Thermoelectric properties of Ba-Cu-Si clathrates

Thermoelectric properties of the type-I clathrates Ba$_8$Cu$_x$Si$_{46-x}$ ($3.6 \leq x \leq 7$, $x$ = nominal Cu content) are investigated both experimentally and theoretically. The polycrystalline samples are prepared either by melting, ball milling and hot pressing or by melt spinning, hand milling and hot pressing techniques. Temperature-dependent electrical resistivity, $\rho(T)$, and the Seebeck coefficient, $S(T)$, measurements reveal metal-like behavior for all samples. For $x = 5$ and 6, density functional theory calculations are performed for deriving the enthalpy of formation and the electronic structure which is exploited for the calculation of Seebeck coefficients and conductivity within Boltzmann's transport theory. For simulating the properties of doped clathrates the rigid band model is applied. On the basis of the density functional theory results the experimentally observed compositional dependence of $\rho(T)$ and $S(T)$ of the whole sample series is analyzed. The highest dimensionless thermoelectric figure of merit $ZT$ of 0.28 is reached for a melt-spun sample at $600^{\circ}$C. The relatively low $ZT$ values in this system are attributed to the too high charge carrier concentrations.Comment: 11 pages, 13 figures, submitted to Phys. Rev.

Unconventional superconductivity in weakly correlated, non-centrosymmetric Mo3Al2C\rm{Mo_3Al_2C}

Electrical resistivity, specific heat and NMR measurements classify non-centrosymmetric $\rm Mo_3Al_2C$ ($\beta$-Mn type, space group $P4_132$) as a strong-coupled superconductor with $T_c = 9$~K deviating notably from BCS-like behaviour. The absence of a Hebbel-Slichter peak, a power law behaviour of the spin-lattice relaxation rate (from $^{27}$Al NMR), a $T^3$ temperature dependence of the specific heat and a pressure enhanced $T_c$ suggest unconventional superconductivity with a nodal structure of the superconducting gap. Relativistic DFT calculations reveal a splitting of degenerate electronic bands due to the asymmetric spin-orbit coupling, favouring a mix of spin-singlet and spin triplet components in the superconducting condensate, in absence of strong correlations among electrons.Comment: 4 pages, 5 figure

Enhancing the thermoelectric properties of single and double filled p-type skutterudites synthesized by an up-scaled ball-milling process

The single and double filled p-type skutterudites Ce0.8Fe3CoSb12 and Ce0.5Yb0.5Fe3.25Co0.75Sb12 have been prepared by mechanical alloying. This offers a rapid method for the preparation of skutterudites that could be scaled up for adoption at industrial level. The large-scale samples prepared by ball-milling exhibit enhanced figures of merit ZT, compared with materials prepared by conventional solid-state reaction. At room temperature ZT is increased by ca. 19 % for both single and double filled skutterudites. Maximum figures of merit, ZT = 0.68 and ZT = 0.93 are attained for Ce0.8Fe3CoSb12 at 773 K and Ce0.5Yb0.5Fe3.25Co0.75Sb12 at 823 K respectively. The improvement in thermoelectric values at room temperature may be traced to a reduction in thermal conductivity in the ball-milled samples arising from the reduced grain size. The influence of the microstructure on the thermoelectric properties, together with the stability in air and the performance of the materials after several heating and cooling cycles has been studied and are detailed in this work. The densified samples prepared by ball-milling also show a higher resistance to oxidation, which starts at 694 K for Ce0.8Fe3CoSb12 and at 783 K for Ce0.5Yb0.5Fe3.25Co0.75Sb12

Unusual Behaviour of (Np,Pu)B2C

Two transuranium metal boron carbides, NpB2C and PuB2C have been synthesized by argon arc melting. The crystal structures of the {Np,Pu}B2C compounds were determined from single crystal X-ray data to be isotypic with the ThB2C-type (space group R3m, a = 0.6532(2) nm; c = 1.0769(3) nm for NpB2C and a = 0.6509(2) nm; c = 1.0818(3) nm for PuB2C; Z=9). Physical properties have been derived from polycrystalline bulk material in the temperature range from 2 K to 300 K and in magnetic fields up to 9 T. Magnetic susceptibility and heat capacity data indicate the occurrence of antiferromagnetic ordering for NpB2C with a Neel temperature T_N = 68 K. PuB2C is a Pauli paramagnet most likely due to a strong hybridisation of s(p,d) electrons with the Pu-5f states. A pseudo-gap, as concluded from the Sommerfeld value and the electronic transport, is thought to be a consequence of the hybridisation. The magnetic behaviour of {Np,Pu}B2C is consistent with the criterion of Hill

Superconductivity in novel Ge-based skutterudites: {Sr,Ba}Pt_4Ge_{12}

Combining experiments and ab initio models we report on $\rm SrPt_4Ge_{12}$ and $\rm BaPt_4Ge_{12}$ as members of a novel class of superconducting skutterudites, where Sr or Ba atoms stabilize a framework entirely formed by Ge-atoms. Below $T_c=5.35$ K, and 5.10 K for $\rm BaPt_4Ge_{12}$ and $\rm SrPt_4Ge_{12}$, respectively, electron-phonon coupled superconductivity emerges, ascribed to intrinsic features of the Pt-Ge framework, where Ge-$p$ states dominate the electronic structure at the Fermi energy.Comment: 4 pages, 4 figures, accepted for publication in PR

Intermediate valence behavior in CeCo9Si4

The novel ternary compound CeCo$_9$Si$_4$ has been studied by means of specific heat, magnetisation, and transport measurements. Single crystal X-ray Rietveld refinements reveal a fully ordered distribution of Ce, Co and Si atoms with the tetragonal space group I4/mcm isostructural with other RCo9Si4. The smaller lattice constants of CeCo9Si4 in comparison with the trend established by other RCo9Si4 is indicative for intermediate valence of cerium. While RCo9Si4 with R= Pr, .. Tb, and Y show ferromagnetism and LaCo9Si4 is nearly ferromagnetic, CeCo9Si4 remains paramagnetic even in external fields as large as 40 T, though its electronic specific heat coefficient (g~190 mJ/molK^2) is of similar magnitude as that of metamagnetic LaCo9Si4 and weakly ferromagnetic YCo9Si4.Comment: 2 pages, 3 figures, submitted to SCES 0

Heavy fermion superconductivity and magnetic order in non-centrosymmetric CePt3SiCePt_3Si

$\rm CePt_3Si$ is a novel heavy fermion superconductor, crystallising in the $\rm CePt_3B$ structure as a tetragonally distorted low symmetry variant of the $\rm AuCu_3$ structure type. $\rm CePt_3Si$ exhibits antiferromagnetic order at $T_N \approx 2.2$ K and enters into a heavy fermion superconducting state at $T_c \approx 0.75$ K. Large values of $H_{c2}' \approx -8.5$ T/K and $H_{c2}(0) \approx 5$ T refer to heavy quasiparticles forming Cooper pairs. Hitherto, $\rm CePt_3Si$ is the first heavy fermion superconductor without a center of symmetry.Comment: 4 pages, 4 figure

Terahertz superlattice parametric oscillator

We report a GaAs/AlAs superlattice parametric oscillator. It was pumped by a microwave field (power few mW) and produced 3rd harmonic radiation (frequency near 300 GHz). The nonlinearity of the active superlattice was due to Bragg reflections of conduction electrons at the superlattice planes. A theory of the nonlinearity indicates that parametric oscillation should be possible up to frequencies above 10 THz. The active superlattice may be the object of further studies of predicted extraordinary nonlinearities for THz fields.Comment: 10 pages, 4 figure