Permittivity-Asymmetric Quasi-Bound States in the Continuum.

Breaking the in-plane geometric symmetry of dielectric metasurfaces allows us to access a set of electromagnetic states termed symmetry-protected quasi-bound states in the continuum (qBICs). Here we demonstrate that qBICs can also be accessed by a symmetry breaking in the permittivity of the comprising materials. While the physical size of atoms imposes a limit on the lowest achievable geometrical asymmetry, weak permittivity modulations due to carrier doping, and electro-optical Pockels and Kerr effects, usually considered insignificant, open the possibility of infinitesimal permittivity asymmetries for on-demand, dynamically tunable resonances of extremely high quality factors. As a proof-of-principle, we probe the excitation of permittivity-asymmetric qBICs (ε-qBICs) using a prototype Si/TiO2 metasurface, in which the asymmetry in the unit cell is provided by the permittivity contrast of the materials. ε-qBICs are also numerically demonstrated in 1D gratings, where quality-factor enhancement and tailored interference phenomena of qBICs are shown via the interplay of geometrical and permittivity asymmetries.

Launching directional hypersonic surface waves in monolithic gallium phosphide nanodisks: two holes are better than one.

The emergence and rapid progress of all-dielectric nanoantennas have provided unprecedented platforms for applications in sensing, optical control of light, opto-mechanics and metrology at the nanoscale. We present a general figure-of-merit (FOM) considering both optical and vibrational responses. Detectable mechanical vibrations ranging from gigahertz to terahertz in gallium phosphide (GaP) structures on sub-wavelength scales are found to surpass their metallic counterparts in a 400-800 nm pump-probe configuration. Then, we tailored low-aspect ratio GaP disks being probed near their optical anapole resonance. We further broke the isotropy of the nanodisks and achieved pronounced directional propagation for launching surface acoustic waves (SAWs) with a double-hole structure rather than with a one-hole configuration, which could be attributed to the constructive superposition of vibration induced by the two holes in the appropriate direction. Finally, we demonstrated that the orbital angular momentum of SAWs could be generated with a spiral distribution of the two-hole nanodisks. Our work paves a new way to monolithic GaP nanoantennas towards photoacoustic applications such as hypersound routers, stirring up inverse designs of individual antennas for phononic metasurfaces, topological phononics as well as quantum phononics.

Large Area Patterning of Highly Reproducible and Sensitive SERS Sensors Based on 10-nm Annular Gap Arrays.

Applicable surface-enhanced Raman scattering (SERS) active substrates typically require low-cost patterning methodology, high reproducibility, and a high enhancement factor (EF) over a large area. However, the lack of reproducible, reliable fabrication for large area SERS substrates in a low-cost manner remains a challenge. Here, a patterning method based on nanosphere lithography and adhesion lithography is reported that allows massively parallel fabrication of 10-nm annular gap arrays on large areas. The arrays exhibit excellent reproducibility and high SERS performance, with an EF of up to 107. An effective wearable SERS contact lens for glucose detection is further demonstrated. The technique described here extends the range of SERS-active substrates that can be fabricated over large areas, and holds exciting potential for SERS-based chemical and biomedical detection.

Radial bound states in the continuum for polarization-invariant nanophotonics.

All-dielectric nanophotonics underpinned by the physics of bound states in the continuum (BICs) have demonstrated breakthrough applications in nanoscale light manipulation, frequency conversion and optical sensing. Leading BIC implementations range from isolated nanoantennas with localized electromagnetic fields to symmetry-protected metasurfaces with controllable resonance quality (Q) factors. However, they either require structured light illumination with complex beam-shaping optics or large, fabrication-intense arrays of polarization-sensitive unit cells, hindering tailored nanophotonic applications and on-chip integration. Here, we introduce radial quasi-bound states in the continuum (radial BICs) as a new class of radially distributed electromagnetic modes controlled by structural asymmetry in a ring of dielectric rod pair resonators. The radial BIC platform provides polarization-invariant and tunable high-Q resonances with strongly enhanced near fields in an ultracompact footprint as low as 2 µm2. We demonstrate radial BIC realizations in the visible for sensitive biomolecular detection and enhanced second-harmonic generation from monolayers of transition metal dichalcogenides, opening new perspectives for compact, spectrally selective, and polarization-invariant metadevices for multi-functional light-matter coupling, multiplexed sensing, and high-density on-chip photonics.

