You are on page 1of 11

Thermoelectric Materials: Principles, Structure, Properties, and Applications

During the 1990s there was a heightened interest in the field of thermoelectrics driven by the need for more efficient materials for electronic refrigeration and power generation (Nolas et al. 2002, Tritt et al. 2000a, Tritt et al. 1998, Tritt et al. 1997). Proposed industrial and military applications of thermoelectric (TE) materials are generating increased activity in this field by demanding higher performance, nearroom-temperature TE materials than those presently in use. Thermoelectric refrigeration is an environmentally ‘‘green’’ method of small-scale localized cooling in computers, infrared detectors, electronics, and opto-electronics as well as many other applications. However, most of the electronics and optoelectronics technologies typically require only small scale or localized spot cooling of small components which do not impose a large heat load. If significant economical cooling can be achieved the resulting ‘‘cold computing’’ could produce speed gains of 30– 200% in some CMOS computer processors. Cooling is perceived by many as the fundamental limit to electronic system performance. Cooling of laser diodes and infrared detectors to temperatures (T ), between 100 K and 200 K, would greatly improve performance and sensitivity and thus is extremely important to many technologies. Thus, the potential payoff for the development of low-temperature thermoelectric refrigeration devices is great, and the requirement for compounds with properties optimized over wide temperature ranges has led to a much-expanded interest in new thermoelectric materials. Utilization of Peltier coolers in relation to refrigeration of biological specimens/samples is an emerging application of thermoelectrics. Power generation applications are being investigated by the automotive industry as a means to develop electrical power from waste engine heat for use in the ‘‘next generation vehicle.’’ These uses range from power generation utilizing waste engine heat from the exhaust and radiator cooling system to seat coolers for comfort or electronic component cooling. Of course, the deep space applications of NASA’s Voyager and Cassini missions using radioactive thermoelectric generators (RTGs) are well established. Given the present energy needs experienced in the United States there is even a more pressing need to investigate alternative energy conversion technologies in this country, e.g., the thermal to electrical energy conversion from natural heat gradients that thermoelectric technologies provide. This has already been identified as important in many European and Asian countries. An overview of the state-of-the-art materials, a theoretical and experimental discussion of the basic principles, as well as an overview of some of the recent develop-

ments and materials is given in the texts of Tritt and Nolas (Nolas et al. 2001a, Tritt 2000a).

1. Thermoelectric Phenomena
1.1 Seebeck and Peltier Effects A discussion of thermoelectric effects and devices should start with the most fundamental phenomena, the Seebeck effect or thermopower (Morelli 1997), (see Thermoelectric Power: Theoretical Concepts). In the early 1800s Seebeck observed that if two dissimilar materials were joined together and the junctions were held at different temperatures (T and T þ DT) a voltage difference (DV) was developed that was proportional to the temperature difference (DT). The ratio of the voltage developed to the temperature gradient (DV/DT) is related to an intrinsic property of the materials called the Seebeck coefficient (a) or the thermopower. The Seebeck coefficient is very low for metals (only a few mV KÀ1) and much larger for semiconductors (typically a few 100 mV KÀ1). A related effect (the Peltier effect) was discovered a few years later by Peltier, who observed that if an electrical current is passed through the junction of two dissimilar materials, heat is either absorbed or rejected at the junction depending on the direction of the current. This effect is due to the difference in Fermi energies (discussed later: Sect. 4.1) of the two materials. The Seebeck effect and the Peltier effect are illustrated in Figs. 1 and 2, respectively. These two effects are related to each other, as shown in the definition of the Peltier coefficient, P;
