Phototransformation of achiral metasurfaces into handedness-selectable transient chiral media.

Chirality is a geometric property describing the lack of mirror symmetry. This unique feature enables photonic spin-selectivity in light-matter interaction, which is of great significance in stereochemistry, drug development, quantum optics, and optical polarization control. The versatile control of optical geometry renders optical metamaterials as an effective platform for engineered chiral properties at prescribed spectral regimes. Unfortunately, geometry-imposed restrictions only allow one circular polarization state of photons to effectively interact with chiral meta-structures. This limitation motivates the idea of discovering alternative techniques for dynamically reconfiguring the chiroptical responses of metamaterials in a fast and facile manner. Here, we demonstrate an approach that enables optical, sub-picosecond conversion of achiral meta-structures to transient chiral media in the visible regime with desired handedness upon the inhomogeneous generation of plasmonic hot electrons. As a proof of concept, we utilize linearly polarized laser pulse to demonstrate near-complete conversion of spin sensitivity in an achiral meta-platform-a functionality yet achieved in a non-mechanical fashion. Owing to the generation, diffusion, and relaxation dynamics of hot electrons, the demonstrated technique for all-optical creation of chirality is inherently fast, opening new avenues for ultrafast spectro-temporal construction of chiral platforms with on-demand spin-selectivity.

Quantifying the ultrafast and steady-state molecular reduction potential of a plasmonic photocatalyst.

Plasmonic materials are promising photocatalysts as they are well suited to convert light into hot carriers and heat. Hot electron transfer is suggested as the driving force in many plasmon-driven reactions. However, to date, there are no direct molecular measures of the rate and yield of plasmon-to-molecule electron transfer or energy of these electrons on the timescale of plasmon decay. Here, we use ultrafast and spectroelectrochemical surface-enhanced Raman spectroscopy to quantify electron transfer from a plasmonic substrate to adsorbed methyl viologen molecules. We observe a reduction yield of 2.4 to 3.5% on the picosecond timescale, with plasmon-induced potentials ranging from [Formula: see text]3.1 to [Formula: see text]4.5 mV. Excitingly, some of these reduced species are stabilized and persist for tens of minutes. This work provides concrete metrics toward optimizing material-molecule interactions for efficient plasmon-driven photocatalysis.

Nonlinear vectorial holography with quad-atom metasurfaces.

Vectorial optical holography represents a solution to control the polarization and amplitude distribution of light in the Fourier space. While vectorial optical holography has been experimentally demonstrated in the linear optical regime, its nonlinear counterpart, which can provide extra degrees of freedom of light-field manipulation through the frequency conversion processes, remains unexplored. Here, we experimentally demonstrate the nonlinear vectorial holography through the second harmonic generation process on a quad-atom plasmonic metasurface. The quad-atom metasurface consists of gold meta-atoms with threefold rotational symmetry. Based on the concept of nonlinear geometric phase, we can simultaneously manipulate the phase and amplitude of the left and right circularly polarized second harmonic waves generated from the quad-atom metasurface. By superposing the two orthogonal polarization components, the quad-atom metasurface can produce nonlinear holographic images with vectorial polarization distributions. The proposed metasurface platform may have important applications in vectorial polarization nonlinear optical source, high-capacity optical information storage, and optical encryption.

Aluminum Cayley trees as scalable, broadband, multiresonant optical antennas.

An optical antenna can convert a propagative optical radiation into a localized excitation and the reciprocal. Although optical antennas can be readily created using resonant nanoparticles (metallic or dielectric) as elementary building blocks, the realization of antennas sustaining multiple resonances over a broad range of frequencies remains a challenging task. Here, we use aluminum self-similar, fractal-like structures as broadband optical antennas. Using electron energy loss spectroscopy, we experimentally evidence that a single aluminum Cayley tree, a simple self-similar structure, sustains multiple plasmonic resonances. The spectral position of these resonances is scalable over a broad spectral range spanning two decades, from ultraviolet to midinfrared. Such multiresonant structures are highly desirable for applications ranging from nonlinear optics to light harvesting and photodetection, as well as surface-enhanced infrared absorption spectroscopy.

