Theoretical search for Chevrel phase based thermoelectric materials

We investigate the thermoelectric properties of some semiconducting Chevrel phases. Band structure calculations are used to compute thermopowers and to estimate of the effects of alloying and disorder on carrier mobility. Alloying on the Mo site with transition metals like Re, Ru or Tc to reach a semiconducting composition causes large changes in the electronic structure at the Fermi level. Such alloys are expected to have low carrier mobilities. Filling with transition metals was also found to be incompatible with high thermoelectric performance based on the calculated electronic structures. Filling with Zn, Cu, and especially with Li was found to be favorable. The calculated electronic structures of these filled Chevrel phases are consistent with low scattering of carriers by defects associated with the filling. We expect good mobility and high thermopower in materials with the composition close to (Li,Cu)$_4$Mo$_6$Se$_8$, particularly when Li-rich, and recommend this system for experimental investigation.Comment: 4 two-column pages, 4 embedded ps figure

Electronic Structure of the Chevrel-Phase Compounds Snx_{x}Mo6_{6}Se7.5_{7.5}: Photoemission Spectroscopy and Band-structure Calculations

We have studied the electronic structure of two Chevrel-phase compounds, Mo$_6$Se$_{7.5}$ and Sn$_{1.2}$Mo$_6$Se$_{7.5}$, by combining photoemission spectroscopy and band-structure calculations. Core-level spectra taken with x-ray photoemission spectroscopy show systematic core-level shifts, which do not obey a simple rigid-band model. The inverse photoemission spectra imply the existence of an energy gap located $\sim 1$ eV above the Fermi level, which is a characteristic feature of the electronic structure of the Chevrel compounds. Quantitative comparison between the photoemission spectra and the band-structure calculations have been made. While good agreement between theory and experiment in the wide energy range was obtained as already reported in previous studies, we found that the high density of states near the Fermi level predicted theoretically due to the Van Hove singularity is considerably reduced in the experimental spectra taken with higher energy resolution than in the previous reports. Possible origins are proposed to explain this observation.Comment: 8 pages, 5 figure

Node-like excitations in superconducting PbMo6S8 probed by scanning tunneling spectroscopy

We present the first scanning tunneling spectroscopy study on the Chevrel phase PbMo6S8, an extreme type II superconductor with a coherence length only slightly larger than in high-Tc cuprates. Tunneling spectra measured on atomically flat terraces are spatially homogeneous and show well-defined coherence peaks. The low-energy spectral weight, the zero bias conductance and the temperature dependence of the gap are incompatible with a conventional isotropic s-wave interpretation, revealing the presence of low-energy excitations in the superconducting state. We show that our data are consistent with the presence of nodes in the superconducting gap.Comment: To appear in PRB; 5 pages, 4 figure

Phonon Mode Spectroscopy, Electron-Phonon Coupling and the Metal-Insulator Transition in Quasi-One-Dimensional M2Mo6Se6

We present electronic structure calculations, electrical resistivity data and the first specific heat measurements in the normal and superconducting states of quasi-one-dimensional M2Mo6Se6 (M = Tl, In, Rb). Rb2Mo6Se6 undergoes a metal-insulator transition at ~170K: electronic structure calculations indicate that this is likely to be driven by the formation of a dynamical charge density wave. However, Tl2Mo6Se6 and In2Mo6Se6 remain metallic down to low temperature, with superconducting transitions at Tc = 4.2K and 2.85K respectively. The absence of any metal-insulator transition in these materials is due to a larger in-plane bandwidth, leading to increased inter-chain hopping which suppresses the density wave instability. Electronic heat capacity data for the superconducting compounds reveal an exceptionally low density of states DEF = 0.055 states eV^-1 atom^-1, with BCS fits showing 2Delta/kBTc >= 5 for Tl2Mo6Se6 and 3.5 for In2Mo6Se6. Modelling the lattice specific heat with a set of Einstein modes, we obtain the approximate phonon density of states F(w). Deconvolving the resistivity for the two superconductors then yields their electron-phonon transport coupling function a^2F(w). In Tl2Mo6Se6 and In2Mo6Se6, F(w) is dominated by an optical "guest ion" mode at ~5meV and a set of acoustic modes from ~10-30meV. Rb2Mo6Se6 exhibits a similar spectrum; however, the optical phonon has a lower intensity and is shifted to ~8meV. Electrons in Tl2Mo6Se6 couple strongly to both sets of modes, whereas In2Mo6Se6 only displays significant coupling in the 10-18meV range. Although pairing is clearly not mediated by the guest ion phonon, we believe it has a beneficial effect on superconductivity in Tl2Mo6Se6, given its extraordinarily large coupling strength and higher Tc compared to In2Mo6Se6.Comment: 16 pages, 13 figure

