Terahertz and Infrared Plasmon Polaritons in PtTe2 Type-II Dirac Topological Semimetal.

Surface plasmon polaritons (SPPs) are electromagnetic excitations existing at the interface between a metal and a dielectric. SPPs provide a promising path in nanophotonic devices for light manipulation at the micro and nanoscale with applications in optoelectronics, biomedicine, and energy harvesting. Recently, SPPs are extended to unconventional materials like graphene, transparent oxides, superconductors, and topological systems characterized by linearly dispersive electronic bands. In this respect, 3D Dirac and Weyl semimetals offer a promising frontier for infrared (IR) and terahertz (THz) radiation tuning by topologically-protected SPPs. In this work, the THz-IR optical response of platinum ditelluride (PtTe2) type-II Dirac topological semimetal films grown on Si substrates is investigated. SPPs generated on microscale ribbon arrays of PtTe2 are detected in the far-field limit, finding an excellent agreement among measurements, theoretical models, and electromagnetic simulation data. The far-field measurements are further supported by near-field IR data which indicate a strong electric field enhancement due to the SPP excitation near the ribbon edges. The present findings indicate that the PtTe2 ribbon array appears an ideal active layout for geometrically tunable SPPs thus inspiring a new fashion of optically tunable materials in the technologically demanding THz and IR spectrum.

Characterization of CuAg Alloys with Low Ag Concentrations.

Copper-based alloys designed to combine high electronic and thermal conductivities with high mechanical strength find a wide range of applications in different fields. Among the principal representatives, strongly diluted CuAg alloys are of particular interest as innovative materials for the realization of accelerating structures when the use of high-gradient fields requires increasingly high mechanical and thermal performances to overcome the limitations induced by breakdown phenomena. This work reports the production and optical characterization of CuAg crystals at low Ag concentrations, from 0.028% wt to 0.1% wt, which guarantee solid solution hardening while preserving the exceptional conductivity of Cu. By means of Fourier Transform Infrared (FTIR) micro-spectroscopy experiments, the low-energy electrodynamics of the alloys are compared with that of pure Cu, highlighting the complete indistinguishability in terms of electronic transport for such low concentrations. The optical data are further supported by Raman micro-spectroscopy and SEM microscopy analyses, allowing the demonstration of the full homogeneity and complete solubility of solid Ag in copper at those concentrations. Together with the solid solution hardening deriving from the alloying process, these results support the advantage of strongly diluted CuAg alloys over conventional materials for their application in particle accelerators.

Optical properties of two-dimensional tin nanosheets epitaxially grown on graphene.

Heterostacks formed by combining two-dimensional materials show novel properties which are of great interest for new applications in electronics, photonics and even twistronics, the new emerging field born after the outstanding discoveries on twisted graphene. Here, we report the direct growth of tin nanosheets at the two-dimensional limit via molecular beam epitaxy on chemical vapor deposited graphene on Al2O3(0001). The mutual interaction between the tin nanosheets and graphene is evidenced by structural and chemical investigations. On the one hand, Raman spectroscopy indicates that graphene undergoes compressive strain after the tin growth, while no charge transfer is observed. On the other hand, chemical analysis shows that tin nanosheets interaction with sapphire is mediated by graphene avoiding the tin oxidation occurring in the direct growth on this substrate. Remarkably, optical measurements show that the absorption of tin nanosheets exhibits a graphene-like behavior with a strong absorption in the ultraviolet photon energy range, therein resulting in a different optical response compared to tin nanosheets on bare sapphire. The optical properties of ultra-thin tin films therefore represent an open and flexible playground for the absorption of light in a broad range of the electromagnetic spectrum and technologically relevant applications for photon harvesting and sensors.

Extraordinary optical transmittance generation on Si3N4 membranes.

