Standoff CARS spectroscopy and imaging using an ytterbium-based laser system.

A laser system for standoff coherent anti-Stokes Raman scattering (CARS) spectroscopy of various materials under ambient light conditions is presented. The system is based on an ytterbium laser and an ultrafast optical parametric amplifier for the generation of a broadband pump tunable from 880 to 930 nm, a Stokes at 1025 nm, and a narrowband probe at 512.5 nm. High-resolution Raman spectra encompassing the fingerprint region (400-1800 cm-1) are obtained in 5 ms for toluene, and 100 ms for two types of sugars, glucose and fructose, at a distance of 1 m. As a demonstration of the potential of the setup, hyperspectral images of a 2×2-cm2 target area are collected for a toluene cuvette and a glucose/fructose pressed disk. Our approach is suitable for implementation of a portable system for standoff CARS imaging of chemical and biological materials.

Tailoring Third-Harmonic Diffraction Efficiency by Hybrid Modes in High-Q Metasurfaces.

Metasurfaces are versatile tools for manipulating light; however, they have received little attention as devices for the efficient control of nonlinearly diffracted light. Here, we demonstrate nonlinear wavefront control through third-harmonic generation (THG) beaming into diffraction orders with efficiency tuned by excitation of hybrid Mie-quasi-bound states in the continuum (BIC) modes in a silicon metasurface. Simultaneous excitation of the high-Q collective Mie-type modes and quasi-BIC modes leads to their hybridization and results in a local electric field redistribution. We probe the hybrid mode by measuring far-field patterns of THG and observe the strong switching between (0,-1) and (-1,0) THG diffraction orders from 1:6 for off-resonant excitation to 129:1 for the hybrid mode excitation, showing tremendous contrast in controlling the nonlinear diffraction patterns. Our results pave the way to the realization of metasurfaces for novel light sources, telecommunications, and quantum photonics.

Third-harmonic light polarization control in magnetically resonant silicon metasurfaces.

Nonlinear metasurfaces have become prominent tools for controlling and engineering light at the nanoscale. Usually, the polarization of the total generated third harmonic is studied. However, diffraction orders may present different polarizations. Here, we design an high quality factor silicon metasurface for third harmonic generation and perform back focal plane imaging of the diffraction orders, which present a rich variety of polarization states. Our results demonstrate the possibility of tailoring the polarization of the generated nonlinear diffraction orders paving the way to a higher degree of wavefront control.

Optical tuning of dielectric nanoantennas for thermo-optically reconfigurable nonlinear metasurfaces.

We demonstrate optically tunable control of second-harmonic generation in all-dielectric nanoantennas: by using a control beam that is absorbed by the nanoresonator, we thermo-optically change the refractive index of the radiating element to modulate the amplitude of the second-harmonic signal. For a moderate temperature increase of roughly 40 K, modulation of the efficiency up to 60% is demonstrated; this large tunability of the single meta-atom response paves the way to exciting avenues for reconfigurable homogeneous and heterogeneous metasurfaces.

Quantitative morphometric analysis of single gold nanoparticles by optical extinction microscopy: Material permittivity and surface damping effects.

Quantifying the optical extinction cross section of a plasmonic nanoparticle has recently emerged as a powerful means to characterize the nanoparticle morphologically, i.e., to determine its size and shape with a precision comparable to electron microscopy while using a simple optical microscope. In this context, a critical piece of information to solve the inverse problem, namely, calculating the particle geometry from the measured cross section, is the material permittivity. For bulk gold, many datasets have been reported in the literature, raising the question of which one is more adequate to describe specific systems at the nanoscale. Another question is how the nanoparticle interface, not present in the bulk material, affects its permittivity. In this work, we have investigated the role of the material permittivities on the morphometric characterization of defect-free ultra-uniform gold nanospheres with diameters of 10 nm and 30 nm, following a quantitative analysis of the polarization- and spectrally-resolved extinction cross section on hundreds of individual nanoparticles. The measured cross sections were fitted using an ellipsoid model. By minimizing the fit error or the variation of the fitted dimensions with color channel selection, the material permittivity dataset and the surface damping parameter g best describing the nanoparticles are found to be the single crystal dataset by Olmon et al. [Phys. Rev. B 86, 235147 (2012)] and g ≈ 1, respectively. The resulting nanoparticle geometries are in good agreement with transmission electron microscopy of the same sample batches, including both 2D projection and tomography.

Evidence of Cascaded Third-Harmonic Generation in Noncentrosymmetric Gold Nanoantennas.

The optimization of nonlinear optical processes on the nanoscale is a crucial step for the integration of complex functionalities into compact photonic devices and metasurfaces. In such systems, photon upconversion can be achieved with higher efficiencies via third-order processes, such as third-harmonic generation (THG), thanks to the resonantly enhanced volume currents. Conversely, second-order processes, such as second-harmonic generation (SHG), are often inhibited by the symmetry of metal lattices and of common nanoantenna geometries. SHG and THG processes in plasmonic nanostructures are generally treated independently because they typically represent small perturbations in the light-matter interaction mechanisms. In this work, we demonstrate that this paradigm does not hold for plasmon-enhanced nonlinear optics by providing evidence of a sum-frequency generation (SFG) process seeded by SHG, which sizably contributes to the overall THG yield. We address this mechanism by unveiling a characteristic fingerprint in the polarization state of the THG emission from gold noncentrosymmetric nanoantennas, which directly reflects the asymmetric distribution of second-harmonic fields within the structure and does not depend on the model one employs to describe photon upconversion. We suggest that such cascaded processes may also appear for structures that exhibit only moderate SHG yields. The presence of this peculiar mechanism in THG from plasmonic nanoantennas at telecommunication wavelengths allows us to gain further insight into the physics of plasmon-enhanced nonlinear optical processes. This could be crucial in the realization of nanoscale elements for photon conversion and manipulation operating at room temperature.

Polarized light absorption in wurtzite InP nanowire ensembles.

We investigate the absorption properties of ensembles of wurtzite (WZ) InP nanowires (NWs) by high-resolution polarization-resolved photoluminescence excitation (PLE) spectroscopy at T = 10 K. The degree of linear polarization of absorbed light, ρ(abs), resulting from the PLE spectra is governed by a competition between the dielectric mismatch effect and the WZ selection rules acting differently on different optical transitions. These two contributions are deconvoluted with the help of finite-difference time-domain simulations, thus providing information about the symmetry of the three highest valence bands (A, B, and C) of WZ InP and the extent of the spin-orbit interaction on these states. Moreover, ρ(abs) shows two characteristic dips corresponding to the two sharp A and B exciton resonances in the PLE spectra. A model developed for the dip in A provides the first experimental evidence of an enhancement in the dielectric mismatch effect originating from the Coulomb interaction between electron and hole.

All-optical free-space routing of upconverted light by metasurfaces via nonlinear interferometry.

All-optical modulation yields the promise of high-speed information processing. In this field, metasurfaces are rapidly gaining traction as ultrathin multifunctional platforms for light management. Among the featured functionalities, they enable light-wavefront manipulation and more recently demonstrated the ability to perform light-by-light manipulation through nonlinear optical processes. Here, by employing a nonlinear periodic metasurface, we demonstrate the all-optical routing of telecom photons upconverted to the visible range. This is achieved via the interference between two frequency-degenerate upconversion processes, namely, third-harmonic and sum-frequency generation, stemming from the interaction of a pump pulse with its frequency-doubled replica. By tuning the relative phase and polarization between these two pump beams, we route the upconverted signal among the diffraction orders of the metasurface with a modulation efficiency of up to 90%. This can be achieved by concurrently engineering the nonlinear emission of the individual elements (meta-atoms) of the metasurface along with its pitch. Owing to the phase control and ultrafast dynamics of the underlying nonlinear processes, free-space all-optical routing could be potentially performed at rates close to the employed optical frequencies divided by the quality factor of the optical resonances at play. Our approach adds a further twist to optical interferometry, which is a key enabling technique employed in a wide range of applications, such as homodyne detection, radar interferometry, light detection and ranging technology, gravitational-wave detection and molecular photometry. In particular, the nonlinear character of light upconversion combined with phase sensitivity is extremely appealing for enhanced imaging and biosensing.

