Thermoelectric materials, which can generate electricity from waste heat or be used as solid-state Peltier coolers, could play an important role in a global sustainable energy solution. Such a development is contingent on identifying materials with higher thermoelectric efficiency than available at present, which is a challenge owing to the conflicting combination of material traits that are required. Nevertheless, because of modern synthesis and characterization techniques, particularly for nanoscale materials, a new era of complex thermoelectric materials is approaching. We review recent advances in the field, highlighting the strategies used to improve the thermopower and reduce the thermal conductivity.

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Complex 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.

New and Old Concepts in Thermoelectric Materials

There has been a renaissance of interest in exploring highly efficient thermoelectric materials as a possible route to address the worldwide energy generation, utilization, and management. This review describes the recent advances in designing high-performance bulk thermoelectric materials. We begin with the fundamental stratagem of achieving the greatest thermoelectric figure of merit ZT of a given material by carrier concentration engineering, including Fermi level regulation and optimum carrier density stabilization. We proceed to discuss ways of maximizing ZT at a constant doping level, such as increase of band degeneracy (crystal structure symmetry, band convergence), enhancement of band effective mass (resonant levels, band flattening), improvement of carrier mobility (modulation doping, texturing), and decrease of lattice thermal conductivity (synergistic alloying, second-phase nanostructuring, mesostructuring, and all-length-scale hierarchical architectures). We then highlight the decoupling of th...

Rationally Designing High-Performance Bulk Thermoelectric Materials

Skutterudites CoSb3 with multiple cofillers Ba, La, and Yb were synthesized and very high thermoelectric figure of merit ZT = 1.7 at 850 K was realized. X-ray diffraction of the densified multiple-filled bulk samples reveals all samples are phase pure. High-resolution scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDS) analysis confirm that multiple guest fillers occupy the nanoscale-cages in the skutterudites. The fillers are further shown to be uniformly distributed and the Co−Sb skutterudite framework is virtually unperturbed from atomic scale to a few micrometers. Our results firmly show that high power factors can be realized by adjusting the total filling fraction of fillers with different charge states to reach the optimum carrier density, at the same time, lattice thermal conductivity can also be significantly reduced, to values near the glass limit of these materials, through combining filler species of different rattling frequencies to achieve broad-fr...

Multiple-filled skutterudites: high thermoelectric figure of merit through separately optimizing electrical and thermal transports.

This review presents an overview of the thermal properties of mesoscopic structures. The discussion is based on the concept of electron energy distribution, and, in particular, on controlling and probing it. The temperature of an electron gas is determined by this distribution: refrigeration is equivalent to narrowing it, and thermometry is probing its convolution with a function characterizing the measuring device. Temperature exists, strictly speaking, only in quasiequilibrium in which the distribution follows the Fermi-Dirac form. Interesting nonequilibrium deviations can occur due to slow relaxation rates of the electrons, e.g., among themselves or with lattice phonons. Observation and applications of nonequilibrium phenomena are also discussed. The focus in this paper is at low temperatures, primarily below $4\phantom{\rule{0.3em}{0ex}}\mathrm{K}$, where physical phenomena on mesoscopic scales and hybrid combinations of various types of materials, e.g., superconductors, normal metals, insulators, and doped semiconductors, open up a rich variety of device concepts. This review starts with an introduction to theoretical concepts and experimental results on thermal properties of mesoscopic structures. Then thermometry and refrigeration are examined with an emphasis on experiments. An immediate application of solid-state refrigeration and thermometry is in ultrasensitive radiation detection, which is discussed in depth. This review concludes with a summary of pertinent fabrication methods of presented devices.

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Opportunities for mesoscopics in thermometry and refrigeration: Physics and applications

Polycrystalline samples of clathrate compounds Ba8Ga16Si30, Ba8Ga16Ge30, Ba8Ga16Sn30, and Sr8Ga16Ge30 were prepared by direct melting and characterized using X-ray powder diffraction and differential thermal analysis. The Ge- and Si-based clathrates melt congruently, whereas Ba8Ga16Sn30 melts incongruently. At room temperature the Ge- and Si-based clathrates possess a moderate negative Seebeck coefficient and a high electron concentration in the range of 7×1020–9×1020 cm−3 while Ba8Ga16Sn30 exhibits substantially lower electron concentration of 2.2×1019 cm−3. The Seebeck coefficient and electrical resistivity were measured over the range 100–870 K. The temperature dependence of transport properties of the clathrates is typical for heavily doped semiconductors. The transport properties were analyzed using a standard semiconductor transport model. There is a good agreement between the assumed model and experimental temperature dependence of the Seebeck coefficient in the extrinsic conductivity range for all...