Self-Constructed Multiple Plasmonic Hotspots on an Individual Fractal to Amplify Broadband Hot Electron Generation.

Plasmonic nanoparticles are ideal candidates for hot-electron-assisted applications, but their narrow resonance region and limited hotspot number hindered the energy utilization of broadband solar energy. Inspired by tree branches, we designed and chemically synthesized silver fractals, which enable self-constructed hotspots and multiple plasmonic resonances, extending the broadband generation of hot electrons for better matching with the solar radiation spectrum. We directly revealed the plasmonic origin, the spatial distribution, and the decay dynamics of hot electrons on the single-particle level by using ab initio simulation, dark-field spectroscopy, pump-probe measurements, and electron energy loss spectroscopy. Our results show that fractals with acute tips and narrow gaps can support broadband resonances (400-1100 nm) and a large number of randomly distributed hotspots, which can provide unpolarized enhanced near field and promote hot electron generation. As a proof-of-concept, hot-electron-triggered dimerization of p-nitropthiophenol and hydrogen production are investigated under various irradiations, and the promoted hot electron generation on fractals was confirmed with significantly improved efficiency.

Massively Parallel Arrays of Size-Controlled Metallic Nanogaps with Gap-Widths Down to the Sub-3-nm Level.

Metallic nanogaps (MNGs) are fundamental components of nanoscale photonic and electronic devices. However, the lack of reproducible, high-yield fabrication methods with nanometric control over the gap-size has hindered practical applications. A patterning technique based on molecular self-assembly and physical peeling is reported here that allows the gap-width to be tuned from more than 30 nm to less than 3 nm. The ability of the technique to define sub-3-nm gaps between dissimilar metals permits the easy fabrication of molecular rectifiers, in which conductive molecules bridge metals with differing work functions. A method is further described for fabricating massively parallel nanogap arrays containing hundreds of millions of ring-shaped nanogaps, in which nanometric size control is maintained over large patterning areas of up to a square centimeter. The arrays exhibit strong plasmonic resonances under visible light illumination and act as high-performance substrates for surface-enhanced Raman spectroscopy, with high enhancement factors of up to 3 × 108 relative to thin gold films. The methods described here extend the range of metallic nanostructures that can be fabricated over large areas, and are likely to find many applications in molecular electronics, plasmonics, and biosensing.

Nanostructured amorphous gallium phosphide on silica for nonlinear and ultrafast nanophotonics.

Nanophotonics based on high refractive index dielectrics relies on appreciable contrast between the indices of designed nanostructures and their immediate surrounding, which can be achieved by the growth of thin films on low-index substrates. Here we propose the use of high index amorphous gallium phosphide (a-GaP), fabricated by radio-frequency sputter deposition, on top of a low refractive index glass substrate and thoroughly examine its nanophotonic properties. Spectral ellipsometry of the amorphous material demonstrates the optical properties to be considerably close to crystalline gallium phosphide (c-GaP), with low-loss transparency for wavelengths longer than 650 nm. When nanostructured into nanopatches, the second harmonic (SH) response of an individual a-GaP patch is characterized to be more than two orders of magnitude larger than the as-deposited unstructured film, with an anapole-like resonant behavior. Numerical simulations are in good agreement with the experimental results over a large spectral and geometrical range. Furthermore, by studying individual a-GaP nanopatches through non-degenerate pump-probe spectroscopy with sub-10 fs pulses, we find a more than 5% ultrafast modulation of the reflectivity that is accompanied by a slower decaying free carrier contribution, caused by absorption. Our investigations reveal a potential for a-GaP as an adequate inexpensive and CMOS-compatible material for nonlinear nanophotonic applications as well as for photocatalysis.

Efficient ultrafast all-optical modulation in a nonlinear crystalline gallium phosphide nanodisk at the anapole excitation.