Metamaterials are attracting increasing attention due to their ability to support novel and engineerable electromagnetic functionalities. In this paper, we investigate one of these functionalities, i.e. the extraordinary optical transmittance (EOT) effect based on silicon nitride (Si3N4) membranes patterned with a periodic lattice of micrometric holes. Here, the coupling between the incoming electromagnetic wave and a Si3N4 optical phonon located around 900 cm-1 triggers an increase of the transmitted infrared intensity in an otherwise opaque spectral region. Different hole sizes are investigated suggesting that the mediating mechanism responsible for this phenomenon is the excitation of a phonon-polariton mode. The electric field distribution around the holes is further investigated by numerical simulations and nano-IR measurements based on a Scattering-Scanning Near Field Microscope (s-SNOM) technique, confirming the phonon-polariton origin of the EOT effect. Being membrane technologies at the core of a broad range of applications, the confinement of IR radiation at the membrane surface provides this technology platform with a novel light-matter interaction functionality.

Cubic Fe-bearing majorite synthesized at 18-25 GPa and 1000 °C: implications for element transport, subducted slab rheology and diamond formation.

The chemistry and mineralogy of slabs subducted into lower mantle control slab rheology and impact the deep volatile cycle. It is known that the metamorphism of little-altered oceanic crust results in eclogite rocks with subequal proportions of garnet and clinopyroxene. With increasing pressure, these minerals react to stabilize pyrope-rich tetragonal majoritic garnet. However, some eclogites contain higher proportions of omphacitic clinopyroxene, caused by Na- and Si-rich metasomatism on the ocean floor or during subduction. The mineralogy of such eclogites is expected to evolve differently. Here, we discuss the results of the crystallization products of omphacitic glass at ~ 18 and ~ 25 GPa and 1000 °C to simulate P-T regimes of cold subduction. The full characterization of the recovered samples indicates evidence of crystallization of Na-, Si-rich cubic instead of tetragonal majorite. This cubic majorite can incorporate large amounts of ferric iron, promoting redox reactions with surrounding volatile-bearing fluids and, ultimately, diamond formation. In addition, the occurrence of cubic majorite in the slab would affect the local density, favoring the continued buoyancy of the slab as previously proposed by seismic observations. Attention must be paid to omphacitic inclusions in sublithospheric diamonds as these might have experienced back-transformation from the HP isochemical cubic phase.

Phonon Anharmonicity and Spin-Phonon Coupling in CrI3.

We report on the far-infrared, temperature-dependent optical properties of a CrI3 transition metal halide single crystal, a van der Waals ferromagnet (FM) with a Curie temperature of 61 K. In addition to the expected phonon modes determined by the crystalline symmetry, the optical reflectance and transmittance spectra of CrI3 single crystals show many other excitations as a function of temperature as a consequence of the combination of a strong lattice anharmonicity and spin-phonon coupling. This complex vibrational spectrum highlights the presence of entangled interactions among the different degrees of freedom in CrI3.

Secondary Structures of MERS-CoV, SARS-CoV, and SARS-CoV-2 Spike Proteins Revealed by Infrared Vibrational Spectroscopy.

All coronaviruses are characterized by spike glycoproteins whose S1 subunits contain the receptor binding domain (RBD). The RBD anchors the virus to the host cellular membrane to regulate the virus transmissibility and infectious process. Although the protein/receptor interaction mainly depends on the spike's conformation, particularly on its S1 unit, their secondary structures are poorly known. In this paper, the S1 conformation was investigated for MERS-CoV, SARS-CoV, and SARS-CoV-2 at serological pH by measuring their Amide I infrared absorption bands. The SARS-CoV-2 S1 secondary structure revealed a strong difference compared to those of MERS-CoV and SARS-CoV, with a significant presence of extended ß-sheets. Furthermore, the conformation of the SARS-CoV-2 S1 showed a significant change by moving from serological pH to mild acidic and alkaline pH conditions. Both results suggest the capability of infrared spectroscopy to follow the secondary structure adaptation of the SARS-CoV-2 S1 to different environments.

Anomalous Optical Properties of KTN:Li Ferroelectric Supercrystals.

We report a spectroscopic investigation of potassium-lithium-tantalate-niobate (KTN:Li) across its room-temperature ferroelectric phase transition, when the sample manifests a supercrystal phase. Reflection and transmission results indicate an unexpected temperature-dependent enhancement of average index of refraction from 450 nm to 1100 nm, with no appreciable accompanying increase in absorption. Second-harmonic generation and phase-contrast imaging indicate that the enhancement is correlated to ferroelectric domains and highly localized at the supercrystal lattice sites. Implementing a two-component effective medium model, the response of each lattice site is found to be compatible with giant broadband refraction.

