We report a study on the hydrogen bonding mechanisms of three aliphatic alcohols (2-propanol, methanol, and ethanol) and one diol (ethylene glycol) in water solution using a time-domain ellipsometer in the THz region. The dielectric response of the pure liquids is nicely modeled by the generalized Debye-Lorentz equation. For binary mixtures, we analyze the data using a modified effective Debye model, which considers H-bond rupture and reformation dynamics and the motion of the alkyl chains and of the OH groups. We focus on the properties of the water-rich region, finding anomalous behavior in the absorption properties at very low solute molar concentrations. These results, first observed in the THz region, are in line with previous findings from different experiments and can be explained by taking into account the amphiphilic nature of the alcohol molecules.
Alcohols , Hydrogen Bonding , Water , Water/chemistry , Alcohols/chemistry , Terahertz Spectroscopy/methods , Ethanol/chemistry , 2-Propanol/chemistry
The monoclinic structures of vanadium dioxide are widely studied as appealing systems due to a plethora of functional properties in several technological fields. In particular, the possibility to obtain the VO2 material in the form of thin film with a high control of structure and morphology represents a key issue for their use in THz devices and sensors. Herein, a fine control of the crystal habit has been addressed through an in-depth study of the metal organic chemical vapor deposition (MOCVD) synthetic approach. The focus is devoted to the key operative parameters such as deposition temperature inside the reactor in order to stabilize the P21/c or the C2/m monoclinic VO2 structures. Furthermore, the compositional purity, the morphology and the thickness of the VO2 films have been assessed through energy dispersive X-ray (EDX) analyses and field-emission scanning electron microscopy (FE-SEM), respectively. THz time domain spectroscopy is used to validate at very high frequency the functional properties of the as-prepared VO2 films.
Using a customized time-domain ellipsometer operating in the THz range, the molecular dynamics of a liquid binary solution based on water and isopropyl alcohol (2-propanol) is investigated. The setup is capable of detecting small changes in the optical properties of the mixture within a single measurement. The complex dielectric response of samples with different concentrations is studied through the direct measurement of the ellipsometric parameters. The results are described using an effective Debye model, from which the relaxation parameters associated with different activation energies can be consistently extracted. Significant deviations between experimental data and the theoretical expectations at an intermediate volume percentage of 2-propanol in water are observed and interpreted as produced by competing effects: the creation/destruction of hydrogen bonding on the one hand, and the presence of cluster/aggregation between water and alcohol molecules on the other.
We experimentally investigate the sensing properties of an open cavity operating in the THz regime and realized by employing as mirrors two thin vanadium dioxide (VO2) films grown on silicon parallel plates and separated by a variable length. The phase transition of VO2 is used to control the behavior of the system between two different responses: a high transmission mode to the incident radiation (VO2 in the insulating state) and a high sensitivity to tiny changes in the cavity refractive index (VO2 in the conducting state). In the first state, the low loss regime enables to adjust the cavity length and easily optimize the resonances due to the Fabry-Perot (FP) effect in the Si plates and in the cavity volume. The activation of the metallic-like state instead, by damping the FP oscillations in the plates, promotes the onset of a comb-like spectrum that can be exploited as a versatile tool for accurate sensing applications. Using both an analytical model and full-wave simulations, we estimate the device response to variation in the refractive index of the cavity volume, showing that the proposed structure can achieve sensitivity values among the highest reported for THz sensors.
Ellipsometry is extensively used in the optical regime to investigate the properties of many materials as well as to evaluate with high precision the surface roughness and thickness of thin films and multilayered systems. Due to the inherent non-coherent detection technique, data analyses in optical ellipsometry tend to be complicated and require the use of a predetermined model, therefore indirectly linking the sample properties to the measured ellipsometric parameters. The aim of this tutorial is to provide an overview of terahertz (THz) time-domain ellipsometry, which is based instead on a coherent detection approach and allows in a simple and direct way the measurement of the material response. After giving a brief description of the technology presently used to generate and detect THz radiation, we introduce the general features of an ellipsometric setup operating in the time domain, putting in evidence similarities and differences with respect to the classical optical counterpart. To back up and validate the study, results of THz ellipsometric measurements carried out on selected samples are presented.
We report the design, fabrication and experimental validation of a THz all-dielectric multi-mode q-plate having a fixed rate of change of the optical axis. The device consists of space-variant birefringent slabs manufactured by 3D printing using melt-extruded Acrylonitrile Butadiene Styrene (ABS). The desired form birefringence is analytically evaluated and experimentally measured by the THz time domain spectroscopy technique. The manufactured q-plate design is characterized using a polarization-sensitive imaging setup. The full electric field spatial maps are acquired from the beam propagating through the q-plate. The device enables the realization of both radial and azimuthal vector beams at discrete frequency intervals by controlling the space-dependent orientation of the ordinary and extraordinary axes in the transverse plane with a multi-mode sequence.