Upper Critical Field of Pressure-Induced Superconductor EuFe2_2As2_2

We have carried out high-field resistivity measurements up to 27\,T in EuFe$_2$As$_2$ at $P$\,=\,2.5\,GPa, a virtually optimal pressure for the $P$-induced superconductivity, where $T_\mathrm{c}$\,=\,30\,K. The $B_\mathrm{c2}-T_\mathrm{c}$ phase diagram has been constructed in a wide temperature range with a minimum temperature of 1.6 K ($\approx 0.05 \times T_\mathrm{c}$), for both $B \parallel ab$ ($B_\mathrm{c2}^\mathrm{ab}$) and $B \parallel c$ ($B_\mathrm{c2}^\mathrm{c}$). The upper critical fields $B_\mathrm{c2}^\mathrm{ab}$(0) and $B_\mathrm{c2}^\mathrm{c}$(0), determined by the onset of resistive transitions, are 25 T and 22 T, respectively, which are significantly smaller than those of other Fe-based superconductors with similar values of $T_\mathrm{c}$. The small $B_\mathrm{c2}(0)$ values and the $B_\mathrm{c2}(T)$ curves with positive curvature around 20 K can be explained by a multiple pair-breaking model that includes the exchange field due to the magnetic Eu$^{2+}$ moments. The anisotropy parameter, $\Gamma=B_\mathrm{c2}^{ab}/B_\mathrm{c2}^{c}$, in EuFe$_2$As$_2$ at low temperatures is comparable to that of other "122" Fe-based systems.Comment: 5 pages, 4 figures, revised version to be published in Phys. Rev. B (Rapid Communications

Resistivity saturation in PrFeAsO1−x_{1-x}Fy_y superconductor: An evidence of strong electron-phonon coupling

We have measured the resistivity of PrFeAsO$_{1-x}$F$_y$ samples over a wide range of temperature in order to elucidate the role of electron-phonon interaction on normal- and superconducting-state properties. The linear T dependence of $\rho$ above 170 K followed by a saturationlike behavior at higher temperature is a clear signature of strong electron-phonon coupling. From the analysis of T dependence of $\rho$, we have estimated several normal-state parameters useful for understanding the origin of superconductivity in this system. Our results suggest that Fe-based oxypnictides are phonon mediated BCS superconductors like Chevrel phases and A15 compounds.Comment: 15 pages, 4 figure

Possible re-entrant superconductivity in EuFe2As2 under pressure

We studied the temperature-pressure phase diagram of EuFe2As2 by measurements of the electrical resistivity. The antiferromagnetic spin-density-wave transition at T_0 associated with the FeAs-layers is continuously suppressed with increasing pressure, while the antiferromagnetic ordering temperature of the Eu 2+ moments seems to be nearly pressure independent up to 2.6 GPa. Above 2 GPa a sharp drop of the resistivity, \rho(T), indicates the onset of superconductivity at T_c \approx 29.5 K. Surprisingly, on further reducing the temperature \rho(T) is increasing again and exhibiting a maximum caused by the ordering of the Eu 2+ moments, a behavior which is reminiscent of re-entrant superconductivity as it is observed in the ternary Chevrel phases or in the rare-earth nickel borocarbides