FTIR microscopy evaluation of the immunogenicity of eco-friendly γFe2O3@Ag@Cs nanocomposite as a platform for the discovery and screening of vaccine adjuvants.

Core-shell nanoparticles have been extensively researched, particularly as multimodal for medical applications. Scientists are interested in combining the optical properties of nano-plasmonic nanoparticles with the magnetic properties of super-paramagnetic nanoparticles. This combination is very important because it reduces metal toxicity and improves nanoparticle targeting. Tuning the shape and size of the nanoparticles significantly reflects their properties and applications. In previous study, we assessed the SPION@Ag@chitosan core-shell nanocomposite (γFe2O3@Ag@Cs NCs) toxicity both in vitro and preclinically in vivo, using traditional toxicological assessment and biochemical parameters. The results showed that up to100 ug/kg is a safe NP dose as evaluated by pathological and biochemical parameters. The aim of the present study was to gain insight into the effect of γFe2O3@Ag@Cs NC at sub-cytotoxic concentrations (100ug/ml) on the biochemical profile of immune organs (inguinal, axillary, spleen and thymus) by combining the investigation of cytokine secretion to ex vivo FTIR spectroscopy. The four immune organs were treated with 100 ug/kg NC and the time dependence of the effects produced by the treatment was analyzed. The Data shows that the used core-shell NC with the indicate dose have a stimulatory effect on the immune system, as evidenced by an increase in antibody secretion (IgG and IgM), lipid, nucleic acid, and protein synthesis after uptake time which depends on the specific immune organ.

Spectroscopic evidence of the radioresistance of Chroococcidiopsis biosignatures: A combined Raman, FT-IR and THz-TDs spectroscopy study.

In the last decades, Mars has been widely studied with on-site missions and observations, showing a planet that could have hosted life in the past. For this reason, the recent and future space missions on the red planet will search for traces of past and, possibly, present life. As a basis for these missions, Space Agencies, such as the European Space Agency, have conducted many experiments on living organisms, studying their behavior in extraterrestrial conditions, learning to recognize their biosignatures with techniques remotely controllable such as Raman spectroscopy. Among these organisms, the radioresistant cyanobacterium Chroococcidiopsis was irradiated during the STARLIFE campaign with strong radiative insults. In this article we have investigated this cyanobacterium using Raman spectroscopy and extended the characterization of its biosignatures and its response to the radiative stress to the mid- Infrared and Terahertz spectral region using the Fourier Transform InfraRed (FT-IR) and Terahertz Time Domain spectroscopy (THz- TDs), which demonstrates the compatibility and suitability of these techniques for future space missions.

Terahertz continuous wave spectroscopy: a portable advanced method for atmospheric gas sensing.

Motivated by the increasing demand to monitor the air-quality, our study proved the feasibility of a new compact and portable experimental approach based on Terahertz (THz) continuous wave high resolution spectroscopy, to detect the presence of the air's contaminants as greenhouse gases (GHG) and volatile organic compounds (VOCs). In this specific work, we first characterized, determining their molar absorption coefficient in the spectral region (0.06-1.2) THz, the pure optical response of the vapor of five VOCs: methanol, ethanol, isopropanol, 1-butanol and 2-butanol. In particular, 1-butanol and 2-butanol are characterized for the first time in literature at THz frequencies. Then we studied the optical response of their mixtures achieved with ambient air and ethanol. The results show that it is possible for a differentiation of single components by describing their spectral absorption in terms of the linear combination of pure compounds absorption. This proof of concept for this apparatus study and set-up paves the way to the use of THz Continuous wave high resolution spectroscopy for the environmental tracking of air pollutants.

High Sensitivity Monitoring of VOCs in Air through FTIR Spectroscopy Using a Multipass Gas Cell Setup.