P ¼ aT ð1Þ

The rate that the Peltier heat is liberated or rejected at the junction (QP) is given by:
QP ¼ aIT ð2Þ

where, I is the current through the junction and T is the temperature in kelvin. There are also a number of thermomagnetic effects such as the Hall, Ettingshausen, and Nernst effects that are beyond the scope of this article. The reader is referred to the text by Nolas et al. (2001a) for a discussion of these effects. 1.2 Thermoelectric Modules—Devices

The Peltier effect is the basis for many modern day TE refrigeration devices and the Seebeck effect is the basis for TE power generation devices (see Thermoelectric Devices: Refrigeration and Power Generations With No Moving Parts). The versatility of TE materials is illustrated in Fig. 3 which shows a diagram of a thermoelectric couple composed of an n-type (negative thermopower and electron carriers) and a p-type (positive thermopower and hole 1

Structure. and localized heating or cooling. s the electrical conductivity.Thermoelectric Materials: Principles. The advantages of TE solid state energy conversion are compactness. 2. Thermoelectric energy conversion utilizes the Peltier heat generated when an electric current is passed through a thermoelectric material to provide a temperature gradient with heat being absorbed on the cold side. The Figure of Merit 2. quietness (no moving parts). closed circle arrows) material and a p-type (holes. This diagram illustrates both power generation (Seebeck effect) and electronic refrigeration (Peltier effect) capabilities of the thermoelectric module. which are arranged electrically in series and thermally in parallel. the lattice 2 . ZT ¼ a2 sT a2 T ¼ k rk ð3Þ where. in which a voltage difference (DV) is generated that is proportional to the temperature gradient (DT) between the ends of the couple. The Peltier effect is the basis for electronic refrigeration discussed in the text.1 Definition and Description of the Figure of Merit The potential of a material for thermoelectric applications is determined in large part to a measure of the material’s dimensionless figure of merit. The Seebeck effect is the basis for power generation discussed in the text. Both refrigeration and power generation may be accomplished using the same module as shown in Fig. Many of the potential applications and importance of these devices have already been discussed in the background and applications section. and k the total thermal conductivity (k ¼ kL þ kE . r the electrical resistivity. Properties. Figure 3 A schematic illustrating a thermoelectric couple or module made of an n-type (electrons. and Applications Figure 1 A schematic illustrating the Seebeck effect of a couple of two dissimilar materials. carriers) semiconductor material connected through metallic electrical contact pads. heat is either absorbed or rejected depending on the direction of the current through the two materials. transferred through (or pumped by) the thermoelectric materials and rejected at the sink. As a current (I) flows through the junction of the two materials. Figure 2 A schematic illustrating the Peltier effect between two dissimilar materials (A and B). open circle arrows) material. A TE module or device is built up of an array of these couples. a is the Seebeck coefficient. 3. thus providing a refrigeration capability.

Since the 1970s. especially at lower temperatures. ZT is maximized when the product RK is minimized. and Applications and electronic contributions. (3)) can be increased by decreasing kL or by increasing either a or s. ZTE1. This value. yet no theoretical or thermodynamic reason exists for a ZTE1 as an upper barrier. Properties. s is tied to the electronic thermal conductivity. This is accomplished when: Ln Ap ¼ Lp An   rp kn 1=2 rn kp ð5Þ and the figure of merit for the couple is given by Eqn. Structure. Due to the extensive investigations of these traditional thermoelectric materials there appears little room for future improvement. where R is the total couple resistance and K is the couple thermal conductance. Several bulk materials are currently under investigation and show some promise. Semiconductors have been primarily the materials of choice for thermoelectric applications. a2sT. entirely new classes of compounds will have to be investigated (Tritt 1996). has been a practical upper limit since the 1970s. (4). an n-type and a p-type. the Peltier heat. in order. as shown in the figure above. 