coherent vacuum ultraviolet (VUV) light will be reported in this talk. The approaches for design, fabrication, and measurement of the metasurface devices with different working principles will be discussed. Our ultracompact metasurfaces are capable of efficiently generating VUV light via various nonlinear processes with effective nonlinear coefficients much better than general nonlinear medias in the targeted regime. They pave the way toward highly efficient and versatile miniaturized VUV nanodevices.

We theoretically predict and experimentally demonstrate by polarization-resolved ultrafast transient absorption that the inhomogeneous space-time distribution of photogenerated hot carriers induces a sub-picosecond symmetry breaking in a plasmonic metasurface made of highly symmetric metaatoms.

Above-threshold light emission from plasmonic tunnel junctions, when emitted photons have energies significantly higher than the energy scale of the incident electrons, has attracted much recent interest in nano-optics, while the underlying physical mechanism remains elusive. We examine above-threshold light emission in electromigrated tunnel junctions. Our measurements over a large ensemble of devices demonstrate a giant material dependence of photon yield (emitted photons per incident electrons), as large as four orders of magnitude. This dramatic effect cannot be explained only by the radiative field enhancement effect due to the localized plasmons in the tunneling gap. Emission is well described by a Boltzmann spectrum with an effective temperature exceeding 2000 K, coupled to a plasmon-modified photonic density of states. The effective temperature is approximately linear in the applied bias, consistent with a suggested theoretical model in which hot carriers are generated by non-radiative decay of electrically excited localized plasmons. Electrically driven hot-carrier generation and the associated non-traditional light emission could open new possibilities for active photochemistry, optoelectronics and quantum optics., 23 pages, 5 figures + supplementary information

Plasmonic hot-carrier-based photodetectors detect light at frequencies below the semiconductor bandgap with room temperature operation and can exhibit spectrally narrowband behavior, potentially el...

Vacuum ultraviolet (VUV) light has important applications in many fields, ranging from device fabrication to photochemistry, from environmental remediation to microscopy and spectroscopy. Methods to produce coherent VUV light frequently utilize high harmonic generation in media such as rare gases or atomic vapors; nonlinear optical crystals that support second harmonic generation into the VUV are quite rare. Here, we demonstrate an all-dielectric metasurface designed for the nonlinear optical generation of VUV light. Consisting of an array of zinc oxide nanoresonators, the device exhibits a magnetic dipole resonance at a wavelength of 394 nm. When excited with ultrafast laser pulses at this wavelength, the second harmonic at 197 nm is readily generated. Manipulation of the metasurface design enables control over the radiation pattern. This work has the potential to open the door toward simple and compact VUV sources for new applications.

The optical control of atomic relocations in a metallic quantum point contact is of great interest because it addresses the fundamental limit of "CMOS scaling". Here, by developing a platform for combined electronics and photonics on the atomic scale, we demonstrate an optically controlled electronic switch based on the relocation of atoms. It is shown through experiments and simulations how the interplay between electrical, optical, and light-induced thermal forces can reversibly relocate a few atoms and enable atomic photodetection with a digital electronic response, a high resistance extinction ratio (70 dB), and a low OFF-state current (10 pA) at room temperature. Additionally, the device introduced here displays an optically induced pinched hysteretic current (optical memristor). The photodetector has been tested in an experiment with real optical data at 0.5 Gbit/s, from which an eye diagram visualizing millions of detection cycles could be produced. This demonstrates the durability of the realized atomic scale devices and establishes them as alternatives to traditional photodetectors.

