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.

Controlling the structure of thermoelectric materials on all length scales (atomic, nanoscale and mesoscale) relevant for phonon scattering makes it possible to increase the dimensionless figure of merit to more than two, which could allow for the recovery of a significant fraction of waste heat with which to produce electricity.

High-performance bulk thermoelectrics with all-scale hierarchical architectures

Approximately 90 per cent of the world's power is generated by heat engines that use fossil fuel combustion as a heat source and typically operate at 30-40 per cent efficiency, such that roughly 15 terawatts of heat is lost to the environment. Thermoelectric modules could potentially convert part of this low-grade waste heat to electricity. Their efficiency depends on the thermoelectric figure of merit ZT of their material components, which is a function of the Seebeck coefficient, electrical resistivity, thermal conductivity and absolute temperature. Over the past five decades it has been challenging to increase ZT > 1, since the parameters of ZT are generally interdependent. While nanostructured thermoelectric materials can increase ZT > 1 (refs 2-4), the materials (Bi, Te, Pb, Sb, and Ag) and processes used are not often easy to scale to practically useful dimensions. Here we report the electrochemical synthesis of large-area, wafer-scale arrays of rough Si nanowires that are 20-300 nm in diameter. These nanowires have Seebeck coefficient and electrical resistivity values that are the same as doped bulk Si, but those with diameters of about 50 nm exhibit 100-fold reduction in thermal conductivity, yielding ZT = 0.6 at room temperature. For such nanowires, the lattice contribution to thermal conductivity approaches the amorphous limit for Si, which cannot be explained by current theories. Although bulk Si is a poor thermoelectric material, by greatly reducing thermal conductivity without much affecting the Seebeck coefficient and electrical resistivity, Si nanowire arrays show promise as high-performance, scalable thermoelectric materials.

Enhanced thermoelectric performance of rough silicon nanowires

Many of the recent advances in enhancing the thermoelectric figure of merit are linked to nanoscale phenomena found both in bulk samples containing nanoscale constituents and in nanoscale samples themselves. Prior theoretical and experimental proof-of-principle studies on quantum-well superlattice and quantum-wire samples have now evolved into studies on bulk samples containing nanostructured constituents prepared by chemical or physical approaches. In this Review, nanostructural composites are shown to exhibit nanostructures and properties that show promise for thermoelectric applications, thus bringing together low-dimensional and bulk materials for thermoelectric applications. Particular emphasis is given in this Review to the ability to achieve 1) a simultaneous increase in the power factor and a decrease in the thermal conductivity in the same nanocomposite sample and for transport in the same direction and 2) lower values of the thermal conductivity in these nanocomposites as compared to alloy samples of the same chemical composition. The outlook for future research directions for nanocomposite thermoelectric materials is also discussed.

https://www.bc.edu/content/dam/files/schools/cas_sites/physics/pdf/Ren/AdvMater_19_1043_2007.pdf

New Directions for Low-Dimensional Thermoelectric Materials**

Approximately 90 per cent of the world’s power is generated by heat engines that use fossil fuel combustion as a heat source and typically operate at 30–40 per cent efficiency, such that roughly 15 terawatts of heat is lost to the environment. Thermoelectric modules could potentially convert part of this low-grade waste heat to electricity. Their efficiency depends on the thermoelectric figure of merit ZT of their material components, which is a function of the Seebeck coefficient, electrical resistivity, thermal conductivity and absolute temperature. Over the past five decades it has been challenging to increase ZT > 1, since the parameters of ZT are generally interdependent. While nanostructured thermoelectric materials can increase ZT > 1 (refs 2–4), the materials (Bi, Te, Pb, Sb, and Ag) and processes used are not often easy to scale to practically useful dimensions. Here we report the electrochemical synthesis of large-area, wafer-scale arrays of rough Si nanowires that are 20–300 nm in diameter. These nanowires have Seebeck coefficient and electrical resistivity values that are the same as doped bulk Si, but those with diameters of about 50 nm exhibit 100-fold reduction in thermal conductivity, yielding ZT = 0.6 at room temperature. For such nanowires, the lattice contribution to thermal conductivity approaches the amorphous limit for Si, which cannot be explained by current theories. Although bulk Si is a poor thermoelectric material, by greatly reducing thermal conductivity without much affecting the Seebeck coefficient and electrical resistivity, Si nanowire arrays show promise as high-performance, scalable thermoelectric materials.

http://absimage.aps.org/image/MAR08/MWS_MAR08-2007-020111.pdf

Enhanced Thermoelectric Performance in Rough Silicon Nanowires

1 Historical Development.- 2 Transport of Heat and Electricity in Solids.- 3 Selection and Optimization Criteria.- 4 Measurement and Characterization.- 5 Review of Established Materials and Devices.- 6 The Phonon-Glass Electron-Crystal Approach to Thermoelectric Materials Research.- 7 Complex Chalcogenide Structures.- 8 Low-Dimensional Thermoelectric Materials.- 9 Thermionic Refrigeration.- References.

