Highly Tunable MOCVD Process of Vanadium Dioxide Thin Films: Relationship between Structural/Morphological Features and Electrodynamic Properties.

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.

Terahertz time-domain ellipsometry: tutorial.

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.

THz Multi-Mode Q-Plate with a Fixed Rate of Change of the Optical Axis Using Form Birefringence.

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.

Accurate THz ellipsometry using calibration in time domain.

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.

Effective EMI shielding behaviour of thin graphene/PMMA nanolaminates in the THz range.

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.

Dispersion diagram of surface plasmon polaritons from angular transmission investigation.

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.

Correction: G. Papari et al. Terahertz Spectroscopy of Amorphous WSe2 and MoSe2 Thin Films. Materials (2018), 11(9), 1613.

The exponential factor in Equation (1) of the paper published in Materials [1] reports a misprintand the correct expression of the transmission function is [...].

Photocatalytic hydrogen evolution by co-catalyst-free TiO2/C bulk heterostructures synthesized under mild conditions.

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.

Encoded-Enhancement of THz Metasurface Figure of Merit for Label-Free Sensing.

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.

Geometrical Dependence on the Onset of Surface Plasmon Polaritons in THz Grid Metasurfaces.

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.

Terahertz Spectroscopy of Amorphous WSe2 and MoSe2 Thin Films.

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 Drude⁻Smith model is applied to retrieve the dielectric function, and from there, the sample conductivity.

Suboptimal Coding Metasurfaces for Terahertz Diffuse Scattering.

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.

Nanoparticle Enhanced Laser-Induced Breakdown Spectroscopy for Microdrop Analysis at subppm Level.

In this paper, nanoparticle enhanced laser-induced breakdown spectroscopy (NELIBS) was applied to the elemental chemical analysis of microdrops of solutions with analyte concentration at subppm level. The effect on laser ablation of the strong local enhancement of the electromagnetic field allows enhancing the optical emission signal up to more than 1 order of magnitude, enabling LIBS to quantify ppb concentration and notably decreasing the limit of detection (LOD) of the technique. At optimized conditions, it was demonstrated that NELIBS can reach an absolute LOD of few picograms for Pb and 0.2 pg for Ag. The effect of field enhancement in NELIBS was tested on biological solutions such as protein solutions and human serum, in order to improve the sensitivity of LIBS with samples where the formation and excitation of the plasma are not as efficient as with metals. Even in these difficult cases, a significant improvement with respect to conventional LIBS was observed.