High-refractive index nanostructured dielectrics have the ability to locally enhance electromagnetic fields with low losses while presenting high third-order nonlinearities. In this work, we exploit these characteristics to achieve efficient ultrafast all-optical modulation in a crystalline gallium phosphide (GaP) nanoantenna through the optical Kerr effect (OKE) and two-photon absorption (TPA) in the visible/near-infrared range. We show that an individual GaP nanodisk can yield differential reflectivity modulations of up to ~40%, with characteristic modulation times between 14 and 66 fs, when probed at the anapole excitation (AE). Numerical simulations reveal that the AE represents a unique condition where both the OKE and TPA contribute with the same modulation sign, maximizing the response. These findings highly outperform previous reports on sub-100-fs all-optical switching from resonant nanoscale dielectrics, which have demonstrated modulation depths no larger than 0.5%, placing GaP nanoantennas as a promising choice for ultrafast all-optical modulation at the nanometer scale.

Near-Field Spectroscopy of Cylindrical Phonon-Polariton Antennas.

Surface phonon polaritons (SPhPs) are hybrid light-matter states in which light strongly couples to lattice vibrations inside the Reststrahlen band of polar dielectrics at mid-infrared frequencies. Antennas supporting localized surface phonon polaritons (LSPhPs) easily outperform their plasmonic counterparts operating in the visible or near-infrared in terms of field enhancement and confinement thanks to the inherently slower phonon-phonon scattering processes governing SPhP decay. In particular, LSPhP antennas have attracted considerable interest for thermal management at the nanoscale, where the emission strongly diverts from the usual far-field blackbody radiation due to the presence of evanescent waves at the surface. However, far-field measurements cannot shed light on the behavior of antennas in the near-field region. To overcome this limitation, we employ scattering-scanning near-field optical microscopy (sSNOM) to unveil the spectral near-field response of 3C-SiC antenna arrays. We present a detailed description of the behavior of the antenna resonances by comparing far-field and near-field spectra and demonstrate the existence of a mode with no net dipole moment, absent in the far-field spectra, but of importance for applications that exploit the heightened electromagnetic near fields. Furthermore, we investigate the perturbation in the antenna response induced by the presence of the AFM tip, which can be further extended toward situations where for example strong IR emitters couple to LSPhP modes.

From Optical to Chemical Hot Spots in Plasmonics.

In recent years, the possibility to induce chemical transformations by using tunable plasmonic modes has opened the question of whether we can control or create chemical hot spots in these systems. This can be rationalized as the reactive analogue of the well-established concept of optical hot spots, which have drawn a great deal of attention to plasmonic nanostructures for their ability to circumvent the far-field diffraction limit of conventional optical elements. Although optical hot spots can be mainly defined by the geometry and permittivity of the nanostructures, the degrees of freedom influencing their photocatalytic properties appear to be much more numerous. In fact, the reactivity of plasmonic systems are deeply influenced by the dynamics and interplay of photons, plasmon-polaritons, carriers, phonons, and molecular states. These degrees of freedom can affect the reaction rates, the product selectivity, or the spatial localization of a chemical reaction. In this Account, we discuss the oportunities to control chemical hot spots by tuning the cascade of events that follows the excitation and decay of plasmonic modes in nanostructures. We discuss a series of techniques to spatially map and image plasmonic nanoscale reactivity at the single photocatalyst level. We show how to optimize the reactivity of carriers by manipulating their excitation and decay mechanisms in plasmonic nanoparticles. In addition, the tailored generation of non-thermal phonons in metallic nanostructures and their dissipation is shown as a promise to understand and exploit thermal photocatalysis at the nanoscale. Understanding and controlling these processes is essential for the rational design of solar nanometric photocatalysts. Nevertheless, the ultimate capability of a plasmonic photocatalyst to trigger a chemical reaction is correlated to its ability to navigate through, or even modify, the potential energy surface of a given chemical reaction. Here we reunite both worlds, the plasmonic photocatalysts and the molecular ones, identifying different energy transfer pathways and their influence on selectivity and efficiency of chemical reactions. We foresee that the migration from optical to chemical hot spots will greatly assist the understanding of ongoing plasmonic chemistry.

Hybrid longitudinal-transverse phonon polaritons.