We report a single particle investigation of the polarized scattering spectra of individual Au nanotriangles (NTs) of the truncated bifrustrum type. We unexpectedly observed a wide diversity in the scattering spectra from a population of NTs with low shape polydispersity. Correlation of the optical measurements with electron microscopy revealed that the different optical responses were not due to distinct NT shapes. Rather, finite element simulations revealed that distinct polarized spectra originated from minute changes in the inclination of the NTs on the substrate. NT inclination resulted in asymmetric image charge formation in the substrate, thus, breaking the degeneracy of the modes supported by the NTs. The degeneracy of the NT modes was extremely sensitive to such symmetry breaking, with inclination angles as small as 2°, producing clearly resolved, nondegenerate, and orthogonally polarized plasmon modes.

Color pixels composed of plasmonic nanostructures provide a highly promising approach for new display technologies, capable of vivid, robust coloration and incorporating the use of low-cost plasmonic materials, such as aluminum. Here we report a plasmonic device that can be tuned continuously across the entire visible spectrum, based on integrating a square array of aluminum nanostructures into an elastomeric substrate. By stretching the substrate in either of its two dimensions, the period and therefore the scattering color can be modified to the blue or the red of the at-rest structure, spanning the entire visible spectrum. The unique two-dimensional design of this structure enables active mechanical color tuning, under gentle elastic modulation with no more than 35% strain. We also demonstrate active image switching with this structure. This design strategy has the potential to open the door for next-generation flexible photonic devices for a wide variety of visible-light applications.

Surface-enhanced infrared absorption (SEIRA) spectroscopy has outstanding potential in chemical detection as a complement to surface-enhanced Raman spectroscopy (SERS), yet it has historically lagged well behind SERS in detection sensitivity. Here we report a new ultrasensitive infrared antenna designed to bring SEIRA spectroscopy into the few-molecule detection range. Our antenna consists of a bowtie-shaped Au structure with a sub-3 nm gap, positioned to create a cavity above a reflective substrate. This three-dimensional geometry tightly confines incident mid-infrared radiation into its ultrasmall junction, yielding a hot spot with a theoretical SEIRA enhancement factor of more than 107, which can be designed to span the range of frequencies useful for SEIRA. We quantitatively evaluated the IR detection limit of this antenna design using mixed monolayers of 4-nitrothiophenol (4-NTP) and 4-methoxythiolphenol (4-MTP). The optimized antenna structure allows the detection of as few as ∼500 molecules of 4-NT...

We report a method to electrically detect heating from excitation of propagating surface plasmon polaritons (SPP). The coupling between SPP and a continuous wave laser beam is realized through lithographically defined gratings in the electrodes of thin film gold "bow tie" nanodevices. The propagating SPPs allow remote coupling of optical energy into a nanowire constriction. Heating of the constriction is detectable through changes in the device conductance and contains contributions from both thermal diffusion of heat generated at the grating and heat generated locally at the constriction by plasmon dissipation. We quantify these contributions through computational modeling and demonstrate that the propagation of SPPs provides the dominant contribution. Coupling optical energy into the constriction via propagating SPPs in this geometry produces an inferred temperature rise of the constriction a factor of 60 smaller than would take place if optical energy were introduced via directly illuminating the constriction. The grating approach provides a path for remote excitation of nanoconstrictions using SPPs for measurements that usually require direct laser illumination, such as surface-enhanced Raman spectroscopy.

With more than a billion people lacking accessible drinking water, there is a critical need to convert nonpotable sources such as seawater to water suitable for human use. However, energy requirements of desalination plants account for half their operating costs, so alternative, lower energy approaches are equally critical. Membrane distillation (MD) has shown potential due to its low operating temperature and pressure requirements, but the requirement of heating the input water makes it energy intensive. Here, we demonstrate nanophotonics-enabled solar membrane distillation (NESMD), where highly localized photothermal heating induced by solar illumination alone drives the distillation process, entirely eliminating the requirement of heating the input water. Unlike MD, NESMD can be scaled to larger systems and shows increased efficiencies with decreased input flow velocities. Along with its increased efficiency at higher ambient temperatures, these properties all point to NESMD as a promising solution for household- or community-scale desalination.

