Endothermic reaction at room temperature enabled by deep-ultraviolet plasmons.

Metallic nanoparticles have been used to harvest energy from a light source and transfer it to adsorbed gas molecules, which results in a reduced chemical reaction temperature. However, most reported reactions, such as ethylene epoxidation, ammonia decomposition and H-D bond formation are exothermic, and only H-D bond formation has been achieved at room temperature. These reactions require low activation energies (<2 eV), which are readily attained using visible-frequency localized surface plasmons (from ~1.75 eV to ~3.1 eV). Here, we show that endothermic reactions that require higher activation energy (>3.1 eV) can be initiated at room temperature by using localized surface plasmons in the deep-UV range. As an example, by leveraging simultaneous excitation of multiple localized surface plasmon modes of Al nanoparticles by using high-energy electrons, we initiate the reduction of CO2 to CO by carbon at room temperature. We employ an environmental transmission electron microscope to excite and characterize Al localized surface plasmon resonances, and simultaneously measure the spatial distribution of carbon gasification near the nanoparticles in a CO2 environment. This approach opens a path towards exploring other industrially relevant chemical processes that are initiated by plasmonic fields at room temperature.

Microstructural Analysis and Mechanical Properties of TiMo20Zr7Ta15Six Alloys as Biomaterials.

TiMoZrTaSi alloys appertain to a new generation of metallic biomaterials, labeled high-entropy alloys, that assure both biocompatibility as well as improved mechanical properties required by further medical applications. This paper presents the use of nondestructive evaluation techniques for new type of alloys, TiMo20Zr7Ta15Six, with x = 0; 0.5; 0.75; 1.0, which were obtained by vacuum melting. In Ti alloys, the addition of Mo improves tensile creep strength, Si improves both the creep and oxidation properties, Zr leads to an α crystalline structure, which increases the mechanical strength and assures a good electrochemical behavior, and Ta is a ß stabilizer sustaining the formation of solid ß-phases and contributes to tensile strength improvement and Young modulus decreasing. The effects of Si content on the mechanical properties of the studied alloys and the effect of the addition of Ta and Zr under the presence of Si on the evolution of crystallographic structure was studied. The influence of composition on fracture behavior and strength was evaluated using X-ray diffraction, resonant ultrasound spectroscopy (RUS) analyses, SEM with energy dispersive X-ray spectroscopy, and acoustic emission (AE) within compression tests. The ß-type TiMo20Zr7Ta15Six alloys had a good compression strength of over 800 MPa, lower Young modulus (69.11-89.03 GPa) and shear modulus (24.70-31.87 GPa), all offering advantages for use in medical applications.

Probing the Optical Properties and Strain-Tuning of Ultrathin Mo1- xW xTe2.

Ultrathin transition metal dichalcogenides (TMDCs) have recently been extensively investigated to understand their electronic and optical properties. Here we study ultrathin Mo0.91W0.09Te2, a semiconducting alloy of MoTe2, using Raman, photoluminescence (PL), and optical absorption spectroscopy. Mo0.91W0.09Te2 transitions from an indirect to a direct optical band gap in the limit of monolayer thickness, exhibiting an optical gap of 1.10 eV, very close to its MoTe2 counterpart. We apply tensile strain, for the first time, to monolayer MoTe2 and Mo0.91W0.09Te2 to tune the band structure of these materials; we observe that their optical band gaps decrease by 70 meV at 2.3% uniaxial strain. The spectral widths of the PL peaks decrease with increasing strain, which we attribute to weaker exciton-phonon intervalley scattering. Strained MoTe2 and Mo0.91W0.09Te2 extend the range of band gaps of TMDC monolayers further into the near-infrared, an important attribute for potential applications in optoelectronics.

The structural phases and vibrational properties of Mo1-xWxTe2 alloys.

