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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.

Significance The ability of certain materials to discriminate between two opposite light polarizations is the basic principle behind several technologies such as liquid crystal displays and three-dimensional glasses. While there are numerous forms of light polarization, only linear and circular polarizations, which have wave motion in a flat sheet or helix, respectively, are typically used. Here, we utilize trochoidal polarizations with cartwheeling wave motion. We demonstrate that single gold nanorod dimers can discriminate between trochoidal fields rotating in opposite directions, which we term trochoidal dichroism. Trochoidal dichroism forms an additional classification of polarized light–matter interaction and could inspire the development of optical studies uniquely sensitive to molecules with cartwheeling charge motion, potentially relevant for probing key light-harvesting antennas., Matter’s sensitivity to light polarization is characterized by linear and circular polarization effects, corresponding to the system’s anisotropy and handedness, respectively. Recent investigations into the near-field properties of evanescent waves have revealed polarization states with out-of-phase transverse and longitudinal oscillations, resulting in trochoidal, or cartwheeling, field motion. Here, we demonstrate matter’s inherent sensitivity to the direction of the trochoidal field and name this property trochoidal dichroism. We observe trochoidal dichroism in the differential excitation of bonding and antibonding plasmon modes for a system composed of two coupled dipole scatterers. Trochoidal dichroism constitutes the observation of a geometric basis for polarization sensitivity that fundamentally differs from linear and circular dichroism. It could also be used to characterize molecular systems, such as certain light-harvesting antennas, with cartwheeling charge motion upon excitation.

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.

Hot carriers reducing thermal barriers Plasmonic catalysts can generate hot charge carriers that can activate reactants and, in turn, reduce the overall barrier to a reaction. Zhou et al. studied the decomposition of ammonia to hydrogen on a copper alloy nanostructure that absorbed light and generated electrons that activated nitrogen atoms on ruthenium surface atoms (see the Perspective by Cortés). By measuring reaction rates at different wavelengths, light intensities, and catalyst surface temperatures, the light-induced reduction of the apparent activation barrier was quantified. Science , this issue p. 69 ; see also p. 28

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...

Engineering a compact, near-infrared plasmonic nanostructure with integrated image-enhancing agents for combined imaging and therapy is an important nanomedical challenge. Recently, we showed that Au@SiO2@Au nanomatryoshkas (NM) are a highly promising nanostructure for hosting either T1 MRI or fluorescent contrast agents with a photothermal therapeutic response in a compact geometry. Here, we show that a near-infrared-resonant NM can provide simultaneous contrast enhancement for both T1 magnetic resonance imaging (MRI) and fluorescence optical imaging (FOI) by encapsulating both types of contrast agents in the internal silica layer between the Au core and shell. We also show that this method of T1 enhancement is even more effective for Fe(III), a potentially safer contrast agent compared to Gd(III). Fe–NM-based contrast agents are found to have relaxivities 2× greater than those found in the widely used gadolinium chelate, Gd(III) DOTA, providing a practical alternative that would eliminate Gd(III) patien...

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.

Many important applications of nanometer-scale metallic complexes arise from the light-induced, near-field interactions between their component structures. Here we examine the near-field interactions in bimetallic Al-Au plasmonic nanodisk heterodimers, where the coupling between the primitive plasmons of nanostructures composed of two different metals is studied. Understanding the correlations between nanoparticle morphology and near-field optical properties, particularly for nanostructures composed of two different metals, requires spectrally resolved near-field spatial information. An ideal tool for such investigations is the recently developed photoinduced force microscopy, where the electromagnetic forces between an optically excited plasmonic nanostructure and an adjacent scanning nanoscale tip are measured. Using this approach, we visualize the wavelength-dependent near-field interactions in these bimetallic heterodimers. This system provides a prime example of the diabatic, antenna-reactor picture of plasmon coupling where for a given wavelength the more resonant primitive "driving" plasmon induces a response, the "forced" plasmon, in the off-resonant component. We critically examine spectrally resolved tip-nanostructure forces, comparing experiment with theory, for tips and nanoscale structures of realistic dimensions relative to frequently used approximations for tip geometries. The contrasting effects of dielectric versus metallic tips on acquired spectral force profiles are also examined.

We demonstrate, experimentally and theoretically, that the photon emission from gold nanorods can be viewed as a Purcell effect enhanced radiative recombination of hot carriers. By correlating the single-particle photoluminescence spectra and quantum yields of gold nanorods measured for five different excitation wavelengths and varied excitation powers, we illustrate the effects of hot carrier distributions evolving through interband and intraband transitions and the photonic density of states on the nanorod photoluminescence. Our model, using only one fixed input parameter, describes quantitatively both emission from interband recombination and the main photoluminescence peak coinciding with the longitudinal surface plasmon resonance.