We report a study of the shape-dependent spectral response of the gold nanoparticle surface plasmon resonance at various electron densities to provide mechanistic insight into the role of capacitive charging, a topic of some debate. We demonstrate a morphology-dependent spectral response for gold nanoparticles due to capacitive charging using single-particle spectroscopy in an inert electrochemical environment. A decrease in plasmon energy and increase in spectral width for gold nanospheres and nanorods was observed as the electron density was tuned through a potential window of -0.3 to 0.1 V. The combined observations could not be explained by existing theories. A new quantum theory for charging based on the random phase approximation was developed. Additionally, the redox reaction of gold oxide formation was probed using single-particle plasmon voltammetry to reproduce the reduction peak from the bulk cyclic voltammetry. These results deepen our understanding of the relationship between optical and electronic properties in plasmonic nanoparticles and provide insight toward their potential applications in directed electrocatalysis.

The coupling of plasmonic resonances is an effective tool to tailor the optical properties of nanostructures. However, the coupling of higher order plasmonic resonances has not received much attention, with most studies focusing on the interaction of dipolar modes. Taking advantage of the high spatial and energy resolution of modern scanning transmission electron microscopes equipped with electron energy loss spectroscopy, we analyze the coupling of edge modes in planar nanostructures with emphasis on the interaction of high order modes and the formation of gap modes. We show that coupling of edge modes can be understood by a simple and intuitive scheme, with three regimes: First, a strong coupling through the edge of the structure resulting in bonding and antibonding gap edge modes; second, coupling through the corners of the structures resulting in bonding and antibonding corner edge modes; and a third behavior where the edge modes do not couple and behave independently of the rest of the structure. The...

Strong coupling between plasmons and excitons in nanocavities can result in the formation of hybrid plexcitonic states. Understanding the dispersion relation of plexcitons is important both for fundamental quantum science and for applications including optoelectronics and nonlinear optics devices. The conventional approach, based on statistics over different nanocavities, suffers from large inhomogeneities from the samples, owing to the nonuniformity of nanocavities and the lack of control over the locations and orientations of the excitons. Here we report the first measurement of the dispersion relationship of plexcitons in an individual nanocavity. Using a single silver nanorod as a Fabry-Perot nanocavity, we realize strong coupling of plasmon in single nanocavity with excitons in a single atomic layer of tungsten diselenide. The plexciton dispersion is measured by in situ redshifting the plasmon energy via successive deposition of a dielectric layer. Room-temperature formation of plexcitons with Rabi s...

Doped semiconductor nanocrystals represent an exciting new type of plasmonic material with optical resonances in the infrared. Unlike noble metal nanoparticles, the plasmon resonance can be tuned by altering the doping density. Recently, it has been shown that silicon nanocrystals can be doped using phosphorus and boron resulting in highly tunable infrared plasmon resonances. Due to the band structure of silicon, doping with phosphorus contributes light (transverse) and heavy (longitudinal) electrons, while boron contributes light and heavy holes and one would expect two distinct plasmon branches. Here we develop a classical hybridization theory and a full quantum mechanical TDLDA approach for two-component carrier plasmas and show that the interaction between the two plasmon branches results in strongly hybridized plasmon modes. The antibonding mode where the two components move in phase is bright and depends sensitively on the doping densities. The low energy bonding mode with opposite charge alignment ...

