Brian C. Sales

Filled Skutterudite Antimonides: A New Class of Thermoelectric Materials

A class of thermoelectric materials has been synthesized with a thermoelectric figure of merit ZT (where T is temperature and Z is a function of thermopower, electrical resistivity, and thermal conductivity) near 1 at 800 kelvin. Although these materials have not been optimized, this value is comparable to the best ZT values obtained for any previously studied thermoelectric material. Calculations indicate that the optimized material should have ZT values of 1.4. These ternary semiconductors have the general formula RM4X12 (where R is lanthanum, cerium, praseodymium, neodymium, or europium; M is iron, ruthenium, or osmium; and X is phosphorus, arsenic, or antimony) and represent a new approach to creating improved thermoelectric materials. Several alloys in the composition range CeFe4−xCoxSb12 or LaFe4−xCoxSb12 (0 < x < 4) have large values of ZT.

Epitaxial YBa2Cu3O7 on Biaxially Textured Nickel (001): An Approach to Superconducting Tapes with High Critical Current Density

In-plane—aligned, c axis—oriented YBa2Cu3O7 (YBCO) films with superconducting critical current densities Jc as high as 700,000 amperes per square centimeter at 77 kelvin have been grown on thermomechanically rolled-textured nickel (001) tapes by pulsed-laser deposition. Epitaxial growth of oxide buffer layers directly on biaxially textured nickel, formed by recrystallization of cold-rolled pure nickel, made possible the growth of YBCO films 1.5 micrometers thick with superconducting properties that are comparable to those observed for epitaxial films on single-crystal oxide substrates. This result represents a viable approach for the production of long superconducting tapes for high-current, high-field applications at 77 kelvin.

Thermoelectric materials: New approaches to an old problem

Thermoelectrics is an old field. In 1823, Thomas Seebeck discovered that a voltage drop appears across a sample that has a temperature gradient. This phenomenon provided the basis for thermocouples used for measuring temperature and for thermoelectric power generators. In 1838, Heinrich Lenz placed a drop of water on the junction of metal wires made of bismuth and antimony. Passing an electric current through the junction in one direction caused the water to freeze, and reversing the current caused the ice to quickly melt; thus thermoelectric refrigeration was demonstrated (figure 1).

Superconductivity at 22 K in Co-Doped BaFe2As2 Crystals

Here we report bulk superconductivity in BaFe1.8Co0.2As2 single crystals below Tc=22 K, as demonstrated by resistivity, magnetic susceptibility, and specific heat data. Hall data indicate that the dominant carriers are electrons, as expected from simple chemical reasoning. This is the first example of superconductivity induced by electron doping in this family of materials. In contrast with cuprates, the BaFe2As2 system appears to tolerate considerable disorder in the FeAs planes. First principles calculations for BaFe1.8Co0.2As2 indicate the interband scattering due to Co is weak.

Localized vibrational modes in metallic solids

Filled skutterudite antimonides, are cubic compounds with the formula RM4Sb12, where R is a rare-earth element (such as La or Ce), and M is a transition metal (for example, Fe or Co). The rare-earth ion is weakly bound in an oversized atomic cage formed by the other atoms. Its presence has been shown to cause a dramatic reduction in the lattice component of the thermal conductivity, while having little effect on the electronic properties of the compound. This combination of properties makes filled skutterudites of interest as thermoelectric materials. It has been suggested that localized, incoherent vibrations of the rare-earth ion are responsible for the reduction in thermal conductivity, but no direct evidence for these local vibrational modes exists. Here we report the observation of local modes in La-filled skutterudites, using heat capacity, elastic constant and inelastic neutron scattering measurements. The La atoms show unusual thermodynamic behaviour, characterized by the presence of two low-energy localized modes. Our results suggest that consideration of local modes will play an important role in the design of the next generation of thermoelectric materials.

Oscillatory oxidation of CO over Pt, Pd and Ir catalysts: Theory

A simple physical model is presented to explain the oscillatory oxidation of CO over Pt, Pd and Ir catalysts. Oscillations are believed to occur between two branches of a Langmuir-Hinshelwood reaction mechanism. The slow oxidation and reduction of the metal surface layer induces transitions between these two branches. The kinetics of the oscillatory oxidation of CO are simulated using three coupled differential equations which describe the time evolution of: the fractional coverage of chemisorbed oxygen on the catalyst surface, θ1, the fractional coverage of chemisorbed carbon monoxide, θ2, and the fraction of surface sites blocked by oxide formation, θ3. A detailed comparison is presented between the model calculations and our experimental results for Pt. Almost all the oscillatory characteristics observed over Pt are quantitatively reproduced by the model.

