Spectroscopy of H3_3S: evidence of a new energy scale for superconductivity

The discovery of a superconducting phase in sulfur hydride under high pressure with a critical temperature above 200 K has provided a new impetus to the search for even higher $T_c$. Theory predicted and experiment confirmed that the phase involved is H$_3$S with Im-3m crystal structure. The observation of a sharp drop in resistance to zero at $T_c$, its downward shift with magnetic field and a Meissner effect confirm superconductivity but the mechanism involved remains to be determined. Here, we provide a first optical spectroscopy study of this new superconductor. Experimental results for the optical reflectivity of H$_3$S, under high pressure of 150 GPa, for several temperatures and over the range 60 to 600 meV of photon energies, are compared with theoretical calculations based on Eliashberg theory using DFT results for the electron-phonon spectral density $\alpha^2$F($\Omega$). Two significant features stand out: some remarkably strong infrared active phonons at $\approx$ 160 meV and a band with a depressed reflectance in the superconducting state in the region from 450 meV to 600 meV. In this energy range, as predicted by theory, H$_3$S is found to become a better reflector with increasing temperature. This temperature evolution is traced to superconductivity originating from the electron-phonon interaction. The shape, magnitude, and energy dependence of this band at 150 K agrees with our calculations. This provides strong evidence of a conventional mechanism. However, the unusually strong optical phonon suggests a contribution of electronic degrees of freedom.Comment: 10 pages, 8 figures. Main manuscript and supplementary informatio

Optical investigation of thermoelectric topological crystalline insulator Pb0.77_{0.77}Sn0.23_{0.23}Se

Pb$_{0.77}$Sn$_{0.23}$Se is a novel alloy of two promising thermoelectric materials PbSe and SnSe that exhibits a temperature dependent band inversion below 300 K. Recent work has shown that this band inversion also coincides with a trivial to nontrivial topological phase transition. To understand how the properties critical to thermoelectric efficiency are affected by the band inversion, we measured the broadband optical response of Pb$_{0.77}$Sn$_{0.23}$Se as a function of temperature. We find clear optical evidence of the band inversion at $160\pm15$ K, and use the extended Drude model to accurately determine a $T^{3/2}$ dependence of the bulk carrier lifetime, associated with electron-acoustic phonon scattering. Due to the high bulk carrier doping level, no discriminating signatures of the topological surface states are found, although their presence cannot be excluded from our data.Comment: 11 pages, 6 figure

Molecular assembling in mixtures of hydrophilic 1-butyl-1-methylpyrrolidinium dicyanamide ionic liquid and water

The infrared absorbance spectrum of the ionic liquid 1-butyl-1-methylpyrrolidinium dicyanamide, mixed with water at two different concentrations, was measured between 160 and 300 K in the mid infrared range. Both mixtures do not crystallize on cooling; however, remarkably, the one with an ionic liquid (IL):water composition of 1:3 displays a cold crystallization process on heating in a restricted temperature range between 240 and 250 K. A portion of the water participates to the cold crystallization. On the contrary, with an IL:water composition of 1:6.6 no crystallization takes place. Upon water addition the vibration frequencies of the anion and of some lines of the cation are blue shifted, while the absorption lines of water are red shifted. These facts are interpreted as the evidence of the occurrence of the hydrogen bonding of water, as the hydrogen bonding acceptor with respect to the anion (anion···O-H bonds develop) and as hydrogen donor for the cation (C-H···O bonds can form). Microscopic inhomogeneities in the samples and their evolution with temperature are discussed

Phonons in the multiferroic langasite Ba_3\_3NbFe_3\_3Si_2\_2O_14\_{14} : evidences for symmetry breaking

The chiral langasite Ba$\_3$NbFe$\_3$Si$\_2$O$\_{14}$ is a multiferroic compound. While its magnetic order below T$\_N$=27 K is now well characterised, its polar order is still controversial. We thus looked at the phonon spectrum and its temperature dependence to unravel possible crystal symmetry breaking. We combined optical measurements (both infrared and Raman spectroscopy) with ab initio calculations and show that signatures of a polar state are clearly present in the phonon spectrum even at room temperature. An additional symmetry lowering occurs below 120~K as seen from emergence of softer phonon modes in the THz range. These results confirm the multiferroic nature of this langasite and open new routes to understand the origin of the polar state