Vacuum ultraviolet (VUV) light is electromagnetic radiation in the wavelength regime between 100nm and 200nm. Due to its high photon energy, VUV light is very important in many advanced applications, such as photochemistry, nanolithography, and novel spectroscopy. While several methods to generate coherent VUV light have been developed, a multifunctional nanophotonic device for efficient VUV light generation and control still remains an outstanding challenge. In this work, we demonstrate an all-dielectric metasurface device (metadevice) which can be used for nonlinearly generating coherent VUV light. Metasurfaces are artificial nanostructures with resonance properties that can be designed by carefully tailoring their geometric parameters. The metadevice demonstrated in this work consists of an array ZnO nano-resonators. To fabricate the metadevice, a 150-nm multicrystalline ZnO was nanopatterned using a focus ion beam system. In the linear transmission measurement, the metadevice shows a resonance dip at around 400nm. This resonance was found to be associated to a magnetic dipole resonance of the nano-resonators. When a visible femtosecond laser beam (wavelength: 394nm) as an excitation source was loosely focused on the metadevice, VUV light originating from second harmonic generation of the metadevice was produced. The dependence of the VUV signal on the excitation power as well as on the incident angle were carefully measured and analyzed. Furthermore, manipulation of the output VUV wavefront was realized by carefully controlling the nano-resonator arrangement. This work paves a novel route toward high-efficiency multifunctional nanophotonic devices for VUV applications [Nano Lett. 18, 5738 (2018)].

Developing highly efficient nanoscale coherent light sources is essential for advances in technological applications such as integrated photonic circuits, bioimaging, and sensing. An on-chip wavelength convertor based on second harmonic generation (SHG) would be a crucial step toward this goal, but the light-conversion efficiency would be low for small device dimensions. Here we demonstrate strongly enhanced SHG with a high conversion efficiency of 4 × 10-5 W-1 from a hybrid plasmonic waveguide consisting of a CdSe nanowire coupled with a Au film. The strong spatial overlap of the waveguide mode with the nonlinear material and momentum conservation between the incident and reflected modes are the key factors resulting in such high efficiency. The SHG emission angles vary linearly with excitation wavelength, indicating a nonlinear steering of coherent light emission at the subwavelength scale. Our work is promising for the realization of efficient and tunable nonlinear coherent sources and opens new approaches for efficient integrated nonlinear nanophotonic devices.

Aluminum nanostructures are a promising alternative material to noble metal nanostructures for several photonic and catalytic applications, but their ultrafast electron dynamics remain elusive. Here, we combine single-particle transient extinction spectroscopy and parameter-free first-principles calculations to investigate the non-equilibrium carrier dynamics in aluminum nanostructures. Unlike gold nanostructures, we find the sub-picosecond optical response of lithographically fabricated aluminum nanodisks to be more sensitive to the lattice temperature than the electron temperature. We assign the rise in the transient transmission to electron-phonon coupling with a pump-power-independent lifetime of 500 ± 100 fs and theoretically confirm this strong electron-phonon coupling behavior. We also measure electron-phonon lifetimes in chemically synthesized aluminum nanocrystals and find them to be even longer (1.0 ± 0.1 ps) than for the nanodisks. We also observe a rise and decay in the transient transmissions with amplitudes that scale with the surface-to-volume ratio of the aluminum nanodisks, implying a possible hot carrier trapping and detrapping at the native oxide shell-metal core interface.

The origin of light emission from plasmonic nanoparticles has been strongly debated lately. It is present as the background of surface-enhanced Raman scattering and, despite the low yield, has been used for novel sensing and imaging applications because of its photostability. Although the role of surface plasmons as an enhancing antenna is widely accepted, the main controversy regarding the mechanism of the emission is its assignment to either radiative recombination of hot carriers (photoluminescence) or electronic Raman scattering (inelastic light scattering). We have previously interpreted the Stokes-shifted emission from gold nanorods as the Purcell effect enhanced radiative recombination of hot carriers. Here we specifically focused on the anti-Stokes emission from single gold nanorods of varying aspect ratios with excitation wavelengths below and above the interband transition threshold while still employing continuous wave lasers. Analysis of the intensity ratios between Stokes and anti-Stokes emission yields temperatures that can only be interpreted as originating from the excited electron distribution and not a thermally equilibrated phonon population despite not using pulsed laser excitation. Consistent with this result as well as previous emission studies using ultrafast lasers, the power-dependence of the upconverted emission is nonlinear and gives the average number of participating photons as a function of emission wavelength. Our findings thus show that hot carriers and photoluminescence play a major role in the upconverted emission.