3 .2 Coefficient of Performance and Efficiency The best thermoelectric materials that are currently in devices have a value of ZTE1. Rowe 1995). The terms in the numerator are. However. The value of ZT (Eqn. (or a2T/r) is typically optimized as a function of carrier concentration (typically around 1019 carriers cmÀ3). Figure 4 A plot of the figure of merit (ZT) as a function of temperature for several bulk thermoelectric materials as indicated in the figure above. High mobility carriers are most desirable in order to have the highest electrical conductivity. Figure 4 shows the ZT as a function of temperature for the Bi2Te3 and Si1ÀxGex materials as The coefficient of performance (f) (refrigeration mode) of the thermoelectric couple is determined by the cooling power or net heat pumping rate (QC ) over the power input (W ) and is given below: j¼ 2 QC ðap À an ÞITC À K DT À 1 2I R ¼ I ½ðap À an ÞDT þ IRŠ W ð6Þ where TC ðTH Þ is the cold side (hot side) temperature and DT ¼ TH–TC. and the Joule heating term due to the total resistance of the couple. respectively). to give the largest ZT. The efficiency (Z) (power generation mode) of the thermoelectric couple is given by the power input to the load (W) over the net heat flow rate (QH ). through doping. 3. and thus. through the Wiedemann–Franz relationship (see Boltzmann Equation and Scattering Mechanisms) and the ratio is essentially constant at a given temperature. Some of the goals of research efforts in the early part of the twenty-first century are to find new materials which either raise the current efficiency of thermoelectric devices (increase ZT ) or have the capability of operating in new and broader temperature regimes. kE . The Bi2Te3 material is the current state-of-the-art refrigeration material and the Si1-xGex alloy is the current state-of-the-art power generation material. The ZT for a single material is somewhat incomplete since an array of TE couples are utilized in a device or module. one can see that the efficiency (Z) is proportional to ð1 þ ZT Þ1=2 . 2. To250 K. The resulting figure of merit for the couple (or a device) is typically given by: ZT ¼ ðap À an Þ2 T ðrn kn Þ1=2 þ ðrp kp Þ1=2 ð4Þ The ZT is not a fixed quantity for the couple and can depend on the relative dimensions of the branches. the thermal conductance heat flow (Fourier heat) due to the DT.Thermoelectric Materials: Principles. There are two materials in the TE couple. alloys based on the Bi2Te3 system [(Bi1ÀxSbx)2(Te1ÀxSex)3] and the Si1ÀxGex system have been extensively studied and optimized for their use as thermoelectric materials to perform a variety of solid state TE refrigeration and power generation applications (Goldsmid 1986. The power factor. where QH is positive for heat flow from the source to the sink and is given below: Z¼ W I ½ðap À an ÞDT À IRŠ ¼ 2 QH K DT þ ðap À an ÞITH À 1 2I R ð7Þ Thus. which is shown in Fig.

the heat per carrier is essentially a product of the electronic specific heat and the temperature divided by the number of carriers (N ). which represents the thermopower of a classical electron gas. respectively. aAB . such that at TE0. and t is the mean scattering time between collisions for the carriers. a charged particle must first be excited across an energy gap EG. In a semiconductor. typically nE1022 carriers cmÀ3.e.5 Thermal Conductivity The thermal conductivity. (aECelT/N) and then a is approximately:   Cel kB kB T aE E Q e EF ð8Þ The electrical conductivity is related to the density of charge carriers (n) and their mobility (m). on the order of 106 (O cm)À1. is related to the transfer of heat through a material. what is actually measured is the difference in the Seebeck coefficients of the two dissimilar materials. kB/eE87mVKÀ1. however these are somewhat arbitrary boundaries. where aAB ¼ aA À aB . Again for semiconductors. and all the states below are occupied. either by the electrons or . For the case of a classical gas each particle has an energy of 3/2 kB T . all states above this energy are vacant.3 Thermopower or Seebeck Coefficient gap is large enough to effectively minimize minority carrier contributions.   