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Electrical and magnetic properties of La$_{0.5}$Rh$_4$Sb$_{12}$ filled skutterudite synthesized at high pressure

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 Added by Soshi Ibuka
 Publication date 2015
  fields Physics
and research's language is English




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A filled skutterudite, La$_{0.5}$Rh$_4$Sb$_{12}$, with a lattice constant of 9.284(2) {AA} was synthesized using a high-pressure technique. The electrical resistivity showed semiconducting behavior and the energy gap was estimated to be more than 0.08 eV. Magnetic susceptibility measurements indicated temperature-independent diamagnetism, which originates from Larmor diamagnetism. The electrical properties of this compound are more similar to those of the La$_{0.5}$Rh$_4$As$_{12}$ semiconductor with an energy gap of 0.03 eV than to those of the La$_{0.6}$Rh$_4$P$_{12}$ superconductor.



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Anomalous metal-insulator transition observed in filled skutterudite CeOs$_4$Sb$_{12}$ is investigated by constructing the effective tight-binding model with the Coulomb repulsion between f electrons. By using the mean field approximation, magnetic susceptibilities are calculated and the phase diagram is obtained. When the band structure has a semimetallic character with small electron and hole pockets at $Gamma$ and H points, a spin density wave transition with the ordering vector $mathbf{Q}=(1,0,0)$ occurs due to the nesting property of the Fermi surfaces. Magnetic field enhances this phase in accord with the experiments.
MHz conductivity, torque magnetometer and magnetization measurements are reported on single crystals of CeOs$_4$Sb$_{12}$ and NdOs$_4$Sb$_{12}$ using temperatures down to 0.5~K and magnetic fields of up to 60~tesla. The field-orientation dependence of the de Haas-van Alphen and Shubnikov-de Haas oscillations is deduced by rotating the samples about the $[010]$ and $[0bar{1}1]$ directions. The results indicate that NdOs$_4$Sb$_{12}$ has a similar Fermi surface topology to that of the unusual superconductor PrOs$_4$Sb$_{12}$, but with significantly smaller effective masses, supporting the importance of local phonon modes in contributing to the low-temperature heat capacity of NdOs$_4$Sb$_{12}$. By contrast, CeOs$_4$Sb$_{12}$ undergoes a field-induced transition from an unusual semimetal into a high-field, high-temperature state characterized by a single, almost spherical Fermi-surface section. The behavior of the phase boundary and comparisons with models of the bandstructure lead us to propose that the field-induced phase transition in CeOs$_4$Sb$_{12}$ is similar in origin to the well-known $alpha-gamma$ transition in Ce and its alloys.
The filled skutterudite compound PrOsSb{} exhibits superconductivity below a critical temperature $T_mathrm{c} = 1.85$ K that develops out of a nonmagnetic heavy Fermi liquid with an effective mass $m^{*} approx 50 m_mathrm{e}$, where $m_mathrm{e}$ is the free electron mass. Analysis of magnetic susceptibility, specific heat, electrical resistivity and inelastic neutron scattering measurements within the context of a cubic crystalline electric field yields a Pr$^{3+}$ energy level scheme that consists of a $Gamma_{3}$ nonmagnetic doublet ground state that carries an electric quadrupole moment, a low lying $Gamma_{5}$ triplet excited state at $sim 10$ K, and $Gamma_{4}$ triplet and $Gamma_{1}$ singlet excited states at much higher temperatures. The superconducting state appears to be unconventional and to consist of two distinct superconducting phases. An ordered phase of magnetic or quadrupolar origin occurs at high fields and low temperatures, suggesting that the superconductivity may occur in the vicinity of a magnetic or electric quadrupolar quantum critical point.
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We report on systematic study of superconducting characteristics and Pr crystalline-electric-field (CEF) levels of filled-skutterudite pra ($T_{rm c}$ = 2.33 K). The temperature dependences of the upper critical field $H_{rm c2}$ and the Ginzburg-Landau (Maki) parameter $kappa_2$ suggest an s-wave clean-limit superconductivity. The electronic specific heat coefficient $gamma sim 95$ mJ/K$^2$mol, being $sim 1.5$ times larger than that for lra, indicates $4f$-originating quasiparticle mass enhancement. Magnetic susceptibility $chi(T)$ indicates that the CEF ground state is a $Gamma_1$ singlet and a $Gamma_4^{(1)}$ triplet first excited state lies at $Delta_{rm CEF}sim 30$ K above. Systematic comparison among pos, prs, pra and La-based reference compounds suggests that inelastic exchange- and aspherical-charge-scatterings of conduction electrons from CEF-split $4f$ levels play an essential role for the quasiparticle mass enhancement and the value of $T_{rm c}$ in the Pr-based filled skutterudites.
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We studied nanoprecipitates and defects in p-type filled skutterudite CeFe4Sb12 prepared by non-equilibrium melt-spinning plus spark plasma sintering method using transmission electron microscopy. Nanoprecipitates with mostly spherical shapes and different sizes (from several nm to several tens of nm) have been observed. The most typically observed nanoprecipitates are shown to be Sb-rich. Superlattices with a periodicity of about 3.576 nm were induced by the ordering of excessive Sb atoms along the c direction. These nanoprecipitates usually share coherent interfaces with the surrounding matrix and induce anisotropic and strong strain fields in the surrounding matrix. Nanoprecipitates with compositions close to CeSb2 are much larger in size (~ 30 nm) and have orthorhombic structures. Various defects were typically observed on the interfaces between these nanoprecipitates and the matrix. The strain fields induced by these nanoprecipitates are less distinct, possibly because part of the strains has been released by the formation of defects.
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