The harmonic generation of light with plasmonic and all-dielectric nanostructures has gained much recent interest. This approach is especially promising for short wavelength (i.e., ultraviolet (UV)) generation, where conventional nonlinear crystals reach their limits both in transparency and in their ability to achieve phase-matching between the input and output fields. Here, we demonstrate that the third harmonic generation of deep UV light in an indium tin oxide (ITO) film can be substantially enhanced by a metasurface consisting of metallic toroidal meta-atoms covered with an alumina layer for protection against laser-induced damage. This approach combines the benefits of the large nonlinear susceptibility of ITO with the unique field enhancement properties of a toroidal metasurface. This ITO-meta-atom combination produces a third harmonic signal at a wavelength of 262 nm that is nominally five times larger than that of an ITO film patterned with a conventional hotspot-enhanced plasmonic dimer array. This result demonstrates the potential for toroidal meta-atoms as the active engineered element in a new generation of enhanced nonlinear optical materials and devices.

Conventional bioethanol for transportation fuel typically consumes agricultural feedstocks also suitable for human consumption and requires large amounts of energy for conversion of feedstock to fuel. Alternative feedstocks, optimally those not also in demand for human consumption, and off-grid energy sources for processing would both contribute to making bioethanol far more sustainable than current practices. Cellulosic bioethanol production involves three steps: the extraction of sugars from cellulosic feedstock, the fermentation of sugars to produce ethanol, and the purification of ethanol through distillation. Traditional production methods for extraction and distillation are energy intensive and therefore costly, limiting the advancement of this approach. Here we report an initial demonstration of the conversion of cellulosic feedstock into ethanol by completely off-grid solar processing steps. Our approach is based on nanoparticle-enabled solar steam generation, in which high-efficiency steam can be...

Plasmonic clusters can exhibit Fano resonances with unique and tunable asymmetric line shapes, which arise due to the coupling of bright and dark plasmon modes within each multiparticle structure. These structures are capable of generating remarkably large local electromagnetic field enhancements and should give rise to high hot carrier yields relative to other plasmonic nanostructures. While the scattering properties of individual plasmonic Fano resonances have been characterized extensively both experimentally and theoretically, their absorption properties, critical for hot carrier generation, have not yet been measured. Here, we utilize single-particle absorption spectroscopy based on photothermal imaging to distinguish between the radiative and nonradiative properties of an individual Fano cluster. In observing the absorption spectrum of individual Fano clusters, we directly verify the theoretical prediction that while Fano interference may be prominent in scattering, it is completely absent in absorption. Our results provide microscopic insight into the nature of Fano interference in systems of coupled plasmonic nanoparticles and should pave the way for the optimization of hot carrier production using plasmonic Fano clusters.

Photocatalysis uses light energy to drive chemical reactions. Conventional industrial catalysts are made of transition metal nanoparticles that interact only weakly with light, while metals such as Au, Ag, and Al that support surface plasmons interact strongly with light but are poor catalysts. By combining plasmonic and catalytic metal nanoparticles, the plasmonic "antenna" can couple light into the catalytic "reactor". This interaction induces an optical polarization in the reactor nanoparticle, forcing a plasmonic response. When this "forced plasmon" decays it can generate hot carriers, converting the catalyst into a photocatalyst. Here we show that precisely oriented, strongly coupled Al-Pd nanodisk heterodimers fabricated using nanoscale lithography can function as directional antenna-reactor photocatalyst complexes. The light-induced hydrogen dissociation rate on these structures is strongly dependent upon the polarization angle of the incident light with respect to the orientation of the antenna-reactor pair. Their high degree of structural precision allows us to microscopically quantify the photocatalytic activity per heterostructure, providing precise photocatalytic quantum efficiencies. This is the first example of precisely designed heterometallic nanostructure complexes for plasmon-enabled photocatalysis and paves the way for high-efficiency plasmonic photocatalysts by modular design.