EG sEs0 exp þ kB T ð13Þ Thus. and a known lead value. and p and mh are the hole concentration and mobility. typically given by s ¼ nem ð11Þ The mobility is given by: m ¼ et=me ð12Þ where EF is the Fermi energy (related to the chemical potential of the material) which is basically the energy. There are two primary ways to achieve a high conductivity in a semiconductor. respectively. Metals have thermopower values much less than 87 mV KÀ1 (on the order of 1–10 mV KÀ1) and decrease with decreasing temperature. where kB is the Boltzmann constant.e. Semiconductors can exhibit either electron conduction (negative thermopower) or hole conduction (positive thermopower). which includes both the sample (aA ) and the lead (aB ) contributions. The absolute thermopower of an unknown sample is then given by the measured aAB . either by having a very small gap to excite across (EGokBT) or by having very high mobility carriers. which are discussed in Sect. In a measurement of the Seebeck effect. EF ckB T ). The thermopower for different carrier types is given by a weighted average to their electrical conductivity values (se and sp ) aE ae se þ ap sp se þ sp ð10Þ The conductivity can occur through the contributions of both holes and electrons s ¼ neme þ pemh ð14Þ It is necessary to dope the semiconductors with either donor or acceptor states to allow extrinsic conduction of the appropriate carrier type. In metals there are many carriers and states available for conduction. 2. For metals. i. The thermopower is thus approximately kB =e. electrons. and Applications well as many of the more recently developed bulk materials. respectively. In this case the thermopower is approximated by:   Cel kB E G aE E Q e kB T ð9Þ where m is the mobility of the carriers.. The quantity. such as Pb or some other known standard. Properties. 2. me is the effective mass. Structure.Thermoelectric Materials: Principles. the carriers must be thermally excited across a gap for conduction to occur. The relative Seebeck coefficient is given by aAB ¼ ÀDV/DT. or holes. 4. is a constant. which is called the relative Seebeck of the couple.4 Electrical Conductivity The thermoelectric power or Seebeck coefficient (a) can be thought of as the heat per carrier over temperature or more simply the entropy per carrier. It is apparent the total thermopower will be lower than that of either of the individual contributions unless the direct band 4 where n and me are the electron concentration and mobility. i. the thermopower is larger than the characteristic value 87 mV KÀ1 and increases with decreasing temperature. (aB ). Typical values of the electrical conductivity lie between 10À4 and 104 (O cm)À1. aEC/q where C is the specific heat and q is the charge of the carrier (Chaiken 1990). 2. Let us estimate an expected magnitude for the thermopower of metals and semiconductors. where e is the charge of the electron. k. The electrical conductivity is then very large for metals..

3. Understanding the various effects and selecting optimization strategies can be an exceedingly difficult 5 . coefficient and electrical conductivity (both in the numerator of ZT—see Eqns. The candidates need to be narrow bandgap semiconductors with high-mobility carriers. The candidate material is typically a narrow bandgap semiconductor (EGE10 kBT or E0. While grain boundary scattering can be an important consideration for reducing the lattice thermal conductivity. Sb. This assumes an elastic scattering mechanism and that the mean scattering time for the electrons and the phonons is the same. Thus.45 Â 10À8 (V2 KÀ2)). L0 ¼ 2. The thermal conductivity of complex materials can often be modified by chemical substitutions. In semiconductors. Te. (3) and (4)) are strong functions of the doping level and chemical composition.. attempts are being made to reduce the lattice part of the thermal conductivity essentially to its minimum