Plasmon-induced hot carrier generation has attracted much recent attention due to its promising potential in photocatalysis and other light harvesting applications. Here we develop a theoretical model for hot carrier relaxation in metallic nanoparticles using a fully quantum mechanical jellium model. Following pulsed illumination, nonradiative plasmon decay results in a highly nonthermal distribution of hot electrons and holes. Using coupled master equations, we calculate the time-dependent evolution of this carrier distribution in the presence of electron–electron, electron–photon, and electron–phonon scattering. Electron–electron relaxation is shown to be the dominant scattering mechanism and results in efficient carrier multiplication where the energy of the initial hot electron–hole pair is transferred to other multiple electron–hole pair excitations of lower energies. During this relaxation, a small but finite fraction of electrons scatter into luminescent states where they can recombine radiatively ...

Plasmon hybridization theory, inspired by molecular orbital theory, has been extremely successful in describing the near-field coupling in clusters of plasmonic nanoparticles, also known as plasmonic molecules. However, the vibrational modes of plasmonic molecules have been virtually unexplored. By designing precisely configured plasmonic molecules of varying complexity and probing them at the individual plasmonic molecule level, intramolecular coupling of acoustic modes, mediated by the underlying substrate, is observed. The strength of this coupling can be manipulated through the configuration of the plasmonic molecules. Surprisingly, classical continuum elastic theory fails to account for the experimental trends, which are well described by a simple coupled oscillator picture that assumes the vibrational coupling is mediated by coherent phonons with low energies. These findings provide a route to the systematic optical control of the gigahertz response of metallic nanostructures, opening the door to new optomechanical device strategies.

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.

Recently, aluminum has been established as an earth-abundant alternative to gold and silver for plasmonic applications. Particularly, aluminum nanocrystals have shown to be promising plasmonic photocatalysts, especially when coupled with catalytic metals or oxides into “antenna-reactor” heterostructures. Here, a simple polyol synthesis is presented as a flexible route to produce aluminum nanocrystals decorated with eight varieties of size-tunable transition-metal nanoparticle islands, many of which have precedence as heterogeneous catalysts. High-resolution and three-dimensional structural analysis using scanning transmission electron microscopy and electron tomography shows that abundant nanoparticle island decoration in the catalytically relevant few-nanometer size range can be achieved, with many islands spaced closely to their neighbors. When coupled with the Al nanocrystal plasmonic antenna, these small decorating islands will experience increased light absorption and strong hot-spot generation. This combination makes transition-metal decorated aluminum nanocrystals a promising material platform to develop plasmonic photocatalysis, surface-enhanced spectroscopies, and quantum plasmonics., This research was financially supported by the National Science Foundation (NSF) grant ECCS-1610229, the Air Force Office of Scientific Research Multidisciplinary Research Program of the University Research Initiative (AFOSR MURI FA9550-15- 1-0022), the Army Research Office (MURI W911NF-12-1- 0407), Defense Threat Reduction Agency (HDTRA 1-16-1- 0042), the Welch Foundation under grants C-1220 (N.H.) and C-1222 (P.N.) and by the American Chemical Society Petroleum Research Fund under grant no. 56256 DNI5 (E.R.). D.S. acknowledges the National Science Foundation for a Graduate Research Fellowship under grant no. 1450681. D.R. acknowledges support by the Department of Defense (DoD) through the National Defense Science and Engineering Graduate Fellowship (NDSEG) Program. R.L. acknowledges a Junior Research Fellowship at Clare College, Cambridge. The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013)/ERC grant agreement 291522-3DIMAGE as well as from the European Union Seventh Framework Programme under grant agreement 312483-ESTEEM2 (Integrated Infrastructure Initiative − I3).

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.

Multifunctional nanoparticles for biomedical applications have shown extraordinary potential as contrast agents in various bioimaging modalities, near-IR photothermal therapy, and for light-triggered therapeutic release processes. Over the past several years, numerous studies have been performed to synthesize and enhance MRI contrast with nanoparticles. However, understanding the MRI enhancement mechanism in a multishell nanoparticle geometry, and controlling its properties, remains a challenge. To systematically examine MRI enhancement in a nanoparticle geometry, we have synthesized MRI-active Au nanomatryoshkas. These are Au core–silica layer–Au shell nanoparticles, where Gd(III) ions are encapsulated within the silica layer between the inner core and outer Au layer of the nanoparticle (Gd-NM). This multifunctional nanoparticle retains its strong near-IR Fano-resonant optical absorption properties essential for photothermal or other near-IR light-triggered therapy, while simultaneously providing increased T1 contrast in MR imaging by concentrating Gd(III) within the nanoparticle. Measurements of Gd-NM revealed a strongly enhanced T1 relaxivity (r1 ∼ 24 mM−1⋅s−1) even at 4.7 T, substantially surpassing conventional Gd(III) chelating agents (r1 ∼ 3 mM−1⋅s−1 at 4.7 T) currently in clinical use. By varying the thickness of the outer gold layer of the nanoparticle, we show that the observed relaxivities are consistent with Solomon–Bloembergen–Morgan (SBM) theory, which takes into account the longer-range interactions between the encapsulated Gd(III) and the protons of the H2O molecules outside the nanoparticle. This nanoparticle complex and its MRI T1-enhancing properties open the door for future studies on quantitative tracking of therapeutic nanoparticles in vivo, an essential step for optimizing light-induced, nanoparticle-based therapies.