Preparation and thermoelectric properties of A8IIB16IIIB30IV clathrate compounds

Polycrystalline samples of the partially filled skutterudites NdxCo4Sb12 have been prepared and characterized by x-ray powder diffraction and differential thermal analysis. The saturation limit of the Nd void filling in CoSb3 was found to be around 13%. All samples decompose incongruently at a temperature of 1149 ± 6 K. Room temperature Hall measurements show that each Nd atom donates approximately 0.8 electrons, which is significantly less than the Nd oxidation state (3+). The temperature dependence of the electrical and thermal transport properties has been measured over the range of 11–700 K. The electrical resistivity and absolute value of the Seebeck coefficient decrease with increasing Nd content and for samples with x > 0.02 the temperature dependence is typical of heavily doped semiconductors. Filling CoSb3 with Nd causes a rapid initial decrease in the lattice thermal conductivity with a minimum at the composition Nd0.1Co4Sb12. Nd-filled skutterudites exhibit the lowest value of the lattice thermal conductivity in comparison with other partially filled skutterudites at x < 0.1, which could be attributed to a smaller radius of Nd than that of other filling elements. At high temperature the ZT value of the Nd-filled skutterudites is limited due to intrinsic conduction caused by the relatively low carrier concentration. The effect of the partial Nd filling on the transport properties of the filled skutterudite compounds is discussed in the context of potential thermoelectric materials.

https://iopscience.iop.org/article/10.1088/0953-8984/15/29/315/pdf

Effect of partial void filling on the transport properties of NdxCo4Sb12 skutterudites

Bi2Te3-based materials possess a figure of merit maximum over a narrow temperature range. When used in a generating mode over a large temperature difference the material operates at a substantially lower overall figure of merit than its maximum value. The conversion efficiency of a thermoelectric generator for low temperature waste heat recovery can be increased by employing functionally graded or segmented materials. In this work functionally graded p-type Bi2Te3-based thermoelectric materials have been prepared from melt by the Bridgman method using double doping technique. Segmented n-type thermoelement has been fabricated by joining two Bi2Te3-based materials with figure of merit maximum at 270 K and 380 K. The thermoelectric properties of the materials and a thermocouple comprised of p-type functionally graded and n-type segmented materials have been measured over a temperature range 200 K–450 K. The material efficiency of the thermocouple over the temperature gradient 223 K–423 K is estimated to be 10% compared with 8.8% for a standard Bi2Te3-based materials.

High performance functionally graded and segmented Bi2Te3-based materials for thermoelectric power generation

Thermoelectric properties and crystal structure of ternary compounds in the Ge(Sn,Pb)Te-Bi 2 Te 3 systems

Intermediate valence compound YbAl3 has been synthesized by the Bridgman method. Temperature dependence of the Seebeck coefficient, electrical resistivity and thermal conductivity has been measured on YbAl3 hot-pressed and single crystal samples. At temperatures below 100 K, the electrical resistivity exhibits a ρ(T) = ρ0 + AT2 dependence, while over the temperature range 300-800 K YbAl3 exhibits metallic behaviour with a linear temperature dependence of the electrical resistivity. The Seebeck coefficient exhibits a temperature dependence typical for heavy fermion compounds and attains a maximum of its absolute value of -79 µV K-1 at around 200-250 K. Combination of a large Seebeck coefficient and low residual resistivity of single crystalline YbAl3 leads to the highest ever reported electrical power factor of 340×10-6 W cm-1 K-2 at 80 K. Thermal conductivity as a function of temperature has a broad peak at 50 K, which originated mainly from the electronic contribution to thermal conductivity. At 300 K the total thermal conductivity of hot-pressed samples ranges from 0.085 to 0.179 W cm-1 K-1 depending on the density of the samples. The calculated figure of merit value attains its maximum of 1×10-3 K-1 at 100-120 K.

https://iopscience.iop.org/article/10.1088/0022-3727/35/17/315/pdf

L. A. Kuznetsova

Papers

Preparation and thermoelectric properties of A8IIB16IIIB30IV clathrate compounds

Effect of partial void filling on the transport properties of NdxCo4Sb12 skutterudites

High performance functionally graded and segmented Bi2Te3-based materials for thermoelectric power generation

Thermoelectric properties and crystal structure of ternary compounds in the Ge(Sn,Pb)Te-Bi 2 Te 3 systems

Electrical and thermal transport properties of intermediate-valence YbAl3