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.

Thermoelectric materials are of interest for applications as heat pumps and power generators. The performance of thermoelectric devices is quantified by a figure of merit, ZT, where Z is a measure of a material's thermoelectric properties and T is the absolute temperature. A material with a figure of merit of around unity was first reported over four decades ago, but since then-despite investigation of various approaches-there has been only modest progress in finding materials with enhanced ZT values at room temperature. Here we report thin-film thermoelectric materials that demonstrate a significant enhancement in ZT at 300 K, compared to state-of-the-art bulk Bi2Te3 alloys. This amounts to a maximum observed factor of approximately 2.4 for our p-type Bi2Te3/Sb2Te3 superlattice devices. The enhancement is achieved by controlling the transport of phonons and electrons in the superlattices. Preliminary devices exhibit significant cooling (32 K at around room temperature) and the potential to pump a heat flux of up to 700 W cm-2; the localized cooling and heating occurs some 23,000 times faster than in bulk devices. We anticipate that the combination of performance, power density and speed achieved in these materials will lead to diverse technological applications: for example, in thermochemistry-on-a-chip, DNA microarrays, fibre-optic switches and microelectrothermal systems.

Thin-film thermoelectric devices with high room-temperature figures of merit

Thermoelectric materials are solid-state energy converters whose combination of thermal, electrical, and semiconducting properties allows them to be used to convert waste heat into electricity or electrical power directly into cooling and heating. These materials can be competitive with fluid-based systems, such as two-phase air-conditioning compressors or heat pumps, or used in smaller-scale applications such as in automobile seats, night-vision systems, and electrical-enclosure cooling. More widespread use of thermoelectrics requires not only improving the intrinsic energy-conversion efficiency of the materials but also implementing recent advancements in system architecture. These principles are illustrated with several proven and potential applications of thermoelectrics.

http://engin1000.pbworks.com/f/TE_rev.pdf

Cooling, heating, generating power, and recovering waste heat with thermoelectric systems.

Graphene’s success has shown that it is possible to create stable, single and few-atom-thick layers of van der Waals materials, and also that these materials can exhibit fascinating and technologically useful properties. Here we review the state-of-the-art of 2D materials beyond graphene. Initially, we will outline the different chemical classes of 2D materials and discuss the various strategies to prepare single-layer, few-layer, and multilayer assembly materials in solution, on substrates, and on the wafer scale. Additionally, we present an experimental guide for identifying and characterizing single-layer-thick materials, as well as outlining emerging techniques that yield both local and global information. We describe the differences that occur in the electronic structure between the bulk and the single layer and discuss various methods of tuning their electronic properties by manipulating the surface. Finally, we highlight the properties and advantages of single-, few-, and many-layer 2D materials in...

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Progress, Challenges, and Opportunities in Two-Dimensional Materials Beyond Graphene

The thermoelectric effect enables direct and reversible conversion between thermal and electrical energy, and provides a viable route for power generation from waste heat The efficiency of thermoelectric materials is dictated by the dimensionless figure of merit, ZT (where Z is the figure of merit and T is absolute temperature), which governs the Carnot efficiency for heat conversion Enhancements above the generally high threshold value of 25 have important implications for commercial deployment, especially for compounds free of Pb and Te Here we report an unprecedented ZT of 26 ± 03 at 923 K, realized in SnSe single crystals measured along the b axis of the room-temperature orthorhombic unit cell This material also shows a high ZT of 23 ± 03 along the c axis but a significantly reduced ZT of 08 ± 02 along the a axis We attribute the remarkably high ZT along the b axis to the intrinsically ultralow lattice thermal conductivity in SnSe The layered structure of SnSe derives from a distorted rock-salt structure, and features anomalously high Gruneisen parameters, which reflect the anharmonic and anisotropic bonding We attribute the exceptionally low lattice thermal conductivity (023 ± 003 W m(-1) K(-1) at 973 K) in SnSe to the anharmonicity These findings highlight alternative strategies to nanostructuring for achieving high thermoelectric performance

Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals

Currently the materials with the highest thermoelectric figure of merit Z are ${\mathrm{Bi}}_{2}$${\mathrm{Te}}_{3}$ alloys. Therefore these compounds are the best thermoelectric refrigeration elements. However, since the 1960s only slow progress has been made in enhancing Z, either in ${\mathrm{Bi}}_{2}$${\mathrm{Te}}_{3}$ alloys or in other thermoelectric materials. So far, the materials used in applications have all been in bulk form. In this paper, it is proposed that it may be possible to increase Z of certain materials by preparing them in quantum-well superlattice structures. Calculations have been done to investigate the potential for such an approach, and also to evaluate the effect of anisotropy on the figure of merit. The calculations show that layering has the potential to increase significantly the figure of merit of a highly anisotropic material such as ${\mathrm{Bi}}_{2}$${\mathrm{Te}}_{3}$, provided that the superlattice multilayers are made in a particular orientation. This result opens the possibility of using quantum-well superlattice structures to enhance the performance of thermoelectric coolers.

Effect of quantum-well structures on the thermoelectric figure of merit.

We investigate the effect on the thermoelectric figure of merit of preparing materials in the form of one-dimensional conductors or quantum wires. Our calculations show that this approach has the potential to achieve a significant increase in the figure of merit over both the bulk value and the calculated superlattice values.

Thermoelectric figure of merit of a one-dimensional conductor.

Recently, it has been shown theoretically that it may be possible to increase the thermoelectric figure of merit ($Z$) of certain materials by preparing them in the form of two-dimensional quantum-well structures. Using $\mathrm{PbTe}/{\mathrm{Pb}}_{1\ensuremath{-}x}{\mathrm{Eu}}_{x}\mathrm{Te}$ multiple-quantum-well structures grown by molecular-beam epitaxy, we have performed thermoelectric and other transport measurements as a function of quantum-well thickness and doping. Our results are found to be consistent with theoretical predictions and indicate that an increase in $Z$ over bulk values may be possible through quantum confinement effects using quantum-well structures.

Experimental study of the effect of quantum-well structures on the thermoelectric figure of merit

Currently, the materials with the highest thermoelectric figure of merit (ZT) are one‐band materials. The presence of both electrons and holes lowers ZT, so two‐band materials such as semimetals are not useful thermoelectric materials. However, by preparing these materials in the form of two‐dimensional quantum‐well superlattices, it is possible to separate the two bands and transform the material to an effective one‐carrier system. We have investigated theoretically the effect of such an approach and our results indicate that a significant increase in ZT may be achieved. This result allows the possibility of using a new class of materials as thermoelectric refrigeration elements.

Use of quantum‐well superlattices to obtain a high figure of merit from nonconventional thermoelectric materials

Currently the materials with the highest thermoelectric figure of merit, Z, are Bi2Te3 alloys. Therefore these compounds are the best thermoelectric refrigeration elements. However, since the 1960's only slow progress has been made in enhancing Z, either in Bi2Te3 alloys or in other thermoelectric materials. So far, the materials used in applications have all been in bulk form. In this paper, it is proposed that it may be possible to increase Z of certain materials by preparing them in quantum well superlattice structures. Calculations have been done to investigate the potential for such an approach, and also to evaluate the effect of anisotropy on the figure of merit. The calculations show that layering has the potential to increase significantly the figure of merit of a highly anisotropic material like Bi2Te3, provided that the superlattice multilayers are made in a particular orientation. This result opens the possibility of using quantum well superlattice structures to enhance the performance of thermoelectric coolers.

L. D. Hicks

Papers

Effect of quantum-well structures on the thermoelectric figure of merit.

Thermoelectric figure of merit of a one-dimensional conductor.

Experimental study of the effect of quantum-well structures on the thermoelectric figure of merit

Use of quantum‐well superlattices to obtain a high figure of merit from nonconventional thermoelectric materials

The Effect of Quantum Well Structures on the Thermoelectric Figure of Merit