Phonon polaritons, hybrid light-matter quasiparticles resulting from strong coupling of the electromagnetic field with the lattice vibrations of polar crystals are a promising platform for mid-infrared photonics but for the moment there has been no proposal allowing for their electrical pumping. Electrical currents in fact mainly generate longitudinal optical phonons, while only transverse ones participate in the creation of phonon polaritons. We demonstrate how to exploit long-cell polytypes of silicon carbide to achieve strong coupling between transverse phonon polaritons and zone-folded longitudinal optical phonons. We develop a microscopic theory predicting the existence of the resulting hybrid longitudinal-transverse excitations. We then provide an experimental observation by tuning the resonance of a nanopillar array through the folded longitudinal optical mode, obtaining a clear spectral anti-crossing. The hybridisation of phonon polaritons with longitudinal phonons could represent an important step toward the development of phonon polariton-based electrically pumped mid-infrared emitters.

Sub-20 fs All-Optical Switching in a Single Au-Clad Si Nanodisk.

Dielectric nanoantennas have recently emerged as promising elements for nonlinear and ultrafast nanophotonics due to their ability to concentrate light on the nanometer scale with low losses, while exhibiting large nonlinear susceptibilities. In this work, we demonstrate that single Si nanodisks covered with a thin 30 nm thick layer of Au can generate positive and negative sub-20 fs reflectivity modulations of ∼0.3% in the vicinity of the first-order anapole mode, when excited around the second-order anapole mode. The experimental results, characterized in the visible to near-infrared spectral range, suggest that the nonlinear optical Kerr effect is the responsible mechanism for the observed all-optical switching phenomena. These findings represent an important step toward nanoscale ultrafast all-optical signal processing.

Acoustic Far-Field Hypersonic Surface Wave Detection with Single Plasmonic Nanoantennas.

The optical properties of small metallic particles allow us to bridge the gap between the myriad of subdiffraction local phenomena and macroscopic optical elements. The optomechanical coupling between mechanical vibrations of Au nanoparticles and their optical response due to collective electronic oscillations leads to the emission and the detection of surface acoustic waves (SAWs) by single metallic nanoantennas. We take two Au nanoparticles, one acting as a source and the other as a receptor of SAWs and, even though these antennas are separated by distances orders of magnitude larger than the characteristic subnanometric displacements of vibrations, we probe the frequency content, wave speed, and amplitude decay of SAWs originating from the damping of coherent mechanical modes of the source. Two-color pump-probe experiments and numerical methods reveal the characteristic Rayleigh wave behavior of emitted SAWs, and show that the SAW-induced optical modulation of the receptor antenna allows us to accurately probe the frequency of the source, even when the eigenmodes of source and receptor are detuned.

Tailored Hypersound Generation in Single Plasmonic Nanoantennas.

Ultrashort laser pulses impinging on a plasmonic nanostructure trigger a highly dynamic scenario in the interplay of electronic relaxation with lattice vibrations, which can be experimentally probed via the generation of coherent phonons. In this Letter, we present studies of hypersound generation in the range of a few to tens of gigahertz on single gold plasmonic nanoantennas, which have additionally been subjected to predesigned mechanical constraints via silica bridges. Using these hybrid gold/silica nanoantennas, we demonstrate experimentally and via numerical simulations how mechanical constraints allow control over their vibrational mode spectrum. Degenerate pump-probe techniques with double modulation are performed in order to detect the small changes produced in the probe transmission by the mechanical oscillations of these single nanoantennas.

Direct electrochemistry of hemoglobin and biosensing for hydrogen peroxide using a film containing silver nanoparticles and poly(amidoamine) dendrimer.

A new architecture for a biosensor is proposed using a glassy carbon electrode (GCE) modified with hemoglobin (Hb) and silver nanoparticles (AgNPs) encapsulated in poly(amidoamine) dendrimer (PAMAM). The biosensors were characterized using ultraviolet-visible spectroscopy, ζ-potential and cyclic voltammetry to investigate the interactions between Hb, AgNPs and the PAMAM film. The biosensor exhibited a well-defined cathodic peak attributed to reduction of the Fe(3+) present in the heme group in Hb, as revealed by cyclic voltammetry in the presence of O2. An apparent heterogeneous electron transfer rate of 4.1s(-1) was obtained. The Hb-AgNPs-PAMAM/GCE third generation biosensor was applied in the amperometric determination of hydrogen peroxide over the linear range from 6.0 × 10(-6) to 9.1 × 10(-5)mol L(-1) with a detection limit of 4.9 × 1 0(-6)mol L(-1). The proposed method can be extended to immobilize and evaluate the direct electron transfer of other redox enzymes.