Joseph R. Sootsman

New and Old Concepts in Thermoelectric Materials

Herein we cover the key concepts in the field of thermoelectric materials research, present the current understanding, and show the latest developments. Current research is aimed at increasing the thermoelectric figure of merit (ZT) by maximizing the power factor and/or minimizing the thermal conductivity. Attempts at maximizing the power factor include the development of new materials, optimization of existing materials by doping, and the exploration of nanoscale materials. The minimization of the thermal conductivity can come through solid-solution alloying, use of materials with intrinsically low thermal conductivity, and nanostructuring. Herein we describe the most promising bulk materials with emphasis on results from the last decade. Single-phase bulk materials are discussed in terms of chemistry, crystal structure, physical properties, and optimization of thermoelectric performance. The new opportunities for enhanced performance bulk nanostructured composite materials are examined and a look into the not so distant future is attempted.

On the origin of increased phonon scattering in nanostructured PbTe based thermoelectric materials.

We have investigated the possible mechanisms of phonon scattering by nanostructures and defects in PbTe-X (X = 2% Sb, Bi, or Pb) thermoelectric materials systems. We find that among these three compositions, PbTe-2% Sb has the lowest lattice thermal conductivity and exhibits a larger strain and notably more misfit dislocations at the precipitate/PbTe interfaces than the other two compositions. In the PbTe-Bi 2% sample, we infer some weaker phonon scattering BiTe precipitates, in addition to the abundant Bi nanostructures. In the PbTe-Pb 2% sample, we also find that pure Pb nanoparticles exhibit stronger phonon scattering than nanostructures with Te vacancies. Within the accepted error range, the theoretical calculations of the lattice thermal conductivity in the three systems are in close agreement with the experimental measurements, highlighting the important role of misfit dislocations, nanoscale particles, and associated interfacial elastic strain play in phonon scattering. We further propose that such particle-induced local elastic perturbations interfere with the phonon propagation pathway, thereby contributing to further reduction in lattice thermal conductivity, and consequently can enhance the overall thermoelectric figure of merit.

Anomalous electronic transport in dual-nanostructured lead telluride

The Pb- and Sb- dual nanostructured PbTe system exhibits anomalous electronic transport behavior wherein the carrier mobility first increases and then decreases with increase in temperature. By combining in situ transmission electron microscopy observations and theoretical calculations based on energy filtering of charge carriers, we propose a plausible mechanism of charge transport based on interphase potential that is mediated by interdiffusion between coexisting Pb and Sb precipitates. These findings promise new strategies to enhance thermoelectric figure of merit via dual and multinanostructuring of miscible precipitates.

High thermoelectric figure of merit and improved mechanical properties in melt quenched PbTe–Ge and PbTe–Ge1−xSix eutectic and hypereutectic composites

We report the synthesis, microstructure, and transport properties of composite thermoelectric materials based on the eutectic phase relationship between PbTe and Ge. When quenched, these eutectic mixtures exhibit considerably stronger mechanical strength and reduced brittleness compared to PbTe itself, while at the same time they possess lower lattice thermal conductivity. Thermal conductivity measurements show values lower than expected based on the law of mixtures and multiphase composites. We find that the thermoelectric performance in these composites can be tuned through the use of hypereutectic compositions and alloying of Ge with Si. PbI2 was used as an n-type dopant, and precise control of the carrier concentration was achieved to optimize the electrical transport and thermoelectric properties. ZT values approaching 1.3 at 778 K have been obtained in samples of PbTe–Ge0.8Si0.2(5%), which represent an ∼62% improvement over that of PbTe.

Role of Self-Organization, Nanostructuring, and Lattice Strain on Phonon Transport in NaPb18-xSnxBiTe20 Thermoelectric Materials

The composition and microstructure of five thermoelectric materials, PbTe, SnTe, Pb(0.65)Sn(0.35)Te and NaPb(18-x)Sn(x)BiTe(20) (x = 5, 9), were investigated by advanced transmission electron microcopy. We confirm that the pure PbTe, SnTe, and Pb(0.65)Sn(0.35)Te have a uniform crystalline structure and homogeneous compositions without any nanoscale inclusions. On the other hand, the nominal NaPb(9)Sn(9)BiTe(20) phase contains extensive inhomogeneities and nanostructures with size distribution of 3-7 nm. We find that the chemical architecture of the NaPb(13)Sn(5)BiTe(20) member of the series to be more complex; besides nanoscale precipitates, self-organized lamellar structures are present which were identified as PbTe and SnTe by composition analysis and transmission electron microscopy image simulations. Density functional theory calculations suggest that the arrangement of the lamellar structures conforms to the lowest total energy configuration. Geometric-phase analyses revealed large distributed elastic strain around the nanoscale inclusions and lamellar structures. We propose that interface-induced elastic perturbations in the matrix play a decisive role in affecting the phonon-propagation pathways. The interfaces further enhance phonon scattering which, in turn, reduces the lattice thermal conductivity in these systems that directly results directly in improvement in the thermoelectric figure of merit.