Lattice and spin excitations in multiferroic h-YMnO3

We used Raman and terahertz spectroscopies to investigate lattice and magnetic excitations and their cross-coupling in the hexagonal YMnO3 multiferroic. Two phonon modes are strongly affected by the magnetic order. Magnon excitations have been identified thanks to comparison with neutron measurements and spin wave calculations but no electromagnon has been observed. In addition, we evidenced two additional Raman active peaks. We have compared this observation with the anti-crossing between magnon and acoustic phonon branches measured by neutron. These optical measurements underly the unusual strong spin-phonon coupling

Grazing-angle reflectivity setup for the low-temperature infrared spectroscopy of two-dimensional systems

A new optical setup is described that allows the reflectivity at grazing incidence to be measured, including ultrathin films and two-dimensional electron systems (2DES) down to liquid-helium temperatures, by exploiting the Berreman effect and the high brilliance of infrared synchrotron radiation. This apparatus is well adapted to detect the absorption of a 2DES of nanometric thickness, namely that which forms spontaneously at the interface between a thin film of LaAlO3 and its SrTiO3 substrate, and to determine its Drude parameters

Low-oxidation-state Ru sites stabilized in carbon-doped RuO2 with low-temperature CO2 activation to yield methane

The generation of methane fuel using surplus renewable energy with CO as the carbon source enables both the decarbonization and substitution of fossil fuel feedstocks. However, high temperatures are usually required for the efficient activation of CO. Here we present a solid catalyst synthesized using a mild, green hydrothermal synthesis that involves interstitial carbon doped into ruthenium oxide, which enables the stabilization of Ru cations in a low oxidation state and a ruthenium oxycarbonate phase to form. The catalyst shows an activity and selectivity for the conversion of CO into methane at lower temperatures than those of conventional catalysts, with an excellent long-term stability. Furthermore, this catalyst is able to operate under intermittent power supply conditions, which couples very well with electricity production systems based on renewable energies. The structure of the catalyst and the nature of the ruthenium species were acutely characterized by combining advanced imaging and spectroscopic tools at the macro and atomic scales, which highlighted the low-oxidation-state Ru sites (Ru, 0 < n < 4) as responsible for the high catalytic activity. This catalyst suggests alternative perspectives for materials design using interstitial dopants.We thank the support of C. Cerdá and M. D. Soriano in the catalyst preparation and testing. This research was funded by the Ministerio de Ciencia, Innovación y Universidades (grant nos. PID2021-1262350B-C31, PID2020-113006-RB-I00, PID2019-110018GA-I00 and MCIN/AEI/10.13039/501100011033), Generalitat Valenciana (grant no. CIAICO/2021/2138), the Department of Economy, Knowledge, Business and the University of the Regional Government of Andalusia (project reference FEDER-UCA18-107139). This study forms part of the Advanced Materials programme and was supported by MCIN with funding from the European Union Next Generation (EU PRTR-C17.11) and by Generalitad Valenciana (ref. MFA/2022/016). C.T.-S. acknowledges the Polytechnical University of Valencia for the economic support through an FPI scholarship associated with the PAID programme ‘Programa de Ayudas de Investigación y Desarrollo’. XAS, XPS and XRD experiments were performed at the ALBA Synchrotron with the collaboration of ALBA staff. Infrared experiments were performed at the SOLEIL Synchrotron with the collaboration of SOLEIL staff

High repetition-rate electro-optic sampling: Recent studies using photonic time-stretch

Single-shot electro-optic sampling (EOS) is a powerful characterization tool for monitoring the shape of electron bunches, and coherent synchrotron radiation pulses. For reaching high acquisition rates, an efficient possibility consists to associate classic EOS systems with the so-called photonic time-stretch technique [1]. We present recent results obtained at SOLEIL and ANKA using this strategy. In particular, we show how a high sensitivity variant of photonic time stretch [2] EOS enabled to monitor the CSR pulses emitted by short electron bunches at SOLEIL [3]. We could thus confirm in a very direct way the theories predicting an interplay between two physical processes. Below a critical bunch charge, we observe a train of identical THz pulses stemming from the shortness of the electron bunches. Above this threshold, CSR emission is dominated by drifting structures appearing through spontaneous self-organization. We also consider the association of time-stretch and EOS for recording electron bunch near fields at high repetition rate. We present preliminary results obtained at ANKA, aiming at recording the electron bunch shape evolution during the microbunching instability