Thermoelectric properties of CoSb3 and related alloys

Seebeck, electrical, and thermal conductivity data are reported on CoSb3, and doped and undoped alloys of Co1−x Ir x Sb3−y As y from 20 to 700 K. n‐type semiconductors were obtained by doping with Ni, Te, or Pd, and the hole concentration in p‐type samples was increased by substitution of Fe, Ru, Os, and Ge. An estimated maximum value for ZT of 0.6 (Z is the figure of merit) was found for a Te‐doped (n‐type) alloy at 700 K. For p‐type alloys, the maximum value of ZT was found to be 0.3 at 550 K. Electrical and thermal transport data also are reported for CoAs3, RhSb3, and IrSb3. Most of the samples investigated were polycrystalline, but a few measurements on CoSb3 single crystals also are discussed.

Two-band superconductivity in LaFeAsO0.89F0.11 at very high magnetic fields.

The recent synthesis of the superconductor LaFeAsO0.89F0.11 with transition temperature Tc ≈ 26 K (refs 1–4) has been quickly followed by reports of even higher transition temperatures in related compounds: 41 K in CeFeAsO0.84F0.16 (ref. 5), 43 K in SmFeAsO0.9F0.1 (ref. 6), and 52 K in NdFeAsO0.89F0.11 and PrFeAsO0.89F0.11 (refs 7, 8). These discoveries have generated much interest in the mechanisms and manifestations of unconventional superconductivity in the family of doped quaternary layered oxypnictides LnOTMPn (Ln: La, Pr, Ce, Sm; TM: Mn, Fe, Co, Ni; Pn: P, As), because many features of these materials set them apart from other known superconductors. Here we report resistance measurements of LaFeAsO0.89F0.11 at high magnetic fields, up to 45 T, that show a remarkable enhancement of the upper critical field Bc2 compared to values expected from the slopes dBc2/dT ≈ 2 T K-1 near Tc, particularly at low temperatures where the deduced Bc2(0) ≈ 63–65 T exceeds the paramagnetic limit. We argue that oxypnictides represent a new class of high-field superconductors with Bc2 values surpassing those of Nb3Sn, MgB2 and the Chevrel phases, and perhaps exceeding the 100 T magnetic field benchmark of the high-Tc copper oxides.

Thermoelectric properties of CoSb{sub 3} and related alloys

Seebeck, electrical, and thermal conductivity data are reported on CoSb3, and doped and undoped alloys of Co1−x Ir x Sb3−y As y from 20 to 700 K. n‐type semiconductors were obtained by doping with Ni, Te, or Pd, and the hole concentration in p‐type samples was increased by substitution of Fe, Ru, Os, and Ge. An estimated maximum value for ZT of 0.6 (Z is the figure of merit) was found for a Te‐doped (n‐type) alloy at 700 K. For p‐type alloys, the maximum value of ZT was found to be 0.3 at 550 K. Electrical and thermal transport data also are reported for CoAs3, RhSb3, and IrSb3. Most of the samples investigated were polycrystalline, but a few measurements on CoSb3 single crystals also are discussed.

Giant anharmonic phonon scattering in PbTe

Understanding the microscopic processes affecting the bulk thermal conductivity is crucial to develop more efficient thermoelectric materials. PbTe is currently one of the leading thermoelectric materials, largely thanks to its low thermal conductivity. However, the origin of this low thermal conductivity in a simple rocksalt structure has so far been elusive. Using a combination of inelastic neutron scattering measurements and first-principles computations of the phonons, we identify a strong anharmonic coupling between the ferroelectric transverse optic mode and the longitudinal acoustic modes in PbTe. This interaction extends over a large portion of reciprocal space, and directly affects the heat-carrying longitudinal acoustic phonons. The longitudinal acoustic-transverse optic anharmonic coupling is likely to play a central role in explaining the low thermal conductivity of PbTe. The present results provide a microscopic picture of why many good thermoelectric materials are found near a lattice instability of the ferroelectric type.