value. Whether one is investigating thin film or bulk thermoelectrics materials. (mE2000 cm2 (V s)À1) while the thermal conductivity must be minimized. it would have the electrical properties of a crystalline material and the thermal properties of an amorphous or glass-like material. there is the relatively recent idea of ‘‘rattling’’ scattering or inserting new atoms in open structure or cage-like systems to essentially ‘‘rattle around inside the cages’’ and thus resonantly scatter the heat carrying or acoustic phonons. ‘‘filled’’ skutterudites. In addition. the successful candidate material requires several specific characteristics. In addition.25 eV at 300 K). Slack suggested that the best thermoelectric material would behave as a ‘‘phononglass. Se. the Seebeck 3.e. This gives encouragement that such materials may be possible. In many areas of research related to new TE materials. It is only these elements which have such small electronegativity differences. These quantities must therefore be optimized for good thermoelectric performance. Understanding these various effects. This is being attempted by scattering phonons in different frequency ranges utilizing a variety of methods such as mass fluctuation scattering (a mixed crystal.Thermoelectric Materials: Principles. Sn. as discussed. the PGEC approach may well be the best strategy to employ. such as: Bi. Dw. between the elements of the material must be as small as possible. and selecting optimization strategies can be an exceedingly difficult problem. In general. where a minimum lattice thermal conductivity is achieved (that is. in that s is tied to kE through the Wiedemann–Franz relationship (see Boltzmann Equation and Scattering Mechanisms): kE ¼ L0 sT ð16Þ The ratio is essentially constant at a given temperature. when all the phonons have a mean free path equal to the interatomic spacing of the constituent atoms). grain boundary scattering due to the size of the grains and interface scattering in thin films or multilayer systems. using the Allred scale. i. the mobility of the carriers must remain high. Investigating New Thermoelectric Materials 3.5 per bond on average. Properties. in ternary and quaternary compounds).2 Minimum Thermal Conductivity (kmin) The thermal conductivity of complex materials can often be modified by chemical substitutions or alloy scattering of the phonons. Currently there are no theoretical or thermodynamic limits to the possible values of ZT . Ge. the electronegativity difference. The electrical conductivity and the thermal conductivity are interrelated. Slack estimated that an optimized PGEC material would have values of ZTE4 in the 77–300 K temperature range (Slack 1995). To maintain a high mobility. respectively). The Lorentz number is given by L0 ¼   p2 kB 2 3 e ð17Þ where.45 Â 10À8 W O KÀ2 (or L0 ¼ 2. preferably less than approximately Dwo0. This high ratio of mobility to thermal conductivity imparts certain demands on the structure of the material. Structure. and Applications via quantized vibrations of the lattice called phonons such that k ¼ kL þ kE ð15Þ (where kL and kE are the lattice and electronic contributions. All these demands insure that the structural elements will be drawn from the heavy metal or metalloid set (p-band electrons) of the periodic table. and clathrates. Also. because in complex materials there are often many possible degrees of freedom. electron-crystal’’ (PGEC) that is. etc. while the thermal conductivity has to be low. The aspect of thermal conductivity reduction utilizing the ‘‘rattling’’ scattering in the cage structure will become much clearer when this aspect is discussed in more detail later in this article in relation to classes of materials called skutterudites. many of the compounds formed by these elements are narrow bandgap semiconductors.1 Phonon-glass: Electron-crystal Approach Slack has described the chemical characteristics of materials that might be candidates for a good thermoelectric material (Slack 1995). it can also be detrimental to carrier mobility. a systematic search and subsequent thorough investigation of promising materials might eventually yield these much-needed materials for the next-generation TE devices.

