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.

Nanocrystals (NCs) discussed in this Review are tiny crystals of metals, semiconductors, and magnetic material consisting of hundreds to a few thousand atoms each. Their size ranges from 2-3 to about 20 nm. What is special about this size regime that placed NCs among the hottest research topics of the last decades? The quantum mechanical coupling * To whom correspondence should be addressed. E-mail: dvtalapin@uchicago.edu. † The University of Chicago. ‡ Argonne National Lab. Chem. Rev. 2010, 110, 389–458 389

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Prospects of Colloidal Nanocrystals for Electronic and Optoelectronic Applications

Graphene and related two-dimensional crystals and hybrid systems showcase several key properties that can address emerging energy needs, in particular for the ever growing market of portable and wearable energy conversion and storage devices. Graphene's flexibility, large surface area, and chemical stability, combined with its excellent electrical and thermal conductivity, make it promising as a catalyst in fuel and dye-sensitized solar cells. Chemically functionalized graphene can also improve storage and diffusion of ionic species and electric charge in batteries and supercapacitors. Two-dimensional crystals provide optoelectronic and photocatalytic properties complementing those of graphene, enabling the realization of ultrathin-film photovoltaic devices or systems for hydrogen production. Here, we review the use of graphene and related materials for energy conversion and storage, outlining the roadmap for future applications.

Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage

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

Thermoelectrics have long been recognized as a potentially transformative energy conversion technology due to their ability to convert heat directly into electricity. Despite this potential, thermoelectric devices are not in common use because of their low efficiency, and today they are only used in niche markets where reliability and simplicity are more important than performance. However, the ability to create nanostructured thermoelectric materials has led to remarkable progress in enhancing thermoelectric properties, making it plausible that thermoelectrics could start being used in new settings in the near future. Of the various types of nanostructured materials, bulk nanostructured materials have shown the most promise for commercial use because, unlike many other nanostructured materials, they can be fabricated in large quantities and in a form that is compatible with existing thermoelectric device configurations. The first generation of these materials is currently being developed for commercialization, but creating the second generation will require a fundamental understanding of carrier transport in these complex materials which is presently lacking. In this review we introduce the principles and present status of bulk nanostructured materials, then describe some of the unanswered questions about carrier transport and how current research is addressing these questions. Finally, we discuss several research directions which could lead to the next generation of bulk nanostructured materials.

Bulk nanostructured thermoelectric materials: current research and future prospects

Despite recent advances, thermoelectric energy conversion will never be as efficient as steam engines. That means thermoelectrics will remain limited to applications served poorly or not at all by existing technology. Bad news for thermoelectricians, but the climate crisis requires that we face bad news head on.

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An inconvenient truth about thermoelectrics.

A model is presented for the high-temperature transport properties of large-grain-size, heavily doped n-type silicon-germanium alloys. Electron and phonon transport coefficients are calculated using standard Boltzmann equation expressions in the relaxation time approximation. Good agreement with experiment is found by considering acoustic phonon and ionized impurity scattering for electrons, and phonon-phonon, point defect, and electron-phonon scattering for phonons. The parameters describing electron transport in heavily doped and lightly doped materials are significantly different and suggest that most carriers in heavily doped materials are in a band formed largely from impurity states. The maximum dimensionless thermoelectric figure of merit for single-crystal, n-type Si(0.8)Ge(0.2) at 1300 K is estimated at ZT about 1.13 with an optimum carrier concentration of n about 2.9 x 10 to the 20th/cu cm.

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A model for the high‐temperature transport properties of heavily doped n‐type silicon‐germanium alloys

The thermoelectric properties of 28 sintered Si(0.8)Ge(0.2) alloys, heavily doped with either B or P and prepared from powders with median particle sizes ranging from about 1 to over 100 microns, have been determined from 300 to 1300 K. The thermal conductivity decreases with decreasing particle size; however, the figure of merit is not significantly increased due to a compensating reduction in the electrical conductivity. The thermoelectric figure of merit is in good agreement with results of Dismukes et al. (1964) on similarly doped alloys prepared by zone-leveling techniques. The electrical and thermal conductivity are found to be sensitive to preparation procedure while the Seebeck coefficient and figure of merit are much less sensitive. The high-temperature electrical properties are consistent with charge carrier scattering by acoustic or optical phonons.

Thermoelectric properties of pressure-sintered Si0.8Ge0.2 thermoelectric alloys

In the 1950s there were hopes that semiconductor thermocouples would replace mechanical refrigerators, just as semiconductor transistors supplanted vacuum tubes. New materials may bring that goal a bit closer.

Semiconductors are cool.

The thermal conductivities of micron-thick epitaxial layers of dilute ${\mathrm{Si}}_{1\ensuremath{-}x}{\mathrm{Ge}}_{x}$ alloys, $2\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}4}lxl0.01$, are measured in the temperature range $297lTl550\phantom{\rule{0.3em}{0ex}}\mathrm{K}$ using time-domain thermoreflectance. These new data are used to test competing models for the strength of phonon scattering by heavy impurity atoms. Even though the mass difference between Ge and Si is much larger than the Si atomic mass, we find that the thermal conductivity of dilute SiGe alloys is adequately described by the scattering strength for point defects derived by perturbation theory by Klemens in 1955.

Cronin B. Vining

Papers

An inconvenient truth about thermoelectrics.

A model for the high‐temperature transport properties of heavily doped n‐type silicon‐germanium alloys

Thermoelectric properties of pressure-sintered Si0.8Ge0.2 thermoelectric alloys

Semiconductors are cool.

Thermal conductivity of epitaxial layers of dilute SiGe alloys