Strongly reduced lattice thermal conductivity in Sn-doped rare-earth (M) filled skutterudites M x Co4Sb12-y Sn y , promoted by Sb-Sn disordering and phase segregation.

CoSb3 thermoelectric skutterudite has been filled with rare-earth metals (M = La, Ce, Yb) and partially doped with Sn in specimens of M x Co4Sb12-y Sn y stoichiometry. This has been achieved under high-pressure conditions at 3.5 GPa in a piston-cylinder hydrostatic press. A structural investigation using synchrotron X-ray diffraction data reveals a phase segregation in twin skutterudite phases with filling fraction fluctuation and different unit-cell sizes. As a result of three effects acting as phonon scatterers, namely the rattling effect of M at the wide 8a cages of the cubic Im3̄ structure, the phase segregation, and the intrinsic disorder introduced by Sn substitution at the Sb sublattice, the total thermal conductivity (κ) dramatically falls to reach minimum values under 2 W m-1 K-1, well below those typically exhibited by other thermoelectric materials based upon single-filled skutterudites. The power factor is substantially enhanced to 1.11 mW m-1 K-2 in Yb0.5Co4Sb11.6Sn0.4 with respect to the unfilled composition, as a result of the charge transfer promoted by the filler.

Ultralong Spin Lifetime in Light Alkali Atom Doped Graphene.

Today's great challenges of energy and informational technologies are addressed with a singular compound, Li- and Na-doped few-layer graphene. All that is impossible for graphite (homogeneous and high-level Na doping) and unstable for single-layer graphene works very well for this structure. The transformation of the Raman G line to a Fano line shape and the emergence of strong, metallic-like electron spin resonance (ESR) modes attest the high level of graphene doping in liquid ammonia for both kinds of alkali atoms. The spin-relaxation time in our materials, deduced from the ESR line width, is 6-8 ns, which is comparable to the longest values found in spin-transport experiments on ultrahigh-mobility graphene flakes. This could qualify our material as a promising candidate in spintronics devices. On the other hand, the successful sodium doping, this being a highly abundant metal, could be an encouraging alternative to lithium batteries.

Giant microwave absorption in fine powders of superconductors.

Enhanced microwave absorption, larger than that in the normal state, is observed in fine grains of type-II superconductors (MgB2 and K3C60) for magnetic fields as small as a few % of the upper critical field. The effect is predicted by the theory of vortex motion in type-II superconductors, however its direct observation has been elusive due to skin-depth limitations; conventional microwave absorption studies employ larger samples where the microwave magnetic field exclusion significantly lowers the absorption. We show that the enhancement is observable in grains smaller than the penetration depth. A quantitative analysis on K3C60 in the framework of the Coffey-Clem (CC) theory explains well the temperature dependence of the microwave absorption and also allows to determine the vortex pinning force constant.

Enhanced figure of merit in nanostructured (Bi,Sb)2Te3 with optimized composition, prepared by a straightforward arc-melting procedure.

Sb-doped Bi2Te3 is known since the 1950s as the best thermoelectric material for near-room temperature operation. Improvements in material performance are expected from nanostructuring procedures. We present a straightforward and fast method to synthesize already nanostructured pellets that show an enhanced ZT due to a remarkably low thermal conductivity and unusually high Seebeck coefficient for a nominal composition optimized for arc-melting: Bi0.35Sb1.65Te3. We provide a detailed structural analysis of the Bi2-xSbxTe3 series (0 ≤ x ≤ 2) based on neutron powder diffraction as a function of composition and temperature that reveals the important role played by atomic vibrations. Arc-melting produces layered platelets with less than 50 nm-thick sheets. The low thermal conductivity is attributed to the phonon scattering at the grain boundaries of the nanosheets. This is a fast and cost-effective production method of highly efficient thermoelectric materials.

Giant Seebeck effect in Ge-doped SnSe.

Thermoelectric materials may contribute in the near future as new alternative sources of sustainable energy. Unprecedented thermoelectric properties in p-type SnSe single crystals have been recently reported, accompanied by extremely low thermal conductivity in polycrystalline samples. In order to enhance thermoelectric efficiency through proper tuning of this material we report a full structural characterization and evaluation of the thermoelectric properties of novel Ge-doped SnSe prepared by a straightforward arc-melting method, which yields nanostructured polycrystalline samples. Ge does not dope the system in the sense of donating carriers, yet the electrical properties show a semiconductor behavior with resistivity values higher than that of the parent compound, as a consequence of nanostructuration, whereas the Seebeck coefficient is higher and thermal conductivity lower, favorable to a better ZT figure of merit.

Nanostructured Bi2Te3 Prepared by a Straightforward Arc-Melting Method.