Transport behavior and thermal conductivity reduction in the composite system PbTe-Pb-Sb

We report the synthesis of nanostructured composite PbTe with excess Pb and Sb metal inclusions. Scanning and transmission electron microscopy reveal these inclusions in both the nano- and macroscales. The electrical conductivity and Seebeck coefficient dependence on temperature show unusual trends which depend on the inclusion Pb/Sb ratio. Several ratios showed marked enhancements in power factor at 700 K. The thermal conductivity of these composites is reported.

Phase Segregation and Thermoelectric Properties of AgPb m SbTe m +2 m =2,4,6, and 8

The preparation and characterization of the AgPbmSbTem+2 family of compounds with m=2, 4, 6, and 8 is reported. Phase segregation was observed in all of these materials. The lattice thermal conductivity of these samples is low (<1.1 W/m-K). Powder x-ray diffraction, thermal analysis, and electron microscope investigations of these systems show that ideal solid solutions are not formed. The transport properties of these composite materials are presented and suggest that they could have promising thermoelectric properties when optimized.

Electron-beam activated thermal sputtering of thermoelectric materials

Thermoelectricity and Seebeck effect have long been observed and validated in bulk materials. With the development of advanced tools of materials characterization, here we report the first observation of such an effect in the nanometer scale: in situ directional sputtering of several thermoelectric materials inside electron microscopes. The temperature gradient introduced by the electron beam creates a voltage-drop across the samples, which enhances spontaneous sputtering of specimen ions. The sputtering occurs along a preferential direction determined by the direction of the temperature gradient. A large number of nanoparticles form and accumulate away from the beam location as a result. The sputtering and re-crystallization are found to occur at temperatures far below the melting points of bulk materials. The sputtering occurs even when a liquid nitrogen cooling holder is used to keep the overall temperature at −170 °C. This unique phenomenon that occurred in the nanometer scale may provide useful clues...

Thermoelectric properties of nanostructured (Pb 1-m Sn m Te) 1-x (PbS) x with Pb and Sb precipitates

We report the physical characterization and thermoelectric properties of (Pb 0.95 Sn 0.05 Te) 0.92 (PbS) 0.08 containing excess Pb and Sb prepared using the matrix encapsulation technique. Samples of (Pb 0.95 Sn 0.05 Te) 0.92 (PbS) 0.08 : Pb 0.5 - 4 at. % rapidly quenched from the melt show microscale Pb inclusions that increase the thermal conductivity while slightly increasing the power factor, compared to (Pb 0.95 Sn 0.05 Te) 0.92 (PbS) 0.08 . Samples of (Pb 0.95 Sn 0.05 Te) 0.92 (PbS) 0.08 : Pb 0.5%, Sb 2% prepared using the same technique show microscale Sb and Pb inclusions that upon heating cause rapid PbS and Sb segregation from the PbTe matrix. This behavior significantly alters the microstructure and degrades the transport properties of the material.

Effects of Antimony on the Thermoelectric Properties of the Cubic Pb 9.6 Sb y Te 10−x Se x Materials

The thermoelectric properties of Pb9.6SbyTe10-xSex were investigated in the intermediate temperature range of 300 – 700 K. The effect of the variation of Sb content (y) on the electronic properties of the materials is remarkable. Samples with compositions Pb9.6Sb0.2Te10xSex (y = 0.2) show the best combination of low thermal conductivity with moderate electrical conductivity and thermopower. For Pb9.6Sb0.2Te8Se2 (x = 2) a maximum figure of merit of ZT~ 1.1 was obtained around 700 K. This value is nearly 1.4 times higher than that of PbTe at 700 K. This enhancement of the figure of merit of Pb9.6Sb0.2Te8Se2 derives from its extremely low thermal conductivity (~0.7 at W/m.K at 700 K). High resolution transmission electron microscopy of Pb9.6Sb0.2Te10-xSex samples shows broadly distributed Sb-rich nanocrystals, which may be the key feature responsible for the suppression of the thermal conductivity.