The structural polymorphism in transition metal dichalcogenides (TMDs) provides exciting opportunities for developing advanced electronics. For example, MoTe2 crystallizes in the 2H semiconducting phase at ambient temperature and pressure, but transitions into the 1T' semimetallic phase at high temperatures. Alloying MoTe2 with WTe2 reduces the energy barrier between these two phases, while also allowing access to the T d Weyl semimetal phase. The Mo1-x WxTe2 alloy system is therefore promising for developing phase change memory technology. However, achieving this goal necessitates a detailed understanding of the phase composition in the MoTe2-WTe2 system. We combine polarization-resolved Raman spectroscopy with x-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) to study bulk Mo1-xWxTe2 alloys over the full compositional range x from 0 to 1. We identify Raman and XRD signatures characteristic of the 2H, 1T', and T d structural phases that agree with density-functional theory (DFT) calculations, and use them to identify phase fields in the MoTe2-WTe2 system, including single-phase 2H, 1T', and T d regions, as well as a two-phase 1T' + T d region. Disorder arising from compositional fluctuations in Mo1-xWxTe2 alloys breaks inversion and translational symmetry, leading to the activation of an infrared 1T'-MoTe2 mode and the enhancement of a double-resonance Raman process in 2H-Mo1-x WxTe2 alloys. Compositional fluctuations limit the phonon correlation length, which we estimate by fitting the observed asymmetric Raman lineshapes with a phonon confinement model. These observations reveal the important role of disorder in Mo1-xWxTe2 alloys, clarify the structural phase boundaries, and provide a foundation for future explorations of phase transitions and electronic phenomena in this system.

Characterization of Few-Layer 1T' MoTe2 by Polarization-Resolved Second Harmonic Generation and Raman Scattering.

We study the crystal symmetry of few-layer 1T' MoTe2 using the polarization dependence of the second harmonic generation (SHG) and Raman scattering. Bulk 1T' MoTe2 is known to be inversion symmetric; however, we find that the inversion symmetry is broken for finite crystals with even numbers of layers, resulting in strong SHG comparable to other transition-metal dichalcogenides. Group theory analysis of the polarization dependence of the Raman signals allows for the definitive assignment of all the Raman modes in 1T' MoTe2 and clears up a discrepancy in the literature. The Raman results were also compared with density functional theory simulations and are in excellent agreement with the layer-dependent variations of the Raman modes. The experimental measurements also determine the relationship between the crystal axes and the polarization dependence of the SHG and Raman scattering, which now allows the anisotropy of polarized SHG or Raman signal to independently determine the crystal orientation.

An Electromagnetic Sensor with a Metamaterial Lens for Nondestructive Evaluation of Composite Materials.

This paper proposes the study and implementation of a sensor with a metamaterial (MM) lens in electromagnetic nondestructive evaluation (eNDE). Thus, the use of a new type of MM, named Conical Swiss Rolls (CSR) has been proposed. These structures can serve as electromagnetic flux concentrators in the radiofrequency range. As a direct application, plates of composite materials with carbon fibers woven as reinforcement and polyphenylene sulphide as matrix with delaminations due to low energy impacts were examined. The evaluation method is based on the appearance of evanescent modes in the space between carbon fibers when the sample is excited with a transversal magnetic along z axis (TMz) polarized electromagnetic field. The MM lens allows the transmission and intensification of evanescent waves. The characteristics of carbon fibers woven structure became visible and delaminations are clearly emphasized. The flaws can be localized with spatial resolution better than λ/2000.

Metallic strip gratings in the sub-subwavelength regime.

Metallic strip gratings (MSG) have different applications, ranging from printed circuits to filters in microwave domains. When they are under the influence of an electromagnetic field, evanescent and/or abnormal modes appear in the region between the traces, their utilization leading to the development of new electromagnetic nondestructive evaluation methods. This paper studies the behavior of MSGs in the sub-subwavelength regime when they are excited with TE(z) or TM(z) polarized plane waves and the slits are filled with different dielectrics. The appearance of propagating, evanescent and abnormal modes is emphasized using an electromagnetic sensor with metamaterials lens realized with two conical Swiss rolls, which allows the extraction of the information carried by the guided evanescent waves. The evanescent waves, manipulated by the electromagnetic sensor with metamaterial lenses, improve the electromagnetic images so that a better spatial resolution is obtained, exceeding the limit imposed by diffraction. Their theoretical and experimental confirmation opens the perspective for development of new types of sensors working in radio and microwave frequencies.

DFT study of the structures and energetics of 98-atom AuPd clusters.

The energetics, structures and segregation of 98-atom AuPd nanoclusters are investigated using a genetic algorithm global optimization technique with the Gupta empirical potential (comparing three different potential parameterisations) followed by local minimizations using Density Functional Theory (DFT) calculations. A shell optimization program algorithm is employed in order to study the energetics of the highly symmetric Leary Tetrahedron (LT) structure and optimization of the chemical ordering of a number of structural motifs is carried out using the Basin Hopping Monte Carlo approach. Although one of the empirical potentials is found to favour the LT structure, it is shown that Marks Decahedral and mixed FCC-HCP motifs are lowest in energy at the DFT level.