We report on the realisation of a customized THz time domain spectroscopic ellipsometer (THz-TDSE) based on fiber-coupled photoconductive antennas, operating in a wide range of incident angles and allowing also standard transmission spectroscopy without any optical realignment. To ensure accurate parameter extraction for a broad range of materials, we developed a fast and effective algorithm-assisted method to calibrate the setup and compensate for the nonideality in the response of the THz system. The procedure allows to minimise errors induced by imperfect response of the antennas and polarizers, imprecise setting of the impinging and receiving angles in the goniometric mechanical arms, and unavoidable mismatches in the THz beam optics. Differently from other calibration methods applied in the literature, our approach compares in time domain the ellipsometric derived electric field s- and p-polarised components at a given angle of incidence with the reconstructed ones, attained by using the complex dielectric function of a known sample. The calibrated response is determined with high precision by setting the system in transmission mode. In order to validate the technique, ellipsometric measurements have been carried out at various angle of incidences on a number of materials both in solid and liquid form, and their data compared with what obtained by conventional THz spectroscopy. Results show that THz-TDSE accompanied with an accurate calibration procedure is an effective technique for material characterization, especially in case of samples with a high absorption rate that are not easily investigated through transmission measurements.
The use of graphene in a form of discontinuous flakes in polymer composites limits the full exploitation of the unique properties of graphene, thus requiring high filler loadings for achieving- for example- satisfactory electrical and mechanical properties. Herein centimetre-scale CVD graphene/polymer nanolaminates have been produced by using an iterative 'lift-off/float-on' process and have been found to outperform, for the same graphene content, state-of-the-art flake-based graphene polymer composites in terms of mechanical reinforcement and electrical properties. Most importantly these thin laminate materials show a high electromagnetic interference (EMI) shielding effectiveness, reaching 60 dB for a small thickness of 33 µm, and an absolute EMI shielding effectiveness close to 3·105 dB cm2 g-1 which is amongst the highest values for synthetic, non-metallic materials produced to date.
A novel, to the best of our knowledge, methodology based on the combination of experimental measurements and simulations of the wave transmission through a metasurface at different angles is presented, enabling us to identify the fundamental and first high-order mode of spoof surface plasmon polaritons (SSPPs) excited in the terahertz regime. The approach offers a new way, an alternative to standard near field imaging, to trace out the presence of SSPPs on a metal-dielectric interface.
In many resonant structures the damping of parasitic or higher order modes is indispensable to guarantee a correct and stable performance. This is particularly true in the microwave region in case of cavities or other resonant systems operating in accelerating structures, where the mitigation of spurious resonance effects is mandatory to achieve high quality particle beams. We present the results on the mode suppression in a real pillbox cavity by inserting a properly designed pyramidal metamaterial that acts as light, small volume damper for specific resonances in the range 3-4 GHz, only slightly perturbing other intrinsic modes. Measurements of the cavity response without and with the metamaterial absorber are presented and compared with full wave simulations. Field distribution for the pillbox intrinsic modes under scrutiny is also presented, showing that damping induced by the metamaterial critically depends on its relative position inside the cavity.
The exponential factor in Equation (1) of the paper published in Materials [1] reports a misprintand the correct expression of the transmission function is [...].
Hydrogen production by photocatalytic water splitting is one of the most promising sustainable routes to store solar energy in the form of chemical bonds. To obtain significant H2 evolution rates (HERs) a variety of defective TiO2 catalysts were synthesized by means of procedures generally requiring highly energy-consuming treatments, e.g. hydrogenation. Even if a complete understanding of the relationship between defects, electronic structure and catalytic active sites is far from being achieved, the band gap narrowing and Ti3+-self-doping have been considered essential to date. In most reports a metal co-catalyst (commonly Pt) and a sacrificial electron donor (such as methanol) are used to improve HERs. Here we report the synthesis of TiO2/C bulk heterostructures, obtained from a hybrid TiO2-based gel by simple heat treatments at 400 °C under different atmospheres. The electronic structure and properties of the grey or black gel-derived powders are deeply inspected by a combination of classical and less conventional techniques, in order to identify the origin of their photoresponsivity. The defective sites of these heterostructures, namely oxygen vacancies, graphitic carbon and unpaired electrons localized on the C matrix, result in a remarkable visible light activity in spite of the lack of band gap narrowing or Ti3+-self doping. The materials provide HER values ranging from about 0.15 to 0.40 mmol h-1 gcat -1, under both UV- and visible-light irradiation, employing glycerol as sacrificial agent and without any co-catalyst.