sE225 mV KÀ1. In most materials. At high temperatures (T4E300 K) the sound velocity and the heat capacity are essentially temperature independent in typical materials. 5. Structure. sE1 m O-cm. ‘‘rattlers’’). while the less ordered element rattles around to inhibit phonon conduction. kmin . Possibilities include phonon drag. and Lph is the mean free path of the phonons. 3. in effect is given by minimizing the thermal conductivity. and kE1. Slack introduced the concept of a minimum lattice thermal conductivity (kmin). This analysis is consistent with estimations of practical limits of ZT by both Slack (1995) and Goldsmid (1986). (see Kondo Systems and Heavy Fermions: Transport Phenomena) and material which exhibit phase transitions. on the order of 0. electronic phase transitions. to achieve a ZTE1 at T ¼ 320 K. and at high temperatures. the electrical conductivity and thermopower are related to the electron density of states near the Fermi energy D(EF).5 at 100 K. More recently this concept has been successfully employed to reduce kL in compounds that possess these ‘‘rattling’’ atoms. It was such a recipe. Then we can rewrite Eqn. Given this description. Typical analysis of kmin results in values of kminE0. The framework should be well ordered for the efficient mobility of charge. slightly rearranged (kE/s ¼ L0T. heavy fermion materials.Thermoelectric Materials: Principles. Therefore. Unless. D(E). One example is the skutterudites.5 ¼ 225 mV KÀ1 for a ZT ¼ 2. Slack defined the minimum thermal conductivity. These values will essentially result in a practical limit for new thermoelectric materials. two or more of which form a highly crystalline framework. 4. in order to achieve a certain value of ZT the material would require that a ¼ (L0)0.5 W mÀ1KÀ1. in Bi2Te3. 4 and a summary is given as to why these materials are interesting for potential TE applications in Sect.3 Minimum Thermopower Therefore for a material to be a viable TE material it must possess a minimum thermopower which is directly related to the value of ZT and L0. C is the heat capacity.g. vS is the velocity of sound. at temperatures far from a phase transition. discussed later. Kondo systems.5 W mÀ1KÀ1 (Slack 1995). of course. The There are certain practical limits for each of the parameters used to calculate ZT. the magnitude and the temperature dependence of kL is basically determined by the mean free path of the phonons.5 ¼ 157 mV KÀ1 for a ZT ¼ 1 and a ¼ (2L0)0. Let us look at the hypothetical situation of a material where the lattice 6 . and effectively yields an upper limit of ZTE2 at room temperature. as well as quasi-onedimensional materials. and exotic transport phenomena which can add structure in D(E) near their Fermi energy. Recent Results and Promising Materials 4.1 Complex Chalcogenides One of the important issues relative to the development of low-temperature thermoelectric materials is the identification of mechanisms which might give high thermopower (a) at low temperatures. 3. We have already discussed the ‘‘ZT barrier’’ which. EF. Properties. Low-dimensional systems are known to be susceptible to van Hove singularities (or cusps) in their density of states. These practical limits must be possible in order to achieve a material viable for thermoelectric applications. a ZTE4 may be achievable. It is practical to investigate materials where the electronic and lattice terms are comparable. For example. while maintaining relatively high power factors.75–1 W mÀ1KÀ1. while the third element occupies a site in which it can create localized disorder (e.25–0.45 Â 10À8 V2 KÀ2)) is well behaved in this material. ZTE1.4 Bulk Materials Approach The discussion thus far indicates that new materials must eventually be able to achieve certain minimum values of important parameters to be considered for a potential thermoelectric material. It does not matter if a material has a kLEkmin. as the thermal conductivity when the mean free path is essentially limited by the interatomic distance between the atoms within the crystal (Slack 1979). (3): ZT ¼ a2 sT a2 ¼ kE L0 ð19Þ where. The lattice thermal conductivity is given by: kL EvS CLph ð18Þ thermal conductivity is zero (kL ¼ 0)! We will also assume the scattering in this system is elastic and that the Wiedemann–Franz relationship. If it cannot be ‘‘tuned’’ or doped to attain a minimum thermopower of aE150 mV KÀ1 then it would not be able to achieve a ZTE1. a material is in serious violation of the Wiedemann–Franz relationship.. Some of the materials that are under investigation are highlighted in Sect. Each of the materials under investigation for thermoelectrics has its own set of challenges that must be overcome. which originally led to the correct prediction that filled skutterudites should have good thermoelectric properties (Slack and Tsoukala 1994). and Applications problem due to the fact that in complex materials there are often many possible degrees of freedom. where L0 ¼ Lorentz number (L0E2. the ideal thermoelectric materials will probably be those containing at least three elements. Based on the predictions by Slack.