Three-dimensional chiral plasmonic nanostructures have been shown to be able to dramatically boost photon-spin selective light-matter interactions, potentially leading to novel photonics, molecular spectroscopy, and light-harvesting applications based on circularly polarized light. Here, we show that chiral split-ring gold nanoresonators interfaced to a wide band gap semiconductor exhibit a contrast in hot-electron transfer rate between left-handed and right-handed visible light that essentially mimics the far-field circular dichroism of the structures. We trace down the origin of this effect to the differential excitation of the thinnest part of the split-ring structures using dichroic-sensitive cathodoluminescence imaging with nanometer spatial resolution. The results highlight the intricate interplay between the near-field and far-field chiral response of a nanostructure and establishes a clear link to the emerging field of hot carrier plasmonics with numerous potential applications in photocatalysis and solar light harvesting.

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.

While there has been a tremendous increase of recent interest in noble metal-based antennas as substrates for surface-enhanced infrared absorption spectroscopy, more abundant and manufacturable metals may offer similar or additional opportunities for this mid-infrared sensing modality. Here we examine the feasibility of aluminum antennas for SEIRA, by designing and fabricating asymmetric aluminum cross antennas with nanometer-scale gaps. The asymmetric cross design enables the simultaneous detection of multiple infrared vibrational resonances over a broad region of the mid-infrared spectrum. The presence of the Al2O3 amorphous surface oxide layer not only passivates the metal antenna structures but also enables a very straightforward covalent binding chemistry for analyte molecules to the antenna through multiple approaches, in this case by the use of carboxylic acid functional groups. The aluminum–oxygen stretching mode of the oxide can be used as a self-calibration standard to quantify the number of ana...

Chromatic devices such as flat panel displays could, in principle, be substantially improved by incorporating aluminum plasmonic nanostructures instead of conventional chromophores that are susceptible to photobleaching. In nanostructure form, aluminum is capable of producing colors that span the visible region of the spectrum while contributing exceptional robustness, low cost, and streamlined manufacturability compatible with semiconductor manufacturing technology. However, individual aluminum nanostructures alone lack the vivid chromaticity of currently available chromophores because of the strong damping of the aluminum plasmon resonance in the visible region of the spectrum. In recent work, we showed that pixels formed by periodic arrays of Al nanostructures yield far more vivid coloration than the individual nanostructures. This progress was achieved by exploiting far-field diffractive coupling, which significantly suppresses the scattering response on the long-wavelength side of plasmonic pixel resonances. In the present work, we show that by utilizing another collective coupling effect, Fano interference, it is possible to substantially narrow the short-wavelength side of the pixel spectral response. Together, these two complementary effects provide unprecedented control of plasmonic pixel spectral line shape, resulting in aluminum pixels with far more vivid, monochromatic coloration across the entire RGB color gamut than previously attainable. We further demonstrate that pixels designed in this manner can be used directly as switchable elements in liquid crystal displays and determine the minimum and optimal numbers of nanorods required in an array to achieve good color quality and intensity.

The optical reshaping of metallic nanostructures typically requires intense laser pulses to first approach or achieve melting, followed by surface-tension-dominated reshaping, transforming the original nanostructures into more spherical morphologies. Here, we report the directional optical reshaping of the Au nanodisk of an Al-Au heterodimer in the illuminated junction of an atomic force microscope (AFM). Both the heightening and the repositioning of the Au nanodisk component are induced, reducing the gap between the two nanodisks. There are three contributors to this process: the photothermal softening of the Au lattice, the optical force applied to the Au nanodisk by the Al nanodisk, and the optical force from the nearby AFM tip. The asymmetric reshaping of the heterodimer is observable structurally, through electron microscopic imaging, and through changes in the heterodimer optical response. This optical-force-directed shape manipulation may have potential applications in nanofabrication, optically induced nanomanufacturing, sensing, and quality control.