Human exposure to Volatile Organic Compounds (VOCs) and their presence in indoor and working environments is recognized as a serious health risk, causing impairments of varying severities. Different detecting systems able to monitor VOCs are available in the market; however, they have significant limitations for both sensitivity and chemical discrimination capability. During the last years we studied systematically the use of Fourier Transform Infrared (FTIR) spectroscopy as an alternative, powerful tool for quantifying VOCs in air. We calibrated the method for a set of compounds (styrene, acetone, ethanol and isopropanol) by using both laboratory and portable infrared spectrometers. The aim was to develop a new, and highly sensitive sensor system for VOCs monitoring. In this paper, we improved the setup performance, testing the feasibility of using a multipass cell with the aim of extending the sensitivity of our system down to the part per million (ppm) level. Considering that multipass cells are now also available for portable instruments, this study opens the road for the design of new high-resolution devices for environmental monitoring.

Optical and thermal responses of silicene in Xene heterostructures.

Stabilization of silicene and preservation of its structural and electronic properties are essential for its processing and future integration into devices. The stacking of silicene on stanene, creating a Xene-based heterostructure, proves to be a viable new route in this respect. Here we demonstrate the effectiveness of a stanene layer in breaking the strong interaction between silicene and the Ag(111) substrate. The role of stanene as a 'buffer' layer is investigated by analyzing the optical response of epitaxial silicene through both power-dependent Raman spectroscopy and reflectivity measurements in the near infrared (NIR)-ultraviolet (UV) spectral range. Finally, we point out a Xene-induced shift of the silver plasma edge that paves the way for the development of a new approach to engineering the metal plasmonic response.

Low energy electrodynamics of CrI3 layered ferromagnet.

We report on the optical properties from terahertz (THz) to Near-Infrared (NIR) of the layered magnetic compound CrI3 at various temperatures, both in the paramagnetic and ferromagnetic phase. In the NIR spectral range, we observe an insulating electronic gap around 1.1 eV which strongly hardens with decreasing temperature. The blue shift observed represents a record in insulating materials and it is a fingerprint of a strong electron-phonon interaction. Moreover, a further gap hardening is observed below the Curie temperature, indicating the establishment of an effective interaction between electrons and magnetic degrees of freedom in the ferromagnetic phase. Similar interactions are confirmed by the disappearance of some phonon modes in the same phase, as expected from a spin-lattice interaction theory. Therefore, the optical properties of CrI3 reveal a complex interaction among electronic, phononic and magnetic degrees of freedom, opening many possibilities for its use in 2-Dimensional heterostructures.

Optical Properties of Stanene-like Nanosheets on Al2O3(0001): Implications for Xene Photonics.

Stanene is one of the most intriguing two-dimensional (2D) materials because of its nontrivial topological properties. Here, the optical properties from THz to UV of molecular beam deposited tin nanosheets on Al2O3(0001) are reported. The experimental absorption coefficient cannot be described in terms of metallic tin or tin oxides. Nonetheless, a similar optical behavior was predicted by theory for freestanding stanene, thus suggesting the formation of the 2D tin nanosheets with stanene-like properties. These findings show that 2D tin bears appealing optical properties in a broad range of the electromagnetic spectrum, thus paving the way to Xenes-based nanophotonics.

Infrared Nanospectroscopy Reveals DNA Structural Modifications upon Immobilization onto Clay Nanotubes.

The growing demand for innovative means in biomedical, therapeutic and diagnostic sciences has led to the development of nanomedicine. In this context, naturally occurring tubular nanostructures composed of rolled sheets of alumino-silicates, known as halloysite nanotubes, have found wide application. Halloysite nanotubes indeed have surface properties that favor the selective loading of biomolecules. Here, we present the first, to our knowledge, structural study of DNA-decorated halloysite nanotubes, carried out with nanometric spatially-resolved infrared spectroscopy. Single nanotube absorption measurements indicate a partial covering of halloysite by DNA molecules, which show significant structural modifications taking place upon loading. The present study highlights the constraints for the use of nanostructured clays as DNA carriers and demonstrates the power of super-resolved infrared spectroscopy as an effective and versatile tool for the evaluation of immobilization processes in the context of drug delivery and gene transfer.

