Electronic band structure and low-temperature transport properties of the type-I clathrate Ba8Ni(x)Ge(46-x-y□y).

We present the evolution of the low-temperature thermodynamic, galvanomagnetic and thermoelectric properties of the type-I clathrate Ba8Ni(x)Ge(46-x-y□y) with the Ni concentration studied on polycrystalline samples with 0.0 ≤ x ≤ 6.0 by means of specific heat, Hall effect, electrical resistivity, thermopower and thermal conductivity measurements in the 2-350 K temperature range and supported by first-principles calculations. The experimental results evidence a 2a × 2a × 2a supercell described in the space group Ia3d for x ≤ 1.0 and a primitive unit cell a × a × a (space group Pm3n) above this Ni content. This concentration also marks the limit between a regime where both electrons and holes contribute to the electrical conduction (x ≤ 1.0) and a conventional, single-carrier regime (x > 1.0). This evolution is traced by the variations in the thermopower and Hall effect with x. In agreement with band structure calculations, increasing the Ni content drives the system from a nearly-compensated semimetallic state (x = 0.0) towards a narrow-band-gap semiconducting state (x = 4.0). A crossover from an n-type to a p-type conduction occurs when crossing the x = 4.0 concentration i.e. for x = 4.1. The solid solution Ba8Ni(x)Ge(46-x-y□y) therefore provides an excellent experimental platform to probe the evolution of the peculiar properties of the parent type-I clathrate Ba8Ge43□3 upon Ge/Ni substitution and filling up of the vacancies, which might be universal among the ternary systems at low substitution levels.

High temperature thermoelectric properties of the type-I clathrate Ba8NixGe46-x-y□y.

Polycrystalline samples of the type-I clathrate Ba(8)Ni(x)Ge(46-x-y)□(y) were synthesized for 0.2 ⩽ x ⩽ 3.5 by melt quenching and for 3.5

Synthesis, crystal structure, and physical properties of the type-I clathrate Ba(8-δ)Ni(x)□(y)Si(46-x-y).

Type-I clathrate phase Ba(8)Ni(x)□(y)Si(46-x-y) (□ = vacancy) was obtained from the elements at 1000 °C with the homogeneity range 2.4 ≤ x ≤ 3.8 and 0 ≤ y ≤ 0.9. In addition, samples with low Ni content (x = 1.4 and 1.6; y = 0) and small Ba deficiency were prepared from the melt by steel-quenching. Compositions were established by microprobe analysis and crystal structure determination. Ba(8-δ)Ni(x)□(y)Si(46-x-y) crystallizes in the space group Pm ̅3n (No. 223) with lattice parameter ranging from a = 10.3088(1) Å for Ba(7.9(1))Ni(1.4(1))Si(44.6(1)) to a = 10.2896(1) Å for Ba(8.00(3))Ni(3.82(4))Si(41.33(6)). Single-crystal X-ray diffraction data together with microprobe analysis indicate an increasing number of framework vacancies toward compositions with higher Ni content. For all compositions investigated, Ni K-edge X-ray absorption spectroscopy measurements showed an electronic state close to that of elemental Ni. All samples exhibit metallic-like behavior with moderate thermopower and low thermal conductivity in the temperature range 300-773 K. Samples with compositions Ba(7.9(1))Ni(1.4(1))Si(44.6(1)) and Ba(7.9(1))Ni(1.6(1))Si(44.4(1)) are superconducting with T(c) values of 6.0 and 5.5 K, respectively.

Determination of gap symmetry from angle-dependent H(c2) measurements on CeCu2Si2.

The tetragonal heavy-fermion compound CeCu2Si2 exhibits a superconducting ground state (S type, T(c) = 0.67 K) close to a magnetic instability. Here, we present angle-resolved resistivity measurements of the upper critical field H(c2). In-plane rotation of S-type CeCu2Si2 single crystals reveals a fourfold oscillation of H(c2). An extended weak-coupling BCS model for a d-wave symmetry including strong Pauli-limiting effects confirms the aforementioned angular dependence and points towards d(xy) symmetry of the order parameter.

Crystal structure and transport properties of Ba8Ge43square3.

