The past two decades have witnessed the rapid growth of thermoelectric (TE) research. Novel concepts and paradigms are described here that have emerged, targeting superior TE materials and higher TE performance. These superior aspects include band convergence, "phonon-glass electron-crystal", multiscale phonon scattering, resonant states, anharmonicity, etc. Based on these concepts, some new TE materials with distinct features have been identified, including solids with high band degeneracy, with cages in which atoms rattle, with nanostructures at various length scales, etc. In addition, the performance of classical materials has been improved remarkably. However, the figure of merit zT of most TE materials is still lower than 2.0, generally around 1.0, due to interrelated TE properties. In order to realize an "overall zT > 2.0," it is imperative that the interrelated properties are decoupled more thoroughly, or new degrees of freedom are added to the overall optimization problem. The electrical and thermal transport must be synergistically optimized. Here, a detailed discussion about the commonly adopted strategies to optimize individual TE properties is presented. Then, four main compromises between the TE properties are elaborated from the point of view of the underlying mechanisms and decoupling strategies. Finally, some representative systems of synergistic optimization are also presented, which can serve as references for other TE materials. In conclusion, some of the newest ideas for the future are discussed.

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/adma.201702816

Compromise and Synergy in High-Efficiency Thermoelectric Materials.

The long-standing popularity of thermoelectric materials has contributed to the creation of various thermoelectric devices and stimulated the development of strategies to improve their thermoelectric performance. In this review, we aim to comprehensively summarize the state-of-the-art strategies for the realization of high-performance thermoelectric materials and devices by establishing the links between synthesis, structural characteristics, properties, underlying chemistry and physics, including structural design (point defects, dislocations, interfaces, inclusions, and pores), multidimensional design (quantum dots/wires, nanoparticles, nanowires, nano- or microbelts, few-layered nanosheets, nano- or microplates, thin films, single crystals, and polycrystalline bulks), and advanced device design (thermoelectric modules, miniature generators and coolers, and flexible thermoelectric generators). The outline of each strategy starts with a concise presentation of their fundamentals and carefully selected examples. In the end, we point out the controversies, challenges, and outlooks toward the future development of thermoelectric materials and devices. Overall, this review will serve to help materials scientists, chemists, and physicists, particularly students and young researchers, in selecting suitable strategies for the improvement of thermoelectrics and potentially other relevant energy conversion technologies.

Advanced Thermoelectric Design: From Materials and Structures to Devices

Based on the concept of band bending at metal/semiconductor interfaces as an energy filter for electrons, we present a theory for the enhancement of the thermoelectric properties of semiconductor materials with metallic nanoinclusions. We show that the Seebeck coefficient can be significantly increased due to a strongly energy-dependent electronic scattering time. By including phonon scattering, we find that the enhancement of $ZT$ due to electron scattering is important for high doping, while at low doping it is primarily due to a decrease in the phonon thermal conductivity.

/pdf/theory-of-enhancement-of-thermoelectric-properties-of-2rvreb7dv1.pdf

Theory of enhancement of thermoelectric properties of materials with nanoinclusions.

Thermoelectric (TE) materials facilitate direct heat-to-electricity conversion. The performance of a TE material is characterised by its figure of merit zT (=S2 σT/κ) that depends on both electronic transport properties, i.e. the Seebeck coefficient S and the electrical conductivity σ, and on thermal transport properties, i.e. the thermal conductivity κ of a material. The intrinsically counter-correlated behaviour between electronic and thermal transport properties makes the enhancement of zT a very challenging task. In the past 10 years, the zTs in bulk TE materials have been significantly enhanced due to intensive exploratory efforts, the discovery of new physical phenomena and effects, and applications of advanced synthesis methods. In this review, we summarise the recent progress in bulk TE materials. After the introduction of fundamental principles of thermoelectricity, the recently achieved enhancements in the TE performance encompassing the use of electronic band structure engineering, lattice phon...

Recent advances in high-performance bulk thermoelectric materials

Excellent thermoelectric performance is obtained over a broad temperature range from 300 K to 800 K by doping single crystals of SnSe. The average value of the figure of merit ZT, of more than 1.17, is measured from 300 K to 800 K along the crystallographic b-axis of 3 at% Na-doped SnSe, with the maximum ZT reaching a value of 2 at 800 K. The room temperature value of the power factor for the same sample and in the same direction is 2.8 mW mK−2, which is an order of magnitude higher than that of the undoped crystal. Calculations show that Na doping lowers the Fermi level and increases the number of carrier pockets in SnSe, leading to a collaborative optimization of the Seebeck coefficient and the electrical conductivity. The resultant optimized carrier concentration and the increased number of carrier pockets near the Fermi level in Na-doped samples are believed to be the key factors behind the spectacular enhancement of the average ZT.