Spectroscopic Evidence of a Dimensionality-Induced Metal-to-Insulator Transition in the Ruddlesden-Popper Lan+1NinO3n+1 Series.

Perovskite-based heterostructures have recently gained remarkable interest, thanks to atomic-scale precision engineering. These systems are very susceptible to small variations of control parameters, such as two-dimensionality, strain, lattice polarizability, and doping. Focusing on the rare-earth nickelate diagram, LaNiO3 (LNO) catches the eye, being the only nickelate that does not undergo a metal-to-insulator transition (MIT). Therefore, the ground state of LNO has been studied in several theoretical and experimental papers. Here, we show by means of infrared spectroscopy that an MIT can be driven by dimensionality control in ultrathin LNO films when the number of unit cells drops to 2. Such a dimensionality tuning can eventually be tailored when a physically implemented monolayer in the ultrathin films is replaced by a digital single layer embedded in the Ruddlesden-Popper Lan+1NinO3n+1 series. We provide spectroscopic evidence that the dimensionality-induced MIT in Ruddlesden-Popper nickelates strongly resembles that of ultrathin LNO films. Our results can pave the way to the employment of Ruddlesden-Popper Lan+1NinO3n+1 to tune the electronic properties of LNO through dimensional transition without the need of physically changing the number of unit cells in thin films.

Experimental signature of a topological quantum dot.

Topological insulator nanoparticles (TINPs) host topologically protected Dirac surface states, just like their bulk counterparts. For TINPs of radius <100 nm, quantum confinement on the surface results in the discretization of the Dirac cone. This system of discrete energy levels is referred to as a topological quantum dot (TQD) with energy level spacing on the order of Terahertz (THz), which is tunable with material-type and particle size. The presence of these discretized energy levels in turn leads to a new electron-mediated phonon-light coupling in the THz range, and the resulting mode can be observed in the absorption cross-section of the TINPs. We present the first experimental evidence of this new quantum phenomenon in Bi2Te3 topological quantum dots, remarkably observed at room temperature.

Fabrication and spectroscopic characterization of graphene transparent electrodes on flexible cyclo-olefin substrates for terahertz electro-optic applications.

We demonstrate graphene on flexible, low-loss, cyclo-olefin polymer films as transparent electrodes for terahertz electro-optic devices and applications. Graphene was grown by chemical vapor deposition and transferred to cyclo-olefin polymer substrates by the thermal release tape method as layers on an approximate area of 4 cm2. The structural and electromagnetic properties of the graphene samples as well as their spatial variation were systematically mapped by means of µRaman, terahertz time-domain and mid-infrared spectroscopy. Thanks to the small thickness and very low intrinsic absorption of the employed substrates, both high transmittance and conductivity were recorded, demonstrating the suitability of the technique for the fabrication of a new class of transparent and flexible electrodes working in the terahertz spectrum.

Retarding Ostwald Ripening to Directly Cast 3D Porous Graphene Oxide Bulks at Open Ambient Conditions.

Graphene aerogels (GAs) with attractive properties have shown tremendous potentials in energy- and environment-related applications. Unfortunately, current assembly methods for GAs such as sol-gel and freeze-casting processes must be conducted in enclosed spaces with unconventional conditions, thus being literally inoperative for in situ and continuous productions. Herein, a direct slurry-casting method at open ambient conditions is established to arbitrarily prepare three-dimensional (3D) porous graphene oxide (GO) bulks without macroscopic dimension limits on a wide range of solid surfaces by retarding Ostwald ripening of 3D liquid GO foams when being dried in air. A subsequent fast thermal reduction (FTR) of GO foams leads to the formation of graphene aerogels (denoted as FTR-GAs) with hierarchical closed-cellular graphene structures. The FTR-GAs show outstanding high-temperature thermal insulation (70% decrease for 400 °C), as well as superelasticity (>1000 compression-recovery cycles at 50% strain), ultralow density (10-28 mg cm-3), large specific surface area (BET, 206.8 m2 g-1), and high conductivity (ca. 100 S m-1). This work provides a viable method to achieve in situ preparations of high-performance GAs as multifunctional structural materials in aircrafts, high-speed trains, or even buildings for the targets of energy efficiency, comfort, and safety.