4 (Caillat et al. have also shown promise as potential lowtemperature thermoelectric materials (Littleton et al. These materials exhibit a ZTE0. as shown in Fig. and could be expected to have a wide range of operating environments. They would be more rugged and easier to prepare than the conventional materials. (E0.6 at TE300 K. To250 K. Properties. Results on a new system of materials grown by the Kanatzidis group at Michigan State University exhibit very promising low-temperature thermoelectric properties and have yielded some of the highest ZT values achieved below TE250 K (Chung et al. The electronic transport properties are typical of a semimetal with low electrical resistivity increasing with increasing temperature (dr/dT 4 0). b-Zn4Sb3 transforms into g-Zn4Sb3. evaluated at E ¼ EF . Hence. The best ZT obtained to date on polycrystalline samples is about 1. This relatively high Seebeck value (for a semimetal) is the result of fairly large effective mass. which results in interplanar scattering for the phonons.4 at 675 K. in fact. which has poorer thermoelectric properties. One aspect of these materials is that they exhibit a very low total thermal conductivity. The figure of merit as a function of temperature is shown in Fig. and found it is nearly temperature independent between 300 K and 650 K. This is similar to the Bi2Te3 system. The compounds contain mixed valence Co ions with itinerant electrons within the layers. The practical use of these materials is limited by the extreme toxicity of the oxides of the Tl. These very low values of kL along with its unusual temperature dependence can be predominantly attributed to the relatively complex crystal structure and to the presence of vacancies in the lattice. as D is increased.Thermoelectric Materials: Principles. This may be an important aspect of future investigations of new materials. however other compounds or derivatives not containing Tl may be possible. 2001). 1998) predict a metallic behavior with improved thermoelectric 7 . 4. These pentatelluride materials exhibit a thermopower that is relatively large over a broad range at low temperatures. especially for power generation applications.8 at TE220 K. Another family of low-dimensional semiconductors or semimetals.65 W mÀ1KÀ1 at 300 K. These materials do. Band structure calculations (Kim et al. exhibit anisotropic transport properties with the high conductivity axis being the growth axis (a-axis) and have a van der Waals gap between the individual layers (perpendicular to the b-axis). 4 for the CsBi4Te6 material.3 Zinc Antimonides (b-Zn4Sb3) b-Zn4Sb3 has been re-investigated for thermoelectric applications by the group at the Jet Propulsion Laboratory (Caillat et al. since typically a 1/T dependence is observed in kL in this temperature range. 1997). They have measured the thermal conductivity of polycrystalline b-Zn4Sb3 samples. with a ZTE0. The Seebeck coefficient also increases with increasing temperature and peaks at 675 K with a value of about 200 mV KÀ1. Above 765 K. These materials are based on CsBi4Te6 and exhibit low-dimensional-anisotropic transport behavior. The materials are members of a large class of layered metal bronzes. However. The class of NaxCo2O4 compounds has displayed surprisingly effective thermoelectric properties (Terasaki et al. b-Zn4Sb3 exhibits values of kLE0. There are many possibilities in this system of materials both in single crystal and polycrystalline form. s typically increases while a decreases. (1999). with the alkali metal ions located within the layers. Quantum well systems take advantage of a low-dimensional character through physical confinement in thin film structures to enhance the electronic properties of a given material (Hicks and Dresselhaus 1993). called pentatellurides (HfTe5 and ZrTe5). 1997). 1997).5 W mÀ1KÀ1) with a lattice thermal conductivity very near that of the estimated minimum thermal The development of air and water-stable refractory metal oxides as thermoelectric materials has potentially numerous advantages over existing hightemperature TE materials. Another group of complex chalcogenides that are of interest are the Tl2SnTe5 and Tl2GeTe5 systems that were identified as potential thermoelectric materials by Sharp et al. The power factor of the Se-doped pentatellurides exceeds that of the optimally doped Bi2Te3 system [(Bi1–xSbx)2(Te1–xSex)3] over the temperature range of measurement. investigations of the thermal conductivity indicate it is too high (kE4–8 W mÀ1KÀ1) for use as a TE material. 2000). wherein the transition metals form edge shared octahedral oxide layers. Structure. cleaving easily along these planes. and Applications conductivity is proportional to D(EF) while a is proportional to   1 dDðE Þ aE D dE E ¼EF ð20Þ conductivity.2 Thermoelectric Oxide Materials (NaxCo2O4) Doping can produce very substantial effects in these types of materials and can drastically change their electronic transport. nearly two times lower than that of Bi2Te3 alloys. This is illustrated more precisely in the Mott relation given below:  2  2    p kB T 1 d s a¼ e s dE E ¼EF 3 ð21Þ 4. This is unusual. and nonstoichiometric amounts of Na þ ions between the layers.