The single phase clathrate-I Ba(8)Ge(43)square(3) (space group Ia3d (no. 230), a = 21.307(1) A) was synthesized by quenching the melt between cold steel plates. Specimens for physical property measurements were characterized by microstructure analysis and X-ray diffraction on polycrystalline samples as well as single crystals. Transport properties including thermopower, electrical resistivity, thermal conductivity and specific heat were investigated in a temperature range of 2-673 K. The electrical resistivity exhibits a metal-like temperature dependence below 300 K turning into a semiconductor-like behaviour above 300 K. The analysis of the specific heat at low temperature indicates a finite density of states at the Fermi level, thus corroborating the metallic character below 300 K. The temperature dependence of the specific heat was modelled assuming Einstein-like localized vibrations of Ba atoms inside the cages of the Ge framework. A conventional crystal-like behaviour of the thermal conductivity with a low lattice contribution (kappa(l)(300 K) = 2.7 W m(-1) K(-1)) has been evidenced.

Violation of critical universality at the antiferromagnetic phase transition of YbRh2Si2.

We report on precise low-temperature specific-heat measurements, C(T), of YbRh2Si2 in the vicinity of the antiferromagnetic phase transition on a single crystal of superior quality (residual resistivity ratio of approximately 150). We observe a very sharp peak at T_{N}=72 mK with absolute values as high as C/T=8 J/mol K2. A detailed analysis of the critical exponent alpha around T_{N} reveals alpha=0.38 which differs significantly from those of the conventional universality classes in the Ginzburg-Landau theory, where alpha< or =0.11. Thermal-expansion measurements corroborate this large positive critical exponent. These results provide insight into the nature of the critical magnetic fluctuations at a temperature-driven phase transition close to a quantum critical point.

New non-magnetically ordered heavy-fermion system CeTiGe.

Investigations of the susceptibility, electrical resistivity, specific heat and thermopower of CeTiGe at low temperatures show that this compound is a Kondo lattice system with an enhanced Sommerfeld coefficient γ≈0.3 J K(-2) mol(-1) and where the whole J = 5/2 multiplet is involved in the formation of the ground state. No magnetic order was observed down to 0.4 K. In the temperature range below 10 K we observed Fermi-liquid behavior as indicated by a ρ(T)∼T(2) dependence in the electrical resistivity and a linear specific heat and thermopower. Because of these results we classify CeTiGe as a moderate heavy-fermion system with a non-magnetic ground state.

Uniaxial pressure effects on CeIrIn5 and CeCoIn5 studied by low-temperature thermal expansion.

We report low-temperature thermal expansion measurements on the tetragonal heavy-fermion superconductors CeMIn5 (M=Ir,Co) in magnetic fields up to 8 T which allow for the analysis of the uniaxial pressure effects on both normal-state and superconducting properties. Our study reveals that T(c) is strongly affected by at least two factors, the lattice anisotropy and the 4f-conduction-electron hybridization strength which is most sensitive to c-axis lattice distortions. Non-Fermi-liquid behavior caused by quantum-critical fluctuations is observed for both systems, most pronounced for CeCoIn5.

Divergence of the grüneisen ratio at quantum critical points in heavy fermion metals.

We present low-temperature volume thermal expansion, beta, and specific heat, C, measurements on high-quality single crystals of CeNi2Ge2 and YbRh2(Si0.95Ge0.05)(2) which are located very near to quantum critical points. For both systems, beta shows a more singular temperature dependence than C, and thus the Grüneisen ratio Gamma proportional to beta/C diverges as T-->0. For CeNi2Ge2, our results are in accordance with the spin-density wave (SDW) scenario for three-dimensional critical spin fluctuations. By contrast, the observed singularity in YbRh2(Si0.95Ge0.05)(2) cannot be explained by the itinerant SDW theory but is qualitatively consistent with a locally quantum critical picture.

First-order superconducting phase transition in CeCoIn5.

The superconducting phase transition in heavy fermion CeCoIn5 (T(c)=2.3 K in zero field) becomes first order when the magnetic field H parallel [001] is greater than 4.7 T, and the transition temperature is below T0 approximately 0.31T(c). The change from second order at lower fields is reflected in strong sharpening of both specific heat and thermal expansion anomalies associated with the phase transition, a strong magnetocaloric effect, and a steplike change in the sample volume. This effect is due to Pauli limiting in a type-II superconductor, and was predicted theoretically in the mid-1960s.