The thermoelectric transport properties of superlattices have been studied using an exact solution of the Boltzmann equation. The role of heat transport along the barrier layers, of carrier tunneling through the barriers, of valley degeneracy and of the well width and energy dependences of the carrier-phonon scattering rates on the thermoelectric figure of merit are given. Calculations are given for Bi2Te3 and for PbTe, and the results of recent experiments are discussed.

The Si/Sil−xGex quantum well system is attractive for high temperature thermoelectric applications and for demonstration of proof-of-principle for enhanced thermoelectric figure of merit Z, since the interfaces and carrier densities can be well controlled in this system. We report here theoretical calculations for Z in this system, and results from theoretical modeling of quantum confinement effects in the presence of δ-doping within the barrier layers. The δ-doping layers are introduced by growing very thin layers of wide band gap materials within the barrier layers in order to increase the effective barrier height within the barriers and thereby reduce the barrier width necessary for the quantum confinement of carriers within the quantum well. The overall figure of merit is thereby enhanced due to the reduced barrier width and hence reduced thermal conductivity, K. The δ-doping should further reduce K in the barriers by introducing phonon scattering centers within the barrier region. The temperature dependence of Z for Si quantum wells is also discussed.

Recent experimental results on semiconductors with the skutterudite crystal structure show that these materials possess attractive transport properties and have a good potential for achieving ZT values substantially larger than for state-of-the-art thermoelectric materials. Both n-type and p-type conductivity samples have been obtained, using several preparation techniques. Associated with a low hole effective mass, very high carrier mobilities, low electrical resistivities and moderate Seebeck coefficients are obtained in p-type skutterudites. For a comparable doping level, the carrier mobilities of n-type samples are about an order of magnitude lower than the values achieved on p-type samples. However, the much larger electron effective masses and Seebeck coefficients make n-type skutterudites promising candidates as well. Unfortunately, the thermal conductivities of the binary skutterudite compounds are too large, particularly at low temperatures, to be useful for thermoelectric applications.

Several approaches to the reduction of the lattice thermal conductivity in skutterudites are being pursued: heavy doping, formation of solid solutions and alloys, study of novel ternary and filled skutterudite compounds. All those approaches have already resulted in skutterudite compositions with substantially lower thermal conductivity values in these materials. Recently, superior thermoelectric properties in the moderate to high temperature range were achieved for compositions combining alloying and “filling” of the skutterudite structure. Experimental results and mechanisms responsible for low thermal conductivity in skutterudites are discussed.

The thermoelectric properties of La-filled skutterudites and β-Zn4Sb3 are discussed from the point of view of their electronic structures. These are calculated from first principles within the local density approximation. The electronic structures are in turn used determine transport related quantities. β-Zn4Sb3 is found to be metallic with a complex Fermi surface topology, which yields a non-trivial dependence of the Hall concentration on the band filling. Calculations of the variation with band filling are used to extract the carrier concentration from the experimental Hall number. At this band filling, which corresponds to 0.1 electrons per 22 atom unit cell, we calculate a Seebeck coefficient and temperature dependence in good agreement with the experimental value. The high Seebeck coefficients in a metallic material are remarkable, and arise because of the strong energy dependence of the Fermiology near the experimental band filling. Virtual crystal calculations for La(Fe,Co)4Sb12 show that the system obeys almost perfect rigid band behavior with varying Co concentration, and has a substantial band gap at a position corresponding to the composition LaFe3CoSb12. The valence band maximum occurs at the Γ point and is due to a singly degenerate dispersive (Fe,Co)-Sb band, which by itself would not be favorable for TE. However, very flat transition metal derived bands occur in close proximity and become active as the doping level is increased, giving a non-trivial dependence of the properties on carrier concentration and explaining the favorable TE properties.

After a brief review of the transport and thermoelectric properties of filled skutterudite antimonides, we present resonant ultrasound, specific heat, and inelastic neutron scattering results that establish the existence of two low-energy vibrational modes in the filled skutterudite LaFe3CoSb12. It is likely that at least one of these modes represents the localized, incoherent vibrations of the La ion in an oversized atomic “cage.” These results support the usefulness of weakly bound, “rattling” ions for the improvement of thermoelectric performance.