Uher 2000). Unfortunately the thermal conductivity is relatively high for a thermoelectric material (on the order of 10–20 W mÀ1KÀ1) and much of the current and future research is related to reducing the thermal conductivity while maintaining the high power factor. and B is the pnictide element such as P.5Pd0. The skutterudite structure is cubic (with space group Im3) and the unit cell contains eight AB3 groups where A is the transition metal element Ir. The half-Heusler alloys exhibit a high negative thermopower (À40 mV KÀ1 to À250 mV KÀ1) and low electrical resistivity values (0. the smaller more massive ions that are incorporated within the skutterudite voids result in the lowest kL. For example. which is facilitated by the filling of the voids within the structure with small diameter. More loosely bound ‘‘rattlers’’ produce local vibrational modes of lower frequency and are thus more effective in scattering the lowerfrequency. &2CO8Sb24. are small band gap semiconductors with a gap of (EGE0. The other metal and pnictide sites are doped to charge compensate for the additional electrons contributed by the rare earth doping and to enhance the electronic properties. 4.. As. heat-carrying phonons.c.5 Skutterudites 4. &. Further optimization of the thermoelectric properties of these materials seems to be limited considering the difficulties with doping them and the restricted compositional variations possible. In context of the doping scheme for thermoelectrics the general crystal structure of these materials can be best described by the following designation. Nd. The reduction in the thermal conductivity of filled skutterudites is due the dynamic.Thermoelectric Materials: Principles.5 eV).2Sn0. the larger the disorder that is produced and therefore the larger the reduction in the lattice thermal conductivity. on the other hand. little success has been obtained experimentally in optimizing the doping level of this compound.c. Shen et al. with the metal atoms on the corners of the eight ‘‘cubes’’ with six (four atom) Sb rings inside the cubes with two ‘‘voids’’ in the remaining ‘‘cubes’’. The heavier and smaller the ion in the voids. large mass interstitials such as trivalent rare-earth ions (Nolas et al. Half-Heusler alloys have a MgAgAs-type crystal structure. The power factor is much larger at TE700 K where it is over 4 W mÀ1KÀ1 making these materials very attractive for potential power generation considerations.8Pd0. Sm. They further state that possible grain size effects may be able to lower kL even further in concert with previous theoretical predictions (Sharp et al.99Sb0.5Hf0. and Applications performance for lower doping levels. sublattices with one Ni sublattice vacant. The compound b-Zn4Sb3 forms a full range of solid solution with the isostructural compound Cd4Sb3 and further reduction in kL can be obtained for Zn4-xCdxSb3 mixed crystals.5 Ni0. 1999 and references therein. 2001). and Sb. see Fig. or Rh. This concept.4 at TE1000 K as shown by the GM. Co.4 Half-Heusler Alloys Another group of materials.1–0.0 W mÀ1KÀ1 at room temperature for small concentrations of Sb. Heusler alloys (e. as compared with the unfilled IrSb3.2–1. Properties. 4. but these crystals appear to be even less temperature stable than b-Zn4Sb3 itself. Some of the recent investigations have centered around the effect of Sb doping on the Sn site (TiNiSn1-xSbx). which are under investigation as potential thermoelectric materials are the half-Heusler alloys (Poon 2000). MNi2Sn) differ from half-Heusler alloys in having the Ni sublