Surprising Eutectics: Enhanced Properties of ZnO-ZnWO4 from Visible to MIR.

Zinc oxide-zinc tungstate (ZnO-ZnWO4 ) is a self-organized eutectic composite consisting of parallel ZnO thin layers (lamellae) embedded in a dielectric ZnWO4 matrix. The electromagnetic behavior of composite materials is affected not only by the properties of single constituent materials but also by their reciprocal geometrical micro-/nano-structurization, as in the case of ZnO-ZnWO4 . The light interacting with microscopic structural features in the composite material provides new optical properties, which overcome the possibilities offered by the constituent materials. Here remarkable active and passive polarization control of this composite over various wavelength ranges are shown; these properties are based on the crystal orientation of ZnO with respect to the biaxiality of the ZnWO4 matrix. In the visible range, polarization-dependent polarized luminescence occurs for blue light emitted by ZnO. Moreover, it is reported on the enhancement of the second harmonic generation of the composite with respect to its constituents, due to the phase matching condition. Finally, in the medium infrared spectral region, the composite behaves as a metamaterial with strong polarization dependence.

Broadband optical spin dependent reflection in self-assembled GaAs-based nanowires asymmetrically hybridized with Au.

Hybridization of semiconductor nanostructures with asymmetric metallic layers offers new paths to circular polarization control and chiral properties. Here we study, both experimentally and numerically, chiral properties of GaAs-based nanowires (NWs) which have two out of six sidewalls covered by Au. Sparse ensembles of vertical, free-standing NWs were fabricated by means of lithography-free self-assembled technique on Si substrates and subsequently covered by Au using tilted evaporation. We report on optical spin-dependent specular reflection in the 680-1000 nm spectral range when the orientation of the golden layers follows the rule of extrinsic chirality. The analysis shows reflection peaks of the chiral medium whose intensity is dependent on the light handedness. We further propose a novel, time-efficient numerical method that enables a better insight into the far-field intensity and distribution of the scattered light from a sparse NW ensembles. The measurements done on three different samples in various orientations show good agreement with theoretical predictions over a broad wavelength range.

Photoacoustics for listening to metal nanoparticle super-aggregates.

Photoacoustic signal detection has been used to build a new strategy to determine the mesoscale self-assembly of metal nanoparticles in terms of size distribution and aggregate packing density (metal nanoparticle filling factor). A synergistic approach integrating photoacoustic signal and theoretical studies, validated by conventional light scattering and electron microscopy techniques, allows us to obtain a well-defined morphological interpretation of nanoparticle-based super-aggregates. By pumping light in a complex system, the acousto-thermal effect was listened to, providing information on the aggregation phenomena. Super-aggregates of covalently interconnected silver nanoparticles (AgNPs) functionalized with an organometallic dithiol are identified in solution, as a proof of concept for the versatility of the photoacoustic approach. According to our results, tiny AgNPs (size less than 10 nm) assembled into a 3D-network of super-aggregates (SA-AgNPs) with sizes in the range 100-200 nm and a filling factor in the range of 30-50%. Low-cost, rapid, and easy photoacoustic measurement in the low frequency range (less than 100 Hz) was revealed to be an innovative method to characterize the fundamental structure/property correlation of metal nanoparticle super-aggregates. This morpho-optical approach, which uses the absorption and scattering properties of nanoparticles in the liquid phase, opens new perspectives for advanced biomedical and structural applications.

Circular Dichroism in the Second Harmonic Field Evidenced by Asymmetric Au Coated GaAs Nanowires.