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...

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

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 ...

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 enhancement that can be designed into their constituent meta-atoms. Here, we demonstrate vacuum ultraviolet (VUV) third harmonic generation from a specially designed dielectric metasurface consisting of a titanium dioxide (TiO

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)].

Photocatalysis with optically active "plasmonic" nanoparticles is a growing field in heterogeneous catalysis, with the potential for substantially increasing efficiencies and selectivities of chemical reactions. Here, the decomposition of nitrous oxide (N

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.

Sivan et al . claim that the methods used to distinguish thermal from hot carrier effects in our recent report are inaccurate and that our data can be explained by a purely thermal mechanism with a fixed activation energy. This conclusion is invalid, because they substantially misinterpret the emissivity of the photocatalyst and assume a linear intensity–dependent temperature in their model that is unrealistic.

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.

Hydrated electrons are important in radiation chemistry and chargetransfer reactions, with applications that include chemical damage of DNA,\ud catalysis, and signaling. Conventionally, hydrated electrons are produced by pulsed\ud radiolysis, sonolysis, two-ultraviolet-photon laser excitation of liquid water, or\ud photodetachment of suitable electron donors. Here we report a method for the\ud generation of hydrated electrons via single-visible-photon excitation of localized\ud surface plasmon resonances (LSPRs) of supported sub-3 nm copper nanoparticles\ud in contact with water. Only excitations at the LSPR maximum resulted in the\ud formation of hydrated electrons, suggesting that plasmon excitation plays a crucial\ud role in promoting electron transfer from the nanoparticle into the solution. The\ud reactivity of the hydrated electrons was confirmed via proton reduction and\ud concomitant H2 evolution in the presence of a Ru/ TiO2 catalyst.

Aluminum nanocrystals have emerged as an earth-abundant material for plasmonics applications. Al nanocrystals readily oxidize in aqueous-based solutions, however, transforming into highly stratified γ-AlOOH nanoparticles with a 700% increase in surface area in a matter of minutes. Here we show that by functionalizing Al nanocrystals with the bioinspired polymer polydopamine, their stability in aqueous media is dramatically increased, maintaining their integrity in aqueous solution for over 2 weeks with no discernible structural changes. Polydopamine functionalization also provides a molecular capture layer that enables the capture of polycyclic aromatic hydrocarbon pollutants in H2O samples and their detection by surface-enhanced Raman spectroscopy, when polydopamine-stabilized Al nanocrystal aggregates are used as substrates. This approach was used to detect a prime carcinogenic H2O pollutant, benzo[a]pyrene with a sensitivity in the sub part-per-billion range.

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 precise size- and shape-controlled synthesis of monodisperse Al nanocrystals remains an open challenge, limiting their utility for numerous applications that would take advantage of their size and shape-dependent optical properties. Here we pursue a molecular-level understanding of the formation of Al nanocrystals by titanium(IV) isopropoxide-catalyzed decomposition of AlH

Of the many plasmonic nanoparticle geometries that have been synthesized, nanocubes have been of particular interest for creating nanocavities, facilitating plasmon coupling, and enhancing phenomena dependent upon local electromagnetic fields. Here we report the straightforward colloidal synthesis of single-crystalline {100} terminated Al nanocubes by decomposing AlH3 with Tebbe’s reagent in tetrahydrofuran. The size and shape of the Al nanocubes is controlled by the reaction time and the ratio of AlH3 to Tebbe’s reagent, which, together with reaction temperature, establish kinetic control over Al nanocube growth. Al nanocubes possess strong localized field enhancements at their sharp corners and resonances highly amenable to coupling with metallic substrates. Their native oxide surface renders them extremely air stable. Chemically synthesized Al nanocubes provide an earth-abundant alternative to noble metal nanocubes for plasmonics and nanophotonics applications.

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.

Inelastic electron tunneling and surface-enhanced optical spectroscopies at the molecular scale require cryogenic local temperatures even under illumination - conditions that are challenging to achieve with plasmonically resonant metallic nanostructures. We report a detailed study of the laser heating of plasmonically active nanowires at substrate temperatures from 5 to 60 K. The increase of the local temperature of the nanowire is quantified by a bolometric approach and could be as large as 100 K for a substrate temperature of 5 K and typical values of laser intensity. We also demonstrate that a $\sim 3\times$ reduction of the local temperature increase is possible by switching to a sapphire or quartz substrate. Finite element modeling of the heat dissipation reveals that the local temperature increase of the nanowire at temperatures below $\sim$50 K is determined largely by the thermal boundary resistance of the metal-substrate interface. The model reproduces the striking experimental trend that in this regime the temperature of the nanowire varies nonlinearly with the incident optical power. The thermal boundary resistance is demonstrated to be a major constraint on reaching low temperatures necessary to perform simultaneous inelastic electron tunneling and surface enhanced Raman spectroscopies., Comment: 20 pages, 5 figures + 17 pages supporting material

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...