Phonon-glass electron-crystal thermoelectric clathrates: Experiments and theory

Type-I clathrate compounds have attracted a great deal of interest in connection with the search for efficient thermoelectric materials. These compounds constitute networked cages consisting of nano-scale tetrakaidecahedrons (14 hedrons) and dodecahedrons (12 hedrons), in which the group 1 or 2 elements in the periodic table are encaged as the so-called rattling guest atom. It is remarkable that, though these compounds have crystalline cubic-structure, they exhibit glass-like phonon thermal conductivity over the whole temperature range depending on the states of rattling guest atoms in the tetrakaidecahedron. In addition, these compounds show unusual glass-like specific heats and THz-frequency phonon dynamics, providing a remarkable broad peak almost identical to those observed in topologically disordered amorphous materials or structural glasses, the so-called Boson peak. An efficient thermoelectric effect is realized in compounds showing these glass-like characteristics. This decade, a number of experimental works dealing with type-I clathrate compounds have been published. These are diffraction experiments, thermal and spectroscopic experiments in addition to those based on heat and electronic transport. These form the raw materials for this article based on advances this decade. The subject of this article involves interesting phenomena from the viewpoint of not only physics but also from the view point of the practical problem of elaborating efficient thermoelectric materials. This review presents a survey of a wide range of experimental investigations of type-I clathrate compounds, together with a review of theoretical interpretations of the peculiar thermal and dynamic properties observed in these materials.Comment: 51pages, 43 figure

Spontaneous strain due to ferroquadrupolar ordering in UCu2_2Sn

The ternary uranium compound UCu$_2$Sn with a hexagonal ZrPt$_2$Al-type structure shows a phase transition at 16 K. We reported previously that huge lattice-softening is accompanied by the phase transition, which originates from ferroquadrupolar ordering of the ground state non-Kramers doublet $\Gamma_5$. A macroscopic strain, which is expected to emerge spontaneously, was not detected by powder X-ray diffraction in the temperature range between 4.2 and 300 K. To search the spontaneous strain, we have carried out thermal expansion measurements on a single-crystalline sample along the $a$, $b$ and $c$ axes using a capacitance technique with the resolution of $10^{-8}$. In the present experiment, we found the spontaneous $e_{xx} - e_{yy}$ strain which couples to the ground state doublet $\Gamma_5$. The effect of uniaxial pressure along the $a$, $b$ and $c$ axes on the transition temperature is also discussed.Comment: 4 pages, 5 figures, submitted to Phys. Rev.

Structural Modification and Metamagnetic Anomaly in the Ordered State of CeOs2Al10

A caged compound CeOs2Al10, crystallizing in the orthorhombic YbFe2Al10-type structure, undergoes a mysterious phase transition at T_0=29 K. We report the results of electron diffraction, magnetization, and magnetoresistance for single crystals. Superlattice reflections characterized by a wave vector q = (0, -2/3, 2/3) observed at 15 K indicate a structural modification in the ordered state. Activation-type behavior of the electrical resistivity along the three principal axes below 50 K suggests gap opening in the conduction band. The magnetic susceptibility \chi = M/B is highly anisotropic, \chi_a>\chi_c>\chi_b, all of which sharply decrease on cooling below T_0. Furthermore, a metamagnetic anomaly in the magnetization and a step in the magnetoresistance occur at B=6-8 T only when the magnetic field is applied parallel to the orthorhombic c axis. However, T_0 hardly changes under magnetic fields up to 14 T, irrespective of the field direction. By using these data, we present a B-T phase diagram and discuss several scenarios for the mysterious transition.Comment: 6 pages, 7 figures, accepted for publication in Phys. Rev.

Magnetic-field tuning of the low-temperature state of YbNiSi3

We present detailed data from low-temperature magnetization, magnetoresistance, and specific heat measurements on single-crystal YbNiSi3 with the magnetic field applied along the easy magnetic axis, H∥b. An initially antiferromagnetic ground state changes into a field-stabilized metamagnetic phase at ∼16kOe (T→0). On further increase of the magnetic field, magnetic order is suppressed at ∼85kOe. No non-Fermi-liquid-like power law was observed in the resistivity in the vicinity of the critical field for T⩾0.4K. Heat capacity measurements suggest that the applied magnetic field splits the nearly degenerate crystal-electric-field levels that form the zero-field ground state of YbNiSi3. The functional behaviors of the resistivity and specific heat are discussed in comparison with those of the few other stoichiometric heavy fermion compounds with established field-induced quantum critical points