Quantitatively linking morphology and optical response of individual silver nanohedra.

The optical response of metal nanoparticles is governed by plasmonic resonances, which are dictated by the particle morphology. A thorough understanding of the link between morphology and optical response requires quantitatively measuring optical and structural properties of the same particle. Here we present such a study, correlating electron tomography and optical micro-spectroscopy. The optical measurements determine the scattering and absorption cross-section spectra in absolute units, and electron tomography determines the 3D morphology. Numerical simulations of the spectra for the individual particle geometry, and the specific optical set-up used, allow for a quantitative comparison including the cross-section magnitude. Silver nanoparticles produced by photochemically driven colloidal synthesis, including decahedra, tetrahedra and bi-tetrahedra are investigated. A mismatch of measured and simulated spectra is found in some cases when assuming pure silver particles, which is explained by the presence of a few atomic layers of tarnish on the surface, not evident in electron tomography. The presented method tightens the link between particle morphology and optical response, supporting the predictive design of plasmonic nanomaterials.

Liquid-Phase Exfoliation of Bismuth Telluride Iodide (BiTeI): Structural and Optical Properties of Single-/Few-Layer Flakes.

Bismuth telluride halides (BiTeX) are Rashba-type crystals with several potential applications ranging from spintronics and nonlinear optics to energy. Their layered structures and low cleavage energies allow their production in a two-dimensional form, opening the path to miniaturized device concepts. The possibility to exfoliate bulk BiTeX crystals in the liquid represents a useful tool to formulate a large variety of functional inks for large-scale and cost-effective device manufacturing. Nevertheless, the exfoliation of BiTeI by means of mechanical and electrochemical exfoliation proved to be challenging. In this work, we report the first ultrasonication-assisted liquid-phase exfoliation (LPE) of BiTeI crystals. By screening solvents with different surface tension and Hildebrandt parameters, we maximize the exfoliation efficiency by minimizing the Gibbs free energy of the mixture solvent/BiTeI crystal. The most effective solvents for the BiTeI exfoliation have a surface tension close to 28 mN m-1 and a Hildebrandt parameter between 19 and 25 MPa0.5. The morphological, structural, and chemical properties of the LPE-produced single-/few-layer BiTeI flakes (average thickness of ∼3 nm) are evaluated through microscopic and optical characterizations, confirming their crystallinity. Second-harmonic generation measurements confirm the non-centrosymmetric structure of both bulk and exfoliated materials, revealing a large nonlinear optical response of BiTeI flakes due to the presence of strong quantum confinement effects and the absence of typical phase-matching requirements encountered in bulk nonlinear crystals. We estimated a second-order nonlinearity at 0.8 eV of |χ(2)| ∼ 1 nm V-1, which is 10 times larger than in bulk BiTeI crystals and is of the same order of magnitude as in other semiconducting monolayers (e.g., MoS2).

Steering and Encoding the Polarization of the Second Harmonic in the Visible with a Monolithic LiNbO3 Metasurface.

Nonlinear metasurfaces constitute a key asset in meta-optics, given their ability to scale down nonlinear optics to sub-micrometer thicknesses. To date, nonlinear metasurfaces have been mainly realized using narrow band gap semiconductors, with operation limited to the near-infrared range. Nonlinear meta-optics in the visible range can be realized using transparent materials with high refractive index, such as lithium niobate (LiNbO3). Yet, efficient operation in this strategic spectral window has been so far prevented by the nanofabrication challenges associated with LiNbO3, which considerably limit the aspect ratio and minimum size of the nanostructures (i.e., meta-atoms). Here we demonstrate the first monolithic nonlinear periodic metasurface based on LiNbO3 and operating in the visible range. Realized through ion beam milling, our metasurface features a second-harmonic (SH) conversion efficiency of 2.40 × 10-8 at a pump intensity as low as 0.5 GW/cm2. By tuning the pump polarization, we demonstrate efficient steering and polarization encoding into narrow SH diffraction orders, opening novel opportunities for polarization-encoded nonlinear meta-optics.