We describe an experimental strategy for the use of Terahertz (THz) metasurfaces as a platform for label-free wide range detection of the dielectric function in biological fluids. Specifically, we propose a metagrid (MG), opportunely infiltrated with a fluid and then capped, as the reference structure for sensing experiments with a high reproducibility character. By combining experiments and full-wave simulations of the transmission T of such a structure, we introduce a reliable set up where the volume of the involved analyte in each unit cell is precisely determined. The unavoidable decrease in the quality factor of the intrinsic resonances due to the lossy fluid and cap layer is circumvented using an appropriate transformation of T that amplifies the change in the MG intrinsic resonances, improving in such a way the sensor sensitivity to values close to the experimental limits. The transformed signal features delta-like peaks enabling an easy readout of frequency positions at resonances.
The transmission response of metallo-dielectric grid metasurfaces is experimentally investigated through Terahertz Time Domain Spectroscopy and the corresponding effective dielectric function is retrieved. Using a lumped element model we can determine the dependence of the effective plasma frequency (the transition frequency) on the metasurface filling factor F. The change of the transition frequency vs. F spans over one order of magnitude and sets the threshold between the metamaterial (homogeneous) and the photonic crystal (diffraction-like) regime, ruling the onset of two different Surface Plasmon Polaritons, spoof and high order. Field symmetry and spatial extension of such excitations are investigated for the possible applications of THz grid metasurfaces in bio- and chemical sensing and sub-wavelength imaging.
Time domain spectroscopy is used to determine the THz electromagnetic response of amorphous transition metal dichalcogenides WSe2 and MoSe2 in thin-film form. The dielectric function is obtained using a rigorous transmission model to account for the large etalon effect. The Drudeâ»Smith model is applied to retrieve the dielectric function, and from there, the sample conductivity.
Coding metasurfaces, composed of only two types of elements arranged according to a binary code, are attracting a steadily increasing interest in many application scenarios. In this study, we apply this concept to attain diffuse scattering at THz frequencies. Building up on previously derived theoretical results, we carry out a suboptimal metasurface design based on a simple, deterministic and computationally inexpensive algorithm that can be applied to arbitrarily large structures. For experimental validation, we fabricate and characterize three prototypes working at 1 THz, which, in accordance with numerical predictions, exhibit significant reductions of the radar cross-section, with reasonably good frequency and angular stability. Besides the radar-signature control, our results may also find potentially interesting applications to diffusive imaging, computational imaging, and (scaled to optical wavelengths) photovoltaics.
We investigate a hybrid re-configurable three dimensional metamaterial based on liquid crystal as tuning element in order to build novel devices operating in the terahertz range. The proposed metadevice is an array of meta-atoms consisting of split ring resonators having suspended conducting cantilevers in the gap region. Adding a "third dimension" to a standard planar device plays a dual role: (i) enhance the tunability of the overall structure, exploiting the birefringence of the liquid crystal at its best, and (ii) improve the field confinement and therefore the ability of the metadevice to efficiently steer the THz signal. We describe the design, electromagnetic simulation, fabrication and experimental characterization of this new class of tunable metamaterials under an externally applied small voltage. By infiltrating tiny quantities of a nematic liquid crystal in the structure, we induce a frequency shift in the resonant response of the order of 7-8% in terms of bandwidth and about two orders of magnitude change in the signal absorption. We discuss how such a hybrid structure can be exploited for the development of a THz spatial light modulator.
We present the experimental characterization of mantle cloaks designed so as to minimize the electromagnetic scattering of moderately-sized dielectric and conducting cylinders at S-band microwave frequencies. Our experimental setup is based on a parallel-plate waveguide system, which emulates a two-dimensional plane-wave scattering scenario, and allows the collection of near-field maps as well as more quantitative assessments in terms of global scattering observables (e.g., total scattering width). Our results, in fairly good agreement with full-wave numerical simulations, provide a further illustration of the mantle- cloak mechanism, including its frequency-sensitivity, and confirm its effectiveness both in restoring the near-field impinging wavefront around the scatterer, and in significantly reducing the overall scattering.
We study the presence of dark and bright modes in a planar metamaterial with a double rod unit cell introducing geometric asymmetry in rod lengths. The dark mode displays a Fano-type resonance with a sharp asymmetric profile, rendering it far more sensitive than the bright mode to slight variations of the dielectric environment. This peculiar feature may envisage the possible application of the asymmetric dimer metamaterial as an optical sensor for chemical or biological analysis, provided that the effect of material losses on the dark mode quality factor is properly taken into account.
We studied the waveguiding properties of a photonic quasicrystal based on an octagonal tiling. The structure exhibits intrinsic localisation in the band gap region, that can be exploited to manipulate the signal transmission through a linear defect. The electromagnetic characteristics are first numerically analysed using a full wave simulation and then experimentally verified by measurements carried out in the X-band microwave region. Possible photonic applications include tunable notch filters having large attenuation.