Broad temperature plateau for high ZTs in heavily doped p-type SnSe single crystals

High thermoelectric figure of merit, zT, of ∼1.85 at 725 K along with significant cyclable temperature stability was achieved in Pb-free p-type Ge1–xSbxTe samples through simultaneous enhancement in Seebeck coefficient and reduction of thermal conductivity. Sb doping in GeTe decreases the carrier concentration due to the donor dopant nature of Sb and enhances the valence band degeneracy by increasing the cubic nature of the sample, which collectively boost Seebeck coefficient in the temperature range of 300–773 K. Significant thermal conductivity reduction was achieved due to collective phonon scattering from various meso-structured domain variants, twin and inversion boundaries, nanostructured defect layers, and solid solution point defects. The high performance Ge0.9Sb0.1Te sample shows mechanical stability (Vickers microhardness) of ∼206 Hv, which is significantly higher compared to other popular thermoelectric materials such as Bi2Te3, PbTe, PbSe, Cu2Se, and TAGS.

High Thermoelectric Performance and Enhanced Mechanical Stability of p-type Ge1–xSbxTe

Inorganic solids with low thermal conductivity are of great interest for thermoelectric applications. The formation of synthetic nanostructures by matrix encapsulation is one of the important strategies for thermal conductivity reduction through phonon scattering. Here, we report the reduction of lattice thermal conductivity near the theoretical minimum limit, κmin, in SnTe via spontaneous formation of nanodomains of the Sb-rich layered intergrowth SnmSb2nTe3n+m compounds, which are natural heterostructures. High-resolution transmission electron microscopy of Sn1−xSbxTe samples reveals the formation of endotaxial Sb rich nanoprecipitates (2–10 nm) along with super-structured intergrowth nanodomains (10–30 nm), which are the key features responsible for the significant reduction of lattice thermal conductivity in SnTe. This mechanism suggests a new avenue for the nanoscale engineering in SnTe to achieve low lattice thermal conductivities. Moreover, the presence of Sb improves the electronic transport properties by aliovalent cation doping which optimizes the hole concentration in SnTe. As a result, an enhanced thermoelectric figure of merit, zT, of ∼1 has been achieved for the composition of Sn0.85Sb0.15Te at 800 K. The high zT sample exhibits the Vickers microhardness value of ∼136 HV which is double that of pristine SnTe and is significantly higher than those of the present state-of-the-art thermoelectric materials.

The origin of low thermal conductivity in Sn1−xSbxTe: phonon scattering via layered intergrowth nanostructures

Thermoelectric materials have received recent attention due to their ability to convert waste heat to electrical energy directly and reversibly. Inorganic materials, especially Bi2Te3, PbTe and Si–Ge based alloys, have been investigated in the temperature range of 300–1000 K, among which PbTe based materials have been extensively studied, and reported to be the leading thermoelectric materials for mid-temperature power generation. However, environmental concern limits their large scale production due to the toxic nature of Pb. As an alternative, GeTe-rich alloys such as TAGS (GeTe–AgSbTe2) have been largely investigated since the 1960s. Most recently, some of the new materials in the GeTe family have been introduced such as Ge0.87Pb0.13Te, the homologous series of Sb2Te3(GeTe)n and Ge0.9Sb0.1Te, and are reported to exhibit high thermoelectric performance, inherently formed nano and microstructure modulations, and high thermal and mechanical stability. These collective enhanced properties of GeTe-rich alloys have generated great interest in investigating further new GeTe based alloys for intermediate temperature thermoelectric applications. In order to provide the fundamental understanding, technological insights, and to further promote the GeTe based alloys, we hereby present a review on (i) the crystal structure, nano/microstructure, phase transition, electronic structure, and thermoelectric properties of GeTe, (ii) correlation of compositional and microstructure modulations and thermoelectric properties of doped GeTe, TAGS based alloys, Ge–Pb–Te materials, and Ge–Sb–Te materials, (iii) mechanical properties, (iv) past and present devices based on GeTe materials and (v) future directions.

High performance thermoelectric materials and devices based on GeTe

Realization of High Thermoelectric Figure of Merit in GeTe by Complementary Co-doping of Bi and In

A promising thermoelectric figure of merit, zT, of ∼1.3 at 725 K was obtained in high quality crystalline ingots of Ge1−xBixTe. The substitution of Bi3+ in a Ge2+ sublattice of GeTe significantly reduces the excess hole concentration due to the aliovalent donor dopant nature of Bi3+. Reduction in carrier density optimizes electrical conductivity, and subsequently enhances the Seebeck coefficient in Ge1−xBixTe. More importantly, a low lattice thermal conductivity of ∼1.1 W m−1 K−1 for Ge0.90Bi0.10Te was achieved, which is due to the collective phonon scattering from meso-structured grain boundaries, nano-structured precipitates, nano-scale defect layers, and solid solution point defects. We have obtained a reasonably high mechanical stability for the Ge1−xBixTe samples. The measured Vickers microhardness value of the high performance sample is ∼165 HV, which is comparatively higher than that of state-of-the-art thermoelectric materials, such as PbTe, Bi2Te3, and Cu2Se.

Suresh Perumal

Papers

High Thermoelectric Performance and Enhanced Mechanical Stability of p-type Ge1–xSbxTe

The origin of low thermal conductivity in Sn1−xSbxTe: phonon scattering via layered intergrowth nanostructures

High performance thermoelectric materials and devices based on GeTe

Realization of High Thermoelectric Figure of Merit in GeTe by Complementary Co-doping of Bi and In

Reduction of thermal conductivity through nanostructuring enhances the thermoelectric figure of merit in Ge1−xBixTe