N. Oeschler

Synthesis and Thermoelectric Characterization of Bi2Te3 Nanoparticles

Here, a novel synthesis for near monodisperse, sub-10 nm Bi2Te3 nanoparticles is reported. A new reduction route to bismuth nanoparticles is described, which are then applied as starting materials in the formation of rhombohedral Bi2Te3 nanoparticles. After ligand removal by a novel hydrazine hydrate etching procedure, the nanoparticle powder is spark plasma sintered to a pellet with preserved crystal grain sizes. Unlike previous works on the properties of Bi2Te3 nanoparticles, the full thermoelectric characterization of such sintered pellets shows a highly reduced thermal conductivity and the same electric conductivity as bulk n-type Bi2Te3.

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.

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.

ZT enhancement in solution-grown Sb(2-x)BixTe3 nanoplatelets.

We report a solution-processed, ligand-supported synthesis of 15-20 nm thick Sb(2-x)BixTe3 nanoplatelets. After complete ligand removal by a facile NH3-based etching procedure, the platelets are spark plasma sintered to a p-type nanostructured bulk material with preserved crystal grain sizes. Due to this nanostructure, the total thermal conductivity is reduced by 60% in combination with a reduction in electric conductivity of as low as 20% as compared to the bulk material demonstrating the feasibility of the phonon-glass electron-crystal concept. An enhancement in the dimensionless thermoelectric figure of merit of up to 15% over state-of-the-art bulk materials is achieved, meanwhile, shifting the maximum to significantly higher temperatures.

Atomic Interactions in the p-Type Clathrate I Ba8Au5.3Ge40.7

Single crystals of Ba(8)Au(5.3)Ge(40.7) [space group Pm(3)n (No. 223), a = 10.79891(8) Å] were prepared by a Bridgman technique. The crystal structure refinement based on single-crystal X-ray diffraction data does not reveal any vacancies in the Au/Ge framework or in the cages. In addition to the ionic bonding between Ba and the anionic framework, a direct interaction between Ba and Au atoms was identified in Ba(8)Au(5.3)Ge(40.7) by applying the electron localizability indicator. As expected by the chemical-bonding picture, Ba(8)Au(5.3)Ge(40.7) is a diamagnet and shows p-type electrical conductivity with a hole carrier concentration of 7.14 × 10(19) cm(-3) at 300 K and very low lattice thermal conductivity of ≈0.6 W m(-1) K(-1) at 500 K. The thermoelectric figure of merit ZT of single crystals of Ba(8)Au(5.3)Ge(40.7) attains 0.3 at 511 K and reaches 0.9 at 680 K in a polycrystalline sample of closely similar composition. This opens up an opportunity for tuning of the thermoelectric properties of materials in the Ba-Au-Ge clathrate system by changing the chemical composition.

Thermoelectric Properties of Lead Chalcogenide Core–Shell Nanostructures

We present the full thermoelectric characterization of nanostructured bulk PbTe and PbTe-PbSe samples fabricated from colloidal core-shell nanoparticles followed by spark plasma sintering. An unusually large thermopower is found in both materials, and the possibility of energy filtering as opposed to grain boundary scattering as an explanation is discussed. A decreased Debye temperature and an increased molar specific heat are in accordance with recent predictions for nanostructured materials. On the basis of these results we propose suitable core-shell material combinations for future thermoelectric materials of large electric conductivities in combination with an increased thermopower by energy filtering.

Facile General Route toward Tunable Magneli Nanostructures and Their Use As Thermoelectric Metal Oxide/Carbon Nanocomposites

Engineering nanoscale interfaces is a requisite for harnessing electrical and thermal transports within nanostructured materials, especially those destined for thermoelectric applications requiring an unusual combination of low thermal conductivity and electrical resistivity. Nanocomposites open up possibilities in this area, but are still bound to a very narrow range of materials. Here, we report a new approach combining the sol-gel process toward hybrid materials with spark plasma sintering (SPS) to yield functional nanocomposites based on substoichiometric titanium oxides Ti(n)O(2n-1), so-called Magnéli phases. The potential of this new approach is demonstrated by three results. First, multiple Ti(n)O(2n-1) compounds (n = 3, 4, 5, 6, 8) are obtained for the first time as sole nano-Magnéli crystalline phases with controlled specific surface areas from 55 to 300 m(2)·g(-1), classified as potential thermoelectric n-type metal oxides and paving the way toward advanced systems for energy-harvesting devices and optoelectronics. Second, this work combines the use of sol-gel and SPS processes to yield percolated nanocomposites based on metal oxide nanoparticles embedded in a carbon matrix with low electrical resistivity (2 × 10(-4) Ω·m for a Ti(4)O(7) compound) and reduced thermal conductivity (1 W·m(-1)·K(-1)) with respect to bulk phases. Finally, the discovered materials are reliable with thermoelectric figures of merit (ZT = 0.08) relatively high for n-type Ti-O-based systems and metal oxides. Thereby this study represents a proof of concept for the development of promising, cheaper, and more efficient thermoelectric conversion devices.

Fermi-surface collapse and dynamical scaling near a quantum-critical point

Quantum criticality arises when a macroscopic phase of matter undergoes a continuous transformation at zero temperature. While the collective fluctuations at quantum-critical points are being increasingly recognized as playing an important role in a wide range of quantum materials, the nature of the underlying quantum-critical excitations remains poorly understood. Here we report in-depth measurements of the Hall effect in the heavy-fermion metal YbRh2Si2, a prototypical system for quantum criticality. We isolate a rapid crossover of the isothermal Hall coefficient clearly connected to the quantum-critical point from a smooth background contribution; the latter exists away from the quantum-critical point and is detectable through our studies only over a wide range of magnetic field. Importantly, the width of the critical crossover is proportional to temperature, which violates the predictions of conventional theory and is instead consistent with an energy over temperature, E/T, scaling of the quantum-critical single-electron fluctuation spectrum. Our results provide evidence that the quantum-dynamical scaling and a critical Kondo breakdown simultaneously operate in the same material. Correspondingly, we infer that macroscopic scale-invariant fluctuations emerge from the microscopic many-body excitations associated with a collapsing Fermi-surface. This insight is expected to be relevant to the unconventional finite-temperature behavior in a broad range of strongly correlated quantum systems.

Magnetism and unconventional superconductivity in CenMmIn3n+2m heavy-fermion crystals

Abstract We review magnetic, superconducting and non-Fermi-liquid properties of the structurally layered heavy-fermion compounds Ce n M m In 3n+2m ( M = Co , Rh , Ir ) . These properties suggest d-wave superconductivity and proximity to an antiferromagetic quantum-critical point.

Crystal structure and transport properties of Ba8Ge43□3

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.