Infrared (IR) photodetection is of major scientific and technical interest since virtually all molecules exhibit characteristic vibrational modes in the mid-infrared region of the spectrum, giving rise to molecular spectroscopy and chemical imaging in this wavelength range. High-resolution IR spectroscopies, such as Fourier Transform IR spectroscopy, typically require large, bulky optical measurement systems and expensive photodetector components. Here, we present a high-responsivity photodetector for the mid-IR spectral region which operates at room temperature. Fabricated from silicon and aluminum, the photodetection mechanism is based on free carrier absorption, giving rise to a photoresponse rivalling commercially available cooled IR photodetectors. We demonstrate that infrared spectra of molecules deposited on this detector can be obtained by a direct electrical read-out. This work could pave the way for simple, fully integrated chemical sensors and other applications, such as chemical imaging, which would benefit from the combination of mid-IR detection, room-temperature operation, and ultracompact portability.Infrared (IR) photodetection is of major scientific and technical interest since virtually all molecules exhibit characteristic vibrational modes in the mid-infrared region of the spectrum, giving rise to molecular spectroscopy and chemical imaging in this wavelength range. High-resolution IR spectroscopies, such as Fourier Transform IR spectroscopy, typically require large, bulky optical measurement systems and expensive photodetector components. Here, we present a high-responsivity photodetector for the mid-IR spectral region which operates at room temperature. Fabricated from silicon and aluminum, the photodetection mechanism is based on free carrier absorption, giving rise to a photoresponse rivalling commercially available cooled IR photodetectors. We demonstrate that infrared spectra of molecules deposited on this detector can be obtained by a direct electrical read-out. This work could pave the way for simple, fully integrated chemical sensors and other applications, such as chemical imaging, which...

For applications seeking to realize on-chip polarization-discriminating nanoantennas, efficient energy conversion from surface waves to far-field radiation is desirable. However, the response of individual nanoantennas to the particular polarization states achievable in surface waves, such as evanescent fields, has not yet been thoroughly investigated. Here, we report the giant modulation of visible light scattering from achiral gold half-rings when switching between evanescent surface wave excitation produced from the total internal reflection of left-handed and right-handed circularly polarized light. The effect is driven by a differing relative phase between the in-plane transverse and longitudinal field oscillations of the evanescent wave depending on the incident light handedness. Because longitudinal field oscillations are not found in free-space excitation, this presents a fundamentally different mechanism for chiroptical responses as traditional mechanisms for circular dichroism only account for purely transversal field oscillations. Although the half-ring scattering modulation is dependent on the wave-vector orientation, an orientation invariant response is also realized in planar chiral nanoantennas composed of 8 half-rings in a rotationally symmetric arrangement, with up to 50% scattering modulation observed at 725 nm. Although both structures are found to produce scattering modulation when switching the handedness of free-space light, the distinct polarization properties of evanescent fields are shown to be strictly required to observe giant scattering modulation. These results ultimately deepen our understanding of the range of possible chiroptical effects in light-matter interactions.

Nanorods are amenable to laser-induced reshaping, a process that can dramatically modify their shape and therefore their plasmonic properties. Here we show that when a broadband spectral distribution of nanorods is irradiated with a femtosecond-pulsed laser, an optical transmission window is formed in the extinction spectrum. Surprisingly, the transmission window that is created does not occur at the laser wavelength but rather is consistently shifted to longer wavelengths, and the optical extinction on the short-wavelength side of the transmission window is increased by the hole-burning process. The laser irradiation results in a wavelength-dependent partial reshaping of the nanorods, creating a range of unusual nanoparticle morphologies. We develop a straightforward theoretical model that explains how the spectral position, depth, and width of the laser-induced transmission window are controlled by laser irradiation conditions. This work serves as an initial example of laser-based processing of speciall...