Thermoelectrics: Basic Principles and New Materials Developments

Transport properties of polycrystalline Ge clathrates with general composition Sr8Ga16Ge30 are reported in the temperature range 5 K⩽T⩽300 K. These compounds exhibit N-type semiconducting behavior with relatively high Seebeck coefficients and electrical conductivity, and room temperature carrier concentrations in the range of 1017–1018 cm−3. The thermal conductivity is more than an order of magnitude smaller than that of crystalline germanium and has a glasslike temperature dependence. The resulting thermoelectric figure of merit, ZT, at room temperature for the present samples is 14 that of Bi2Te3 alloys currently used in devices for thermoelectric cooling. Extrapolating our measurements to above room temperature, we estimate that ZT>1 at T>700 K, thus exceeding that of most known materials.

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Semiconducting Ge clathrates: Promising candidates for thermoelectric applications

▪ Abstract Recently there has been a resurgence of research efforts related to the investigation of new and novel materials for small-scale thermoelectric refrigeration and power generation applications. These materials need to couple and optimize a variety of properties in order to exhibit the necessary figure of merit, i.e. the numerical expression that is commonly used to compare one potential thermoelectric material with another. The figure of merit is related to the coefficient of performance or efficiency of a particular device made from a material. The best thermoelectric material should possess thermal properties similar to that of a glass and electrical properties similar to that of a perfect single-crystal material, i.e. a poor thermal conductor and a good electrical conductor. Skutterudites are materials that appear to have the potential to fulfill such criteria. These materials exhibit many types of interesting properties. For example, skutterudites are members of a family of compounds we call...

SKUTTERUDITES : A phonon-glass-electron crystal approach to advanced thermoelectric energy conversion applications

The thermal conductivity of polycrystalline semiconductors with type-I clathrate hydrate crystal structure is reported. Ge clathrates (doped with Sr and/or Eu) exhibit lattice thermal conductivities typical of amorphous materials. Remarkably, this behavior occurs in spite of the well-defined crystalline structure and relatively high electron mobility ( $\ensuremath{\sim}100{\mathrm{cm}}^{2}/\mathrm{V}\mathrm{s}$). The dynamics of dopant ions and their interaction with the polyhedral cages of the structure are a likely source of the strong phonon scattering.

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Glasslike Heat Conduction in High-Mobility Crystalline Semiconductors

Polycrystalline samples of antimonides with the skutterudite crystal structure with La partially filling the voids have been prepared in an effort to quantify the impact of partial void filling on the lattice thermal conductivity of these compounds. It is observed that a relatively small concentration of La in the voids results in a relatively large decrease in the lattice thermal conductivity. In addition, the largest decrease in the lattice thermal conductivity, compared to ‘‘unfilled’’ CoSb 3 is not observed near 100% filling of the voids with La, as was previously believed. This suggests a point-defect-type phonon scattering effect due to the partial, random distribution of La in the voids as well as the ‘‘rattling’’ effect of the La ions, resulting in the scattering of a larger spectrum of phonons than in the case of 100% filling. An additional benefit of partial filling in thermoelectric materials is that it may be one way of adjusting the electronic properties of these compounds. Seebeck, resistivity, Hall effect and structural data for these skutterudite compounds are also presented. @S0163-1829~98!02926-9#

/pdf/effect-of-partial-void-filling-on-the-lattice-thermal-23imhna14j.pdf

George S. Nolas

Papers

Thermoelectrics: Basic Principles and New Materials Developments

Semiconducting Ge clathrates: Promising candidates for thermoelectric applications

SKUTTERUDITES : A phonon-glass-electron crystal approach to advanced thermoelectric energy conversion applications

Glasslike Heat Conduction in High-Mobility Crystalline Semiconductors

Effect of partial void filling on the lattice thermal conductivity of skutterudites