Circular dichroism in a plasmonic array of elliptical nanoholes with square lattice.

Chiral properties of plasmonic metasurfaces, especially related to different absorption of left and right circularly polarized light leading to circular dichroism (CD), are a research hot topic in nanophotonics. There is often a need to understand the physical origin of CD for different chiral metasurfaces, and to get guidelines for the design of structures with optimized and robust CD. In this work, we numerically study CD at normal incidence in square arrays of elliptic nanoholes etched in thin metallic layers (Ag, Au, Al) on a glass substrate and tilted with respect to the symmetry axes. Strong CD arises in absorption spectra at the same wavelength region of extraordinary optical transmission, indicating highly resonant coupling between light and surface plasmon polaritons at the metal/glass and metal/air interfaces. We elucidate the physical origin of absorption CD by a careful comparison of optical spectra for different polarizations (linear and circular), with the aid of static and dynamic simulations of local enhancement of the electric field. Furthermore, we optimize the CD as a function of the ellipse parameters (diameters and tilt), the thickness of the metallic layer, and the lattice constant. We find that silver and gold metasurfaces are most useful for CD resonances above 600 nm, while aluminum metasurfaces are convenient for achieving strong CD resonances in the short-wavelength range of the visible regime and in the near UV. The results give a full picture of chiral optical effects at normal incidence in this simple nanohole array, and suggest interesting applications for chiral biomolecules sensing in such plasmonic geometries.

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.

Titanium and Silicon Dioxide-Coated Fabrics for Management and Tuning of Infrared Radiation.

Far infrared radiation (FIR) is emitted by every body at a given temperature, including the human body. FIR ranging between 4-14 µm is considered useful for cell growth, and the human body emits a maximum of infrared (IR) radiation at the wavelength of approximately 9.3 µm. In the present study, fabrics based on five different raw textiles having the same yarn count as well as the same weaving patterns were designed and created. Some of them were subjected to a coating process. The fabrics to be tested were as follows: coated with TiO2 nanoparticles, coated with SiO2 nanoparticles, coated fabric that does not contain bioceramic nanoparticle (BNFC), and non-coated fabrics (NCF). The structural characterization of the resulting samples was performed using scanning electron microscopy (SEM), abrasion tests, and air permeability. Following the structural characterization, the infrared emissivity properties were investigated using infrared thermography as well as attenuated total reflectance Fourier-transform infrared spectroscopy in the 8-14 IR range. According to the experimental findings, the fabrics coated with TiO2 and SiO2 displayed increased infrared emissivity values compared to the uncoated ones. In addition, it was observed that the use of bioceramic powders had no effect on air permeability and abrasion properties.

In-Plane Thermal Diffusivity Measurements of Polyethersulfone Woven Textiles by Infrared Thermography.

Lock-in thermography was applied to the measurement of the in-plane thermal diffusivity of three polyethersulfone (PES) textiles characterized by different weaving pattern as well as different mass density of interlacing fibers. The experimental results showed that the in-plane thermal diffusivity in each direction decreased with the increase of the fibers' linear mass density, thus leading to an anisotropic behavior of the thermal diffusivity in the specimen where PES fibers with different density were interlaced. A new theoretical model for the study of the heat diffusion in textiles was specifically developed and, thereafter, employed for the analysis of the experimental results. As such, our textile model approach, shedding light on the role of different textile and fibers parameters on the resulting thermal diffusivity, paves the way for the development and design of textiles with tailored thermal behavior.

Study of the interaction mechanism between hydrophilic thiol capped gold nanoparticles and melamine in aqueous medium.

In the last years, intense efforts have been made in order to obtain colloidal-based systems capable of pointing out the presence of melamine in food samples. In this work, we reported about the recognition of melamine in aqueous solution, using gold nanoparticles stabilized with 3-mercapto-1-propanesulfonate (AuNPs-3MPS), with the aim of deepening how the recognition process works. AuNPs were synthesized using a wet chemical reduction method. The synthesized AuNPs-3MPS probe was fully characterized, before and after the recognition process, by both physicochemical (UV-vis, FT-IR, 1H-NMR, DLS and ζ-potential) and morphostructural techniques (AFM, HR-TEM). The chemical and electronic structure was also investigated by SR-XPS. The sensing method is based on the melamine-induced aggregation of AuNPs; the presence of melamine was successfully detected in the range of 2.5-500 ppm. The results achieved also demonstrate that negatively charged AuNPs-3MPS are potentially useful for determining melamine contents in aqueous solution. SR-XPS measurements allowed to understand interaction mechanism between the probe and the analyte. The presence of sulfonate groups allows a mutual interaction mediated by electrostatic bonds between nanoparticles surface thiols and positively charged amino groups of melamine molecules.

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.

Hybrid thermal Yagi-Uda nanoantennas for directional and narrow band long-wavelength IR radiation sources.

We investigate the possibility of spatially and spectrally controlling the thermal infrared emission by exploitation of the Yagi-Uda antenna design. Hybrid antennas composed of both SiC and Au rods are considered and the contributions of emission from all the elements, at a given equilibrium temperature, are taken into account. We show that the detrimental effect due to thermal emission from the not ideal parasitic elements drastically affect the performances of conventional thermal Au antennas in the 12 µm wavelength range. Nevertheless, our results show that the hybrid approach allows the development of efficient narrow-band and high directivity sources. The possibility of exploiting the Yagi-Uda design both in transmission and in reception modes, may open the way to the realization of miniaturized, efficient, robust and cheap sensor devices for mass-market 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.

Control of Au nanoantenna emission enhancement of magnetic dipolar emitters by means of VO2 phase change layers.

Active, ultra-fast external control of the emission properties at the nanoscale is of great interest for chip-scale, tunable and efficient nanophotonics. Here we investigated the emission control of dipolar emitters coupled to a nanostructure made of an Au nanoantenna, and a thin vanadium dioxide (VO2) layer that changes from semiconductor to metallic state. If the emitters are sandwiched between the nanoantenna and the VO2 layer, the enhancement and/or suppression of the nanostructure's magnetic dipole resonance enabled by the phase change behavior of the VO2 layer can provide a high contrast ratio of the emission efficiency. We show that a single nanoantenna can provide high magnetic field in the emission layer when VO2 is metallic, leading to high emission of the magnetic dipoles; this emission is then lowered when VO2 switches back to semiconductor. We finally optimized the contrast ratio by considering different orientation, distribution and nature of the dipoles, as well as the influence of a periodic Au nanoantenna pattern. As an example of a possible application, the design is optimized for the active control of an Er3+ doped SiO2 emission layer. The combination of the emission efficiency increase due to the plasmonic nanoantenna resonances and the ultra-fast contrast control due to the phase-changing medium can have important applications in tunable efficient light sources and their nanoscale integration.

Enhanced Near-Field Chirality in Periodic Arrays of Si Nanowires for Chiral Sensing.

Nanomaterials can be specially designed to enhance optical chirality and their interaction with chiral molecules can lead to enhanced enantioselectivity. Here we propose periodic arrays of Si nanowires for the generation of enhanced near-field chirality. Such structures confine the incident electromagnetic field into specific resonant modes, which leads to an increase in local optical chirality. We investigate and optimize near-field chirality with respect to the geometric parameters and excitation scheme. Specially, we propose a simple experiment for the enhanced enantioselectivity, and optimize the average chirality depending on the possible position of the chiral molecule. We believe that such a simple achiral nanowire approach can be functionalized to give enhanced chirality in the spectral range of interest and thus lead to better discrimination of enantiomers.

Demonstration of extrinsic chirality of photoluminescence with semiconductor-metal hybrid nanowires.

Chiral optical response is an inherent property of molecules and nanostructures, which cannot be superimposed on their mirror images. In specific cases, optical chirality can be observed also for symmetric structures. This so-called extrinsic chirality requires that the mirror symmetry is broken by the geometry of the structure together with the incident or emission angle of light. From the fabrication point of view, the benefit of extrinsic chirality is that there is no need to induce structural chirality at nanoscale. This paper reports demonstration extrinsic chirality of photoluminescence emission from asymmetrically Au-coated GaAs-AlGaAs-GaAs core-shell nanowires fabricated on silicon by a completely lithography-free self-assembled method. In particular, the extrinsic chirality of PL emission is shown to originate from a strong symmetry breaking of fundamental HE11 waveguide modes due to the presence of the asymmetric Au coating, causing preferential emission of left and right-handed emissions in different directions in the far field.

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.