Optical circular dichroism (CD) is an important phenomenon in nanophotonics, that addresses top level applications such as circular polarized photon generation in optics, enantiomeric recognition in biophotonics and so on. Chiral nanostructures can lead to high CD, but the fabrication process usually requires a large effort, and extrinsic chiral samples can be produced by simpler techniques. Glancing angle deposition of gold on GaAs nanowires can (NWs) induces a symmetry breaking that leads to an optical CD response that mimics chiral behavior. The GaAs NWs have been fabricated by a self-catalyzed, bottom-up approach, leading to large surfaces and high-quality samples at a relatively low cost. Here, we investigate the second harmonic generation circular dichroism (SHG-CD) signal on GaAs nanowires partially covered with Au. SHG is a nonlinear process of even order, and thus extremely sensitive to symmetry breaking. Therefore, the visibility of the signal is very high when the fabricated samples present resonances at first and second harmonic frequencies (i.e., 800 and 400 nm, in our case).

Correlation between in situ structural and optical characterization of the semiconductor-to-metal phase transition of VO2 thin films on sapphire.

A detailed structural investigation of the semiconductor-to-metal transition (SMT) in vanadium dioxide thin films deposited on sapphire substrates by pulsed laser deposition was performed by in situ temperature-dependent X-ray diffraction (XRD) measurements. The structural results are correlated with those of infrared radiometry measurements in the SWIR (2.5-5 µm) and LWIR (8-10.6 µm) spectral ranges. The main results indicate a good agreement between XRD and optical analysis, therefore demonstrating that the structural transition from monoclinic to tetragonal phases is the dominating mechanism for controlling the global properties of the SMT transition. The picture that emerges is a SMT transition in which the two phases (monoclinic and tetragonal) coexist during the transition. Finally, the thermal hysteresis, measured for thin films with different thickness, showed a clear dependence of the transition temperature and the width of the hysteresis loop on the film thickness and on the size of the crystallites.

Chiral near-field manipulation in Au-GaAs hybrid hexagonal nanowires.

We demonstrate the control of enhanced chiral field distribution at the surface of hybrid metallo-dielectric nanostructures composed of self-assembled vertical hexagonal GaAs-based nanowires having three of the six sidewalls covered with Au. We show that weakly-guided modes of vertical GaAs nanowires can generate regions of high optical chirality that are further enhanced by the break of the symmetry introduced by the gold layer. Changing the angle of incidence of a linearly polarized plane wave it is possible to tailor and optimize the maps of the optical chirality in proximity of the gold plated walls. The low cost feasibility of the sample combined to the simple control by using linearly polarized light and the easy positioning of chiral molecules by functionalization of the gold plates make our proposed scheme very promising for enhanced enantioselective spectroscopy applications.

Precise detection of circular dichroism in a cluster of nano-helices by photoacoustic measurements.

Compact samples of nano-helices built by means of a focused ion beam technology with large bandwidth and high dichroism for circular polarization are promising for the construction of built-in-chip sensors, where the ideal transducer must be sufficiently confined without compromising its filtering ability. Direct all-optical measurements revealed the sample's dichroic character with insufficient details because of scattering and diffraction interference. On the other hand, photoacoustic measurements resulted to be a possible alternative investigation, since they directly deal with absorbed power and allow to get clear evidences of the differential selection for the two opposite polarization states. Multi-level numerical simulations confirmed the experimental results, proving once again the reliability of photoacoustic technique and the versatility of this class of dichroic artificial materials.

Photo-acoustic spectroscopy revealing resonant absorption of self-assembled GaAs-based nanowires.

III-V semiconductors nanowires (NW) have recently attracted a significant interest for their potential application in the development of high efficiency, highly-integrated photonic devices and in particular for the possibility to integrate direct bandgap materials with silicon-based devices. Here we report the absorbance properties of GaAs-AlGaAs-GaAs core-shell-supershell NWs using photo-acoustic spectroscopy (PAS) measurements in the spectral range from 300 nm to 1100 nm wavelengths. The NWs were fabricated by self-catalyzed growth on Si substrates and their dimensions (length ~5 µm, diameter ~140-150 nm) allow for the coupling of the incident light to the guided modes in near-infrared (IR) part of the spectrum. This coupling results in resonant absorption peaks in the visible and near IR clearly evidenced by PAS. The analysis reveal broadening of the resonant absorption peaks arising from the NW size distribution and the interaction with other NWs. The results show that the PAS technique, directly providing scattering independent absorption spectra, is a very useful tool for the characterization and investigation of vertical NWs as well as for the design of NW ensembles for photonic applications, such as Si-integrated light sources, solar cells, and wavelength dependent photodetectors.