Plasmonic excitation of Au nanoparticles deposited on a MoS2 monolayer changes the absorption and photoluminescence characteristics of the material. Hot electrons generated from the Au nanoparticles are transferred into the MoS2 monolayers, resulting in n-doping. The doping effect of plasmonic hot electrons modulates the dielectric permittivity of materials, resulting in a red shift of both the absorption and the photoluminescence spectrum. This spectroscopic tuning was further investigated experimentally by using different Au nanoparticle concentrations, excitation laser wavelengths, and intensities. An analytical model for the photoinduced modulation of the MoS2 dielectric function and its exciton binding energy change is developed and used to estimate the doping density of plasmonic hot electrons. Our approach is important for the development of photonic devices for active control of light by light.

Fabrication of high-density plasmonic dimers on a large (wafer) scale is crucial for applications in surface-enhanced spectroscopy, bio- and molecular sensing, and optoelectronics. Here, we present an experimental approach based on nanoimprint lithography and shadow evaporation that allows for the fabrication of high-density, large-scale homo- (Au-Au and Ag-Ag) and hetero- (Au-Ag) dimer substrates with precise and consistent sub-10-nm gaps. We performed scanning electron, scanning transmission electron, and atomic force microscopy studies along with a complete electron energy-loss spectroscopy (EELS) characterization. We observed distinct plasmonic modes on these dimers, which are well interpreted by finite-difference time-domain (FDTD) and plasmon hybridization calculations.

Electron energy-loss spectroscopy (EELS) is a unique tool that is extensively used to investigate the plasmonic response of metallic nanostructures. We present here a novel approach for EELS calculations using the finite-difference time-domain (FDTD) method (EELS-FDTD). We benchmark our approach by direct comparison with results from the well-established boundary element method (BEM) and published experimental results. In particular, we compute EELS spectra for spherical nanoparticles, nanoparticle dimers, nanodisks supported by various substrates, and a gold bowtie antenna on a silicon nitride substrate. Our EELS-FDTD method can be easily extended to more complex geometries and configurations. This implementation can also be directly exported beyond the FDTD framework and implemented in other Maxwell’s equation solvers.

In a standing wave optical cavity, the coupling of cavity modes, for example, through a nonlinear medium, results in a rich variety of nonlinear dynamical phenomena, such as frequency pushing and pulling, mode-locking and pulsing, modal instabilities, even complex chaotic behavior. Metallic nanowires of finite length support a hierarchy of longitudinal surface plasmon modes with standing wave properties: the plasmonic analog of a Fabry-Pérot cavity. Here we show that positioning the nanowire within the gap of a plasmonic nanoantenna introduces a passive, hybridization-based coupling of the standing-wave nanowire plasmon modes with the antenna structure, mediating an interaction between the nanowire plasmon modes themselves. Frequency pushing and pulling, and the enhancement and suppression of specific plasmon modes, can be controlled and manipulated by nanoantenna position and shape.

The discovery of the photoelectric effect by Heinrich Hertz in 1887 set the foundation for over 125 years of hot carrier science and technology. In the early 1900s it played a critical role in the development of quantum mechanics, but even today the unique properties of these energetic, hot carriers offer new and exciting opportunities for fundamental research and applications. Measurement of the kinetic energy and momentum of photoejected hot electrons can provide valuable information on the electronic structure of materials. The heat generated by hot carriers can be harvested to drive a wide range of physical and chemical processes. Their kinetic energy can be used to harvest solar energy or create sensitive photodetectors and spectrometers. Photoejected charges can also be used to electrically dope two-dimensional materials. Plasmon excitations in metallic nanostructures can be engineered to enhance and provide valuable control over the emission of hot carriers. This Review discusses recent advances in the understanding and application of plasmon-induced hot carrier generation and highlights some of the exciting new directions for the field.