Interfacial engineering of plasmonic nanoparticle metasurfaces.

SignificanceMolecules interacting with metallic nanostructures can show tunable exciton-plasmon coupling, ranging from weak to strong. One factor that influences the interactions is the spatial organization of the molecules relative to the localized plasmon-enhanced electromagnetic fields. In this work, we show that the arrangement of aromatic dye molecules can be tuned within plasmonic hotspots by interfacial engineering of nanoparticle surfaces. By controlling the local chemical and physical interactions, we could modulate lasing thresholds. Surface-functionalized plasmonic metasurfaces open prospects for programmable light-matter interactions at the nanoscale.

Molecularly Detailed View of Strong Coupling in Supramolecular Plexcitonic Nanohybrids.

Plexcitons constitute a peculiar example of light-matter hybrids (polaritons) originating from the (strong) coupling of plasmonic modes and molecular excitations. Here we propose a fully quantum approach to model plexcitonic systems and test it against existing experiments on peculiar hybrids formed by Au nanoparticles and a well-known porphyrin derivative, involving the Q branch of the organic dye absorption spectrum. Our model extends simpler descriptions of polaritonic systems to account for the multilevel structure of the dyes, spatially varying interactions with a given plasmon mode, and the simultaneous occurrence of plasmon-molecule and intermolecular interactions. By keeping a molecularly detailed view, we were able to gain insights into the local structure and individual contributions to the resulting plexcitons. Our model can be applied to rationalize and predict energy funneling toward specific molecular sites within a plexcitonic assembly, which is highly valuable for designing and controlling chemical transformations in the new polaritonic landscapes.

Plasmonic Diamond Membranes for Ultrafast Silicon Vacancy Emission.

Silicon vacancy centers (SiVs) in diamond have emerged as a promising platform for quantum sciences due to their excellent photostability, minimal spectral diffusion, and substantial zero-phonon line emission. However, enhancing their slow nanosecond excited-state lifetime by coupling to optical cavities remains an outstanding challenge, as current demonstrations are limited to ∼10-fold. Here, we couple negatively charged SiVs to sub-diffraction-limited plasmonic cavities and achieve an instrument-limited ≤8 ps lifetime, corresponding to a 135-fold spontaneous emission rate enhancement and a 19-fold photoluminescence enhancement. Nanoparticles are printed on ultrathin diamond membranes on gold films which create arrays of plasmonic nanogap cavities with ultrasmall volumes. SiVs implanted at 5 and 10 nm depths are examined to elucidate surface effects on their lifetime and brightness. The interplay between cavity, implantation depth, and ultrathin diamond membranes provides insights into generating ultrafast, bright SiV emission for next-generation diamond devices.

Enhanced Green Light Emission from a Silicon-Based Metal-Encapsulated Nanoplasmonic Waveguide.

Integrated silicon plasmonic circuitry is becoming integral for communications and data processing. One key challenge in implementing such optical networks is the realization of optical sources on silicon platforms, due to silicon's indirect bandgap. Here, we present a silicon-based metal-encapsulated nanoplasmonic waveguide geometry that can mitigate this issue and efficiently generate light via third-harmonic generation (THG). Our waveguides are ideal for such applications, having strong power confinement and field enhancement, and an effective use of the nonlinear core area. This unique device was fabricated, and experimental results show efficient THG conversion efficiencies of η = 4.9 × 10-4, within a core footprint of only 0.24 µm2. Notably, this is the highest absolute silicon-based THG conversion efficiency presented to date. Furthermore, the nonlinear emission is not constrained by phase matching. These waveguides are envisioned to have crucial applications in signal generation within integrated nanoplasmonic circuits.

Few-Cycle Surface Plasmon Polaritons.