Quantitative optical microspectroscopy, electron microscopy, and modelling of individual silver nanocubes reveal surface compositional changes at the nanoscale.

The optical response of metal nanoparticles is governed by plasmonic resonances, which depend often intricately on the geometry and composition of the particle and its environment. In this work we describe a method and analysis pipeline unravelling these relations at the single nanoparticle level through a quantitative characterization of the optical and structural properties. It is based on correlating electron microscopy with microspectroscopy measurements of the same particle immersed in media of different refractive indices. The optical measurements quantify the magnitude of both the scattering and the absorption cross sections, while the geometry measured in electron microscopy is used for numerical simulations of the cross section spectra accounting for the experimental conditions. We showcase the method on silver nanocubes of nominal 75 nm edge size. The large amount of information afforded by the quantitative cross section spectra and measuring the same particle in two environments, allows us to identify a specific degradation of the cube surface. We find a layer of tarnish, only a few nanometers thick, a fine surface compositional change of the studied system which would be hardly quantifiable otherwise.

Quantitative Measurement of the Optical Cross Sections of Single Nano-objects by Correlative Transmission and Scattering Microspectroscopy.

The scattering and absorption of light by nano-objects is a key physical property exploited in many applications, including biosensing and photovoltaics. Yet, its quantification at the single object level is challenging and often requires expensive and complicated techniques. We report a method based on a commercial transmission microscope to measure the optical scattering and absorption cross sections of individual nano-objects. The method applies to microspectroscopy and wide-field image analysis, offering fine spectral information and high throughput sample characterization. Accurate cross-section determination requires detailed modeling of the measurement, which we develop, accounting for the geometry of the illumination and detection as well as for the presence of a sample substrate. We demonstrate the method on three model systems (gold spheres, gold rods, and polystyrene spheres), which include metallic and dielectric particles, spherical and elongated, placed in a homogeneous medium or on a dielectric substrate. Furthermore, by comparing the measured cross sections with numerical simulations, we are able to determine structural parameters of the studied system, such as the particle diameter and aspect ratio. Our method therefore holds the potential to complement electron microscopy as a simpler and cost-effective tool for structural characterization of single nano-objects.

Temperature Dependence of Interband Transitions in Wurtzite InP Nanowires.

Semiconductor nanowires (NWs) formed by non-nitride III-V compounds grow preferentially with wurtzite (WZ) lattice. This is contrary to bulk and two-dimensional layers of the same compounds, where only zincblende (ZB) is observed. The absorption spectrum of WZ materials differs largely from their ZB counterparts and shows three transitions, referred to as A, B, and C in order of increasing energy, involving the minimum of the conduction band and different critical points of the valence band. In this work, we determine the temperature dependence (T = 10-310 K) of the energy of transitions A, B, and C in ensembles of WZ InP NWs by photoluminescence (PL) and PL excitation (PLE) spectroscopy. For the whole temperature and energy ranges investigated, the PL and PLE spectra are quantitatively reproduced by a theoretical model taking into account contribution from both exciton and continuum states. WZ InP is found to behave very similarly to wide band gap III-nitrides and II-VI compounds, where the energy of A, B, and C displays the same temperature dependence. This finding unveils a general feature of the thermal properties of WZ materials that holds regardless of the bond polarity and energy gap of the crystal. Furthermore, no differences are observed in the temperature dependence of the fundamental band gap energy in WZ InP NWs and ZB InP (both NWs and bulk). This result points to a negligible role played by the WZ/ZB differences in determining the deformation potentials and the extent of the electron-phonon interaction that is a direct consequence of the similar nearest neighbor arrangement in the two lattices.