A series of new, metastable ternary crystalline compounds with the skutterudite crystal structure have been synthesized using modulated elemental reactants. The initial reactants are made up of multiple repeats of a ˜25Å thick unit containing elemental layers of the desired ternary metal, iron and antimony. Low temperature annealing (150°C) results in interdiffusion of the elemental layers to form amorphous reaction intermediates. Annealing these intermediates at temperatures between 200°C and 250°C results in exothermic crystallization of the desired skutterudite crystal structure. Most of the new compounds prepared are only kinetically stable, decomposing exothermically to form thermodynamically more stable mixtures of binary compounds and elements. Low angle x-ray diffraction studies show that the resulting films are exceedingly smooth. These films have an ideal geometry for measuring properties of importance for thermoelectric devices—the Seebeck coefficient and the electrical conductivity. Thermal conductivity can be measured using a modification of the 3ω technique of Cahill. Samples can be produced rapidly, allowing for systematic screening and subsequent optimization as a function of composition and doping levels.

Polycrystalline CoSb3 films were grown on a variety of electrically insulating substrates by pulsed laser ablation from a stoichiometric hot-pressed target. These films are fully crystallized in the skutterudite structure, and the grains exhibit a strongly preferred alignment of the cubic [310]-axis perpendicular to the substrate surface. The film quality is studied for different single-crystal substrates and as a function of growth temperature and background gas.

Hall measurements show that the films are p-type semiconducting with a room-temperature carrier density of 3×1020 holes/cm3. The Hall mobility is found to be 50 to 60 cm2 /Vs, which is high for such a heavily-doped material. The Seebeck coefficient and the resistivity are measured as a function of temperature and are compared to bulk measurements.

A review is presented of the thermoelectric properties of rare earth compounds. A discussion is presented of the prospects for future improvements in the figure of merit.

We review thermoelectric transport in a magnetic field. The key physical effect for thermomagnetic cooling is the Ettingshausen effect. We describe the design principles, measurement difficulties and areas where more work can prove fruitful in an exploration of cryogenic refrigeration based on this effect. New principles are discussed to guide the search for new materials and their development.

Non-cubic materials, when structurally aligned, possess sufficient anisotropy to exhibit thermoelectric effects where the electrical and thermal currents are orthogonal (“off-diagonal” thermoelectricity). We discuss the benefits of this form of thermoelectricity for devices and describe a search for suitable properties in the air-stable conducting polymers polyaniline and polypyrrole. We find the simple and general correlation that the logarithm of the electrical conductivity scales linearly with the Seebeck coefficient on doping but with proportionality in excess of the conventional prediction for thermoelectricity. The correlation is unexpected in its universality and unfavorable for thermoelectric applications. A simple model suggests that mobile charges of both signs exist in these polymers, and this leads to reduced thermoelectric efficiency. We also briefly discuss non air-stable polyacetylene, where “ambipolar” transport does not appear to occur, and where properties seem more favorable for thermoelectricity.

We have measured the resistivity and thermopower of single crystals as well as polycrystalline pressed powders of the low-dimensional pentatelluride materials: HfTe5 and ZrTe5. We have performed these measurements as a function of temperature between 5K and 320K. In the single crystals there is a peak in the resistivity for both materials at a peak temperature, Tp where Tp ≈ 80K for HfTe5 and Tp ≈ 145K for ZrTe5. Both materials exhibit a large p-type thermopower around room temperature which undergoes a change to n-type below the peak. This data is similar to behavior observed previously in these materials. We have also synthesized pressed powders of polycrystalline pentatelluride materials, HfTe5 and ZrTe5. We have measured the resistivity and thermopower of these polycrystalline materials as a function of temperature between 5K and 320K. For the polycrystalline material, the room temperature thermopower for each of these materials is relatively high, +95 μV/K and +65 μV/K for HfTe5 and ZrTe5 respectively. These values compare closely to thermopower values for single crystals of these materials. At 77 K, the thermopower is +55 μV/K for HfTe5 and +35 μV/K for ZrTe5. In fact, the thermopower for the polycrystals decreases monotonically with temperature to T ≈ 5K, thus exhibiting p-type behavior over the entire range of temperature. As expected, the resistivity for the polycrystals is higher than the single crystal material, with values of 430 mΩ-cm and 24 mΩ-cm for Hfre5 and ZrTe5 respectively, compared to single crystal values of 0.35 mΩ-cm (HfTe5) and 1.0 mΩ-cm (ZrTe5). We have found that the peak in the resistivity evident in both single crystal materials is absent in these polycrystalline materials. We will discuss these materials in relation to their potential as candidates for thermoelectric applications.