Surface plasmon polaritons (SPPs) can confine and guide light in nanometer volumes and are ideal tools for achieving electric field enhancement and the construction of nanophotonic circuitry. The realization of the highest field strengths and fastest switching requires confinement also in the temporal domain. Here, we demonstrate a tapered plasmonic waveguide with an optimized grating structure that supports few-cycle surface plasmon polaritons with >70 THz bandwidth while achieving >50% light-field-to-plasmon coupling efficiency. This enables us to observe the─to our knowledge─shortest reported SPP wavepackets. Using time-resolved photoelectron microscopy with suboptical-wavelength spatial and sub-10 fs temporal resolution, we provide full spatiotemporal imaging of co- and counter-propagating few-cycle SPP wavepackets along tapered plasmonic waveguides. By comparing their propagation, we track the evolution of the laser-plasmon phase, which can be controlled via the coupling conditions.

Thermal Stability of Au Rhombic Dodecahedral Nanocrystals Can Be Greatly Enhanced by Coating Their Surface with an Ultrathin Shell of Pt.

Rhombic dodecahedral nanocrystals have been considered particularly difficult to synthesize because they are enclosed by {110}, a low-index facet with the greatest surface energy. Recently, we demonstrated the use of seed-mediated growth for the facile and robust synthesis of Au rhombic dodecahedral nanocrystals (AuRD). While the unique shape and surface structure of AuRD are desirable for potential applications in plasmonics and catalysis, respectively, their high surface energy makes them highly susceptible to thermal degradation. Here we demonstrate that it is feasible to greatly improve the thermal stability with some sacrifice to the plasmonic properties of the original AuRD by coating their surface with an ultrathin shell made of Pt. Our in situ electron microscopy analysis indicates that the ultrathin Pt coating can increase the thermal stability from 60 up to 450 °C, a trend that is also supported by the results from a computational study.

Electroluminescence as a Probe of Strong Exciton-Plasmon Coupling in Few-Layer WSe2.

The manipulation of coupled quantum excitations is of fundamental importance in realizing novel photonic and optoelectronic devices. We use electroluminescence to probe plasmon-exciton coupling in hybrid structures consisting of a nanoscale plasmonic tunnel junction and few-layer two-dimensional transition-metal dichalcogenide transferred onto the junction. The resulting hybrid states act as a novel dielectric environment that affects the radiative recombination of hot carriers in the plasmonic nanostructure. We determine the plexcitonic spectrum from the electroluminescence and find Rabi splittings exceeding 50 meV in the strong coupling regime. Our experimental findings are supported by electromagnetic simulations that enable us to explore systematically and in detail the emergence of plexciton polaritons as well as the polarization characteristics of their far-field emission. Electroluminescence modulated by plexciton coupling provides potential applications for engineering compact photonic devices with tunable optical and electrical properties.

Twist-Angle-Controlled Nonlinear Circular Dichroism on Gold-Crystal Hybrid Metasurfaces.

Optical chirality, which plays important roles in liquid crystal display and biological and chemical detection, has been attracting scientists' attention due to its potential applications in optical information processing. Usually, the chiral optical response of natural molecules is very weak. However, the emergence of metasurfaces offers a promising solution to solve this issue. By judiciously designing the geometry of meta-atoms, we have realized strong optical circular dichroism (CD) in both linear and nonlinear optical regimes. However, tuning of the CD with a metasurface remains challenging. Here, we propose the twist-angle-controlled nonlinear CD effect by using the second-harmonic generation process on a gold-crystal hybrid metasurface. The CD effect of the second-harmonic waves can be tuned well by controlling the twist angle between the two constituent materials. The proposed hybrid metasurface may open new avenues for developing ultracompact and multifunctional nonlinear optical devices.

Mass Transport Limitations in Plasmonic Photocatalysis.