Self-Phase-Matched Second-Harmonic and White-Light Generation in a Biaxial Zinc Tungstate Single Crystal.

Second-order nonlinear optical materials are used to generate new frequencies by exploiting second-harmonic generation (SHG), a phenomenon where a nonlinear material generates light at double the optical frequency of the input beam. Maximum SHG is achieved when the pump and the generated waves are in phase, for example through birefringence in uniaxial crystals. However, applying these materials usually requires a complicated cutting procedure to yield a crystal with a particular orientation. Here we demonstrate the first example of phase matching under the normal incidence of SHG in a biaxial monoclinic single crystal of zinc tungstate. The crystal was grown by the micro-pulling-down method with the (102) plane perpendicular to the growth direction. Additionally, at the same time white light was generated as a result of stimulated Raman scattering and multiphoton luminescence induced by higher-order effects such as three-photon luminescence enhanced by cascaded third-harmonic generation. The annealed crystal offers SHG intensities approximately four times larger than the as grown one; optimized growth and annealing conditions may lead to much higher SHG intensities.

Electron microscopy reveals a soluble hybrid network of individual nanocrystals self-anchored by bifunctional thiol fluorescent bridges.

Today, nanochemistry research of hybrid materials growth in liquid media represents a new challenge for tailoring specific nano-sized materials directly related to the hybrid electron-optical properties. Distinctive assumptions about the origin, the growth, and the functionalization of hybrid nanoparticles have recently been proposed by scientific research to attend the different aspects of observable behaviors. Therefore, appropriate morpho-structural observation of the hybrid nanoparticles is the most important factor for controlling the chemical and physical properties. Here, we report how the gold nanocrystals (Au-NCs) structurally covered by an outer layer material of 9,9-didodecyl-2,7-bisthiofluorene (FL) bifunctional stabilizer evolve into a self-organized 2D-network as a function of different nano-structural features. Detailed morpho-structural investigation of this hybrid material through electron microscopy techniques has been performed from the atomic-scale to hundreds of nanometers. The experimental information gathered allowed us to figure out the evolution growth of the gold-FL nanoparticles (AuFL-NPs) from the early stage of the gold-organic nucleation to the final assembled bi-dimensional network. The reported results represent a valuable background toward the full comprehension of growth mechanisms of organic-inorganic materials responsible for the final chemical and physical properties.

Chiral light intrinsically couples to extrinsic/pseudo-chiral metasurfaces made of tilted gold nanowires.

Extrinsic or pseudo-chiral (meta)surfaces have an achiral structure, yet they can give rise to circular dichroism when the experiment itself becomes chiral. Although these surfaces are known to yield differences in reflected and transmitted circularly polarized light, the exact mechanism of the interaction has never been directly demonstrated. Here we present a comprehensive linear and nonlinear optical investigation of a metasurface composed of tilted gold nanowires. In the linear regime, we directly demonstrate the selective absorption of circularly polarised light depending on the orientation of the metasurface. In the nonlinear regime, we demonstrate for the first time how second harmonic generation circular dichroism in such extrinsic/pseudo-chiral materials can be understood in terms of effective nonlinear susceptibility tensor elements that switch sign depending on the orientation of the metasurface. By providing fundamental understanding of the chiroptical interactions in achiral metasurfaces, our work opens up new perspectives for the optimisation of their properties.

Second harmonic generation on self-assembled tilted gold nanowires.

Here we present measurements on a metasurface composed by tilted gold nanowires. The metasurface can induce an optical chiral response of the whole sample when the light impinges on the sample out of the normal incidence angle. In order to investigate the symmetry breaking induced by the geometry, we measured the second harmonic generation (SHG) signal generated by circular polarized pulsed light. This technique has demonstrated to be a powerful method in order to investigate the chiral morphology of nanostructures.