The electrical transport properties of β-FeSi2 single crystals have been investigated in dependence on the purity of the source material and on doping with 3d transition metals. The transport properties included are electrical conducticvity, Hall conductivity and thermopower mainly in the temperature range from 4K to 300K. The single crystals have been prepared by chemical transport reaction in a closed system with iodine as transport agent. In undoped single crystals prepared with 5N Fe both electrical conductivity and thermopower depend on the composition within the homogeinity range of β-FeSi2 which is explained by different intrinsic defects at the Sirich and Fe-rich phase boundaries. In both undoped and doped single crystals impurity band conduction is observed at low temperatures but above 100K extrinsic behaviour determined by shallow impurity states. The thermopower shows between 100K and 200K a significant phonon drag contribution which depends on intrinsic defects and additional doping. The Hall resistivity is considered mainly with respect to an anomalous contribution found in p-type and n-type single crystals and thin films. In addition doped single crystals show at temperatures below about 130K an hysteresis of the Hall voltage. These results make former mobility data uncertain. Comparison will be made between the transport properties of single crystals and polycrystalline material.

β-FeSi2 is a promising material for the application of various electronic, optoelectronic and energy devices. We present here the semiconducting properties of β-FeSi2 films on Si(100) substrate prepared by laser ablation method. Samples were grown using poly-crystalline bulk β-FeSi2 prepared by horizontal gradient freeze method. For the monitoring of growth, in-situ observation of ablation plume was made through fluorescence spectroscopy. Reflection of highenergy electron beam diffraction (RHEED) was also made in-situ to see the surface morphology. Characterization of the films by X-ray diffraction presented purely P3(220) orientation. Raman scattering measurements at room temperature also indicated that the grown films are semiconducting β-FeSi2. Optical absorption spectra at room temperature showed absorption coefficient higher than 105 cm−1 above the band-gap (˜1.2 eV). It was revealed that high quality semiconducting β-FeSi2 films can be fabricated by laser ablation method without post-annealing.

The technology base for air conditioning, refrigeration, component cooling below ambient temperatures and power generation will be required to meet several new challenges. The main lines of these challenges will be presented in a way which relates them to the several new thermoelectric materials and materials engineering options being pursued by the research community. The potential benefits of thermoelectric devices are only partially met by enhancing the figure of merit ZT, the nature of the design challenge and the resulting systems approach are presented. The research and the industry are entering into a new era.

A combination of environmental, economic, and technological drivers has led to a reassessment of the potential for using thermoelectric devices in several automotive applications. In order for this technology to achieve its ultimate potential, new materials with enhanced thermoelectric properties are required. Experimental results on the fundamental physical properties of some new thermoelectric materials, including filled skutterudites and 1–1–1 intermetallic semiconductors, are presented.

This paper presents current NASA biomedical developments and applications using thermoelectrics. Discussion will include future technology enhancements that would be most beneficial to the application of thermoelectric technology.

A great deal of thermoelectric applications have focused on electronic cooling. As with all technological developments within NASA, if the application cannot be related to the average consumer, the technology will not be mass-produced and widely available to the public (a key to research and development expenditures and thermoelectric companies). Included are discussions of thermoelectric applications to cool astronauts during launch and reentry. The earth-based applications, or spin-offs, include such innovations as tank and race car driver cooling, to cooling infants with high temperatures, as well as, the prevention of hair loss during chemotherapy. In order to preserve the scientific value of metabolic samples during long-term space missions, cooling is required to enable scientific studies. Results of one such study should provide a better understanding of osteoporosis and may lead to a possible cure for the disease.

In the space environment, noise has to be kept to a minimum. In long-term space applications such as the International Space Station, thermoelectric technology provides the acoustic relief and the reliability for food, as well as, scientific refrigeration/freezers. Applications and future needs are discussed as NASA moves closer to a continued space presence in Mir, International Space Station, and Lunar-Mars Exploration.

We have investigated the magnetic and transport properties of CeyCo4Sb12 filled skutterudites with the filling fraction y ≤ 0.1. These compounds are n-type materials that develop a magnetic moment upon the presence of trivalent cerium. Cerium has a strong influence on all transport properties and even in small amounts it drastically reduces the lattice thermal conductivity. The resulting figures of merit are comparable to the values established previously for the p-type filled skutterudites.

We report the measurement of the thermal conductivity, electrical resistivity, and thermoelectric power on two quasicrystalline compounds, A170Pd20Re10 and A162.5Cu25Fe12.5. These materials are found to posses a thermal conductivity of order 1 W/m K, while retaining their semimetallic conductivity. These features coupled with moderately large thermopowers, up to 55 μV/K, imply that the general class of quasicrystalline compounds warrants careful investigation for their potential as new thermoelectric materials.