The interpretation of mechanisms governing hot carrier reactivity on metallic nanostructures is critical, yet elusive, for advancing plasmonic photocatalysis. In this work, we explored the influence of the diffusion of molecules on the hot carrier extraction rate at the solid-liquid interface, which is of fundamental interest for increasing the efficiency of photodevices. Through a spatially defined scanning photoelectrochemical microscopy investigation, we identified a diffusion-controlled regime hindering the plasmon-driven photochemical activity of metallic nanostructures. Using low-power monochromatic illumination (<2 W cm-2), we unveiled the hidden influence of mass transport on the quantum efficiency of plasmonic photocatalysts. The availability of molecules at the solid-liquid interface directly limits the extraction of hot holes, according to their nature and energy, at the reactive spots in Au nanoislands on an ultrathin TiO2 substrate. An intriguing question arises: does the mass transport enhancement caused by thermal effects unlock the reactivity of nonthermal carriers under steady state?

Plasmonic Optical Wells-Based Enhanced Rate PCR.

Rapid, sensitive, inexpensive point-of-care molecular diagnostics are crucial for the efficient control of spreading viral diseases and biosecurity of global health. However, the gold standard, polymerase chain reaction (PCR) is time-consuming and expensive and needs specialized testing laboratories. Here, we report a low-cost yet fast, selective, and sensitive Plasmonic Optical Wells-Based Enhanced Rate PCR: POWER-PCR. We optimized the efficient optofluidic design of 3D plasmonic optical wells via the computational simulation of light-to-heat conversion and thermophoretic convection in a self-created plasmonic cavity. The POWER-PCR chamber with a self-passivation layer can concentrate incident light to accumulate molecules, generate rapid heat transfer and thermophoretic flow, and minimize the quenching effect on the naked Au surface. Notably, we achieved swift photothermal cycling of nucleic acid amplification in POWER-PCR on-a-chip in 4 min 24 s. The POWER-PCR will provide an excellent solution for affordable and sensitive molecular diagnostics for precision medicine and preventive global healthcare.

Universal Chiral-Plasmon-Induced Upward and Downward Transfer of Circular Dichroism to Achiral Molecules.

Electromagnetic chirality transfer represents an effective means of the nanoscale manipulation of optical chirality. While most of the previous reports have exclusively focused on the circular dichroism (CD) transfer from UV-responsive chiral molecules toward visible-resonant achiral colloidal nanoparticles, here we demonstrate a reverse process in which plasmonic chirality can be transferred to achiral molecules, either upward from visible to UV or downward from visible to near infrared (NIR). By hybridizing achiral UV- or NIR-responsive dye molecules with chiral metal nanoparticles in solution, we observe a chiral-plasmon-induced CD (CPICD) signal at the intrinsically achiral molecular absorption bands. Full-wave electromagnetic modeling reveals that both near-field Coulomb interaction and far-field radiative coupling contribute to the observed CPICD, indicating that the mechanism considered here is universal for different material systems and types of optical resonances. Our study provides a set of design guidelines for broadband nanophotonic chiral sensing from the UV to NIR spectral regime.

Enhanced Light-Matter Interaction in Metallic Nanoparticles: A Generic Strategy of Smart Void Filling.

The intrinsic properties of materials play a substantial role in light-matter interactions, impacting both bulk metals and nanostructures. While plasmonic nanostructures exhibit strong interactions with photons via plasmon resonances, achieving efficient light absorption/scattering in other transition metals remains a challenge, impeding various applications related to optoelectronics, chemistry, and energy harvesting. Here, we propose a universal strategy to enhance light-matter interaction, through introducing voids onto the surface of metallic nanoparticles. This strategy spans nine metals including those traditionally considered optically inactive. The absorption cross section of void-filled nanoparticles surpasses the value of plasmonic (Ag/Au) counterparts with tunable resonance peaks across a broad spectral range. Notably, this enhancement is achieved under arbitrary polarizations and varied particle sizes and in the presence of geometric disorder, highlighting the universal adaptability. Our strategy holds promise for inspiring emerging devices in photocatalysis, bioimaging, optical sensing, and beyond, particularly when metals other than gold or silver are preferred.