Thermoelectric materials constitute an alternative source of sustainable energy, harvested from waste heat. Bi2Te3 is the most utilized thermoelectric alloy. We show that it can be readily prepared in nanostructured form by arc-melting synthesis, yielding mechanically robust pellets of highly oriented polycrystals. This material has been characterized by neutron powder diffraction (NPD), scanning electron microscopy (SEM), and electronic and thermal transport measurements. A microscopic analysis from NPD data demonstrates a near-perfect stoichiometry of Bi2Te3 and a fair amount of anharmonicity of the chemical bonds. The as-grown material presents a metallic behavior, showing a record-low resistivity at 320 K of 2 µΩ m, which is advantageous for its performance as a thermoelectric material. SEM analysis shows a stacking of nanosized sheets, each of them presumably single-crystalline, with large surfaces perpendicular to the c crystallographic axis. This nanostructuration notably affects the thermoelectric properties, involving many surface boundaries that are responsible for large phonon scattering factors, yielding a thermal conductivity as low as 1.2 W m(-1) K(-1) around room temperature.

Phase separation enhanced magneto-electric coupling in La0.7Ca0.3MnO3/BaTiO3 ultra-thin films.

We study the origin of the magnetoelectric coupling in manganite films on ferroelectric substrates. We find large magnetoelectric coupling in La0.7Ca0.3MnO3/BaTiO3 ultra-thin films in experiments based on the converse magnetoelectric effect. The magnetization changes by around 30-40% upon applying electric fields on the order of 1 kV/cm to the BaTiO3 substrate, corresponding to magnetoelectric coupling constants on the order of α = (2-5) · 10(-7) s/m. Magnetic anisotropy is also affected by the electric field induced strain, resulting in a considerable reduction of coercive fields. We compare the magnetoelectric effect in pre-poled and unpoled BaTiO3 substrates. Polarized neutron reflectometry reveals a two-layer behavior with a depressed magnetic layer of around 30 Å at the interface. Magnetic force microscopy (MFM) shows a granular magnetic structure of the La0.7Ca0.3MnO3. The magnetic granularity of the La0.7Ca0.3MnO3 film and the robust magnetoelastic coupling at the La0.7Ca0.3MnO3/BaTiO3 interface are at the origin of the large magnetoelectric coupling, which is enhanced by phase separation in the manganite.

Reversible electric-field control of magnetization at oxide interfaces.

Electric-field control of magnetism has remained a major challenge which would greatly impact data storage technology. Although progress in this direction has been recently achieved, reversible magnetization switching by an electric field requires the assistance of a bias magnetic field. Here we take advantage of the novel electronic phenomena emerging at interfaces between correlated oxides and demonstrate reversible, voltage-driven magnetization switching without magnetic field. Sandwiching a non-superconducting cuprate between two manganese oxide layers, we find a novel form of magnetoelectric coupling arising from the orbital reconstruction at the interface between interfacial Mn spins and localized states in the CuO2 planes. This results in a ferromagnetic coupling between the manganite layers that can be controlled by a voltage. Consequently, magnetic tunnel junctions can be electrically toggled between two magnetization states, and the corresponding spin-dependent resistance states, in the absence of a magnetic field.

Effect of interface-induced exchange fields on cuprate-manganite spin switches.

We examine the anomalous inverse spin switch behavior in La0.7Ca0.3MnO3(LCMO)/YBa2Cu3O7-δ (YBCO)/LCMO trilayers by combined transport studies and polarized neutron reflectometry. Measuring magnetization profiles and magnetoresistance in an in-plane rotating magnetic field, we prove that, contrary to many accepted theoretical scenarios, the relative orientation between the two LCMO's magnetizations is not sufficient to determine the magnetoresistance. Rather the field dependence of magnetoresistance is explained by the interplay between the applied magnetic field and the (exponential tail of the) induced exchange field in YBCO, the latter originating from the electronic reconstruction at the LCMO/YBCO interfaces.

Magnetite (Fe3O4): a new variant of relaxor multiferroic?

The electric polarization, dielectric permittivity, magnetoelectric effect, heat capacity, magnetization and ac susceptibility of magnetite films and polycrystals were investigated. The electric polarization of magnetite films with saturation values between 4 and 8 µC cm(-2) was found to vanish between 32 and 38 K, but in polycrystals no phase transition was detected in this range by heat capacity. Both types of samples showed magnetoelectric effects at low temperatures below a frequency-dependent crossover. This is interpreted as arising from multiferroic relaxor behavior.

Electronic and magnetic reconstructions in La0.7Sr0.3MnO3/SrTiO3 heterostructures: a case of enhanced interlayer coupling controlled by the interface.

We report on the magnetic coupling of La0.7Sr0.3MnO3 layers through SrTiO3 spacers in La0.7Sr0.3MnO3/SrTiO3 epitaxial heterostructures. Combined aberration-corrected microscopy and electron-energy-loss spectroscopy evidence charge transfer to the empty conduction band of the titanate. Ti d electrons interact via superexchange with Mn, giving rise to a Ti magnetic moment as demonstrated by x-ray magnetic circular dichroism. This induced magnetic moment in the SrTiO3 controls the bulk magnetic and transport properties of the superlattices when the titanate layer thickness is below 1 nm.