Far-Field Petahertz Sampling of Plasmonic Fields.

The response of metal nanostructures to optical excitation leads to localized surface plasmon (LSP) generation with nanoscale field confinement driving applications in, for example, quantum optics and nanophotonics. Field sampling in the terahertz domain has had a tremendous impact on the ability to trace such collective excitations. Here, we extend such capabilities and introduce direct sampling of LSPs in a more relevant petahertz domain. The method allows to measure the LSP field in arbitrary nanostructures with subcycle precision. We demonstrate the technique for colloidal nanoparticles and compare the results to finite-difference time-domain calculations, which show that the build-up and dephasing of the plasmonic excitation can be resolved. Furthermore, we observe a reshaping of the spectral phase of the few-cycle pulse, and we demonstrate ad-hoc pulse shaping by tailoring the plasmonic sample. The methodology can be extended to single nanosystems and applied in exploring subcycle, attosecond phenomena.

Probing the Interaction between Individual Metal Nanocrystals and Two-Dimensional Metal Oxides via Electron Energy Loss Spectroscopy.

Metal nanoparticles can photosensitize two-dimensional metal oxides, facilitating their electrical connection to devices and enhancing their abilities in catalysis and sensing. In this study, we investigated how individual silver nanoparticles interact with two-dimensional tin oxide and antimony-doped indium oxide using electron energy loss spectroscopy (EELS). The measurement of the spectral line width of the longitudinal plasmon resonance of the nanoparticles in absence and presence of 2D materials allowed us to quantify the contribution of chemical interface damping to the line width. Our analysis reveals that a stronger interaction (damping) occurs with 2D antimony-doped indium oxide due to its highly homogeneous surface. The results of this study offer new insight into the interaction between metal nanoparticles and 2D materials.

Determining Transmission Characteristics from Shot-Noise-Driven Electroluminescence in Single-Molecule Junctions.

Biased metal-molecule-metal junctions emit light through electroluminescence, a phenomenon at the intersection of molecular electronics and nanoplasmonics. This can occur when the junction plasmon mode is excited by inelastic electron current fluctuations. Here, we simultaneously measure the conductance and electroluminescence intensity from single-molecule junctions with time resolution in a solution environment at room temperature. We use current versus bias data to determine the molecular junction transport parameters and then relate these to the expected current shot noise. We find that the electroluminescence signal accurately matches the theoretical prediction of shot-noise-driven emission in a large fraction of the molecular junctions studied. This introduces a novel experimental method for qualitatively estimating finite-frequency shot noise in single-molecule junctions under ambient conditions. We further demonstrate that electroluminescence can be used to obtain the level alignment of the frontier orbital dominating transport in the molecular junction.

Ultrafast Laser-Induced Dynamics of Non-Equilibrium Electron Spill-Out in Nanoplasmonic Bilayers.

Contemporary quantum plasmonics capture subtle corrections to the properties of plasmonic nano-objects in equilibrium. Here, we demonstrate non-equilibrium spill-out redistribution of the electronic density at the ultrafast time scale. As revealed by time-resolved 2D spectroscopy of nanoplasmonic Fe/Au bilayers, an injection of the laser-excited non-thermal electrons induces transient electron spill-out thus changing the plasma frequency. The response of the local electronic density switches the electronic density behavior from spill-in to strong (an order of magnitude larger) spill-out at the femtosecond time scale. The superdiffusive transport of hot electrons and the lack of a direct laser heating indicate significantly non-thermal origin of the underlying physics. Our results demonstrate an ultrafast and non-thermal way to control surface plasmon dispersion through transient variations of the spatial electron distribution at the nanoscale. These findings expand quantum plasmonics into previously unexplored directions by introducing ultrashort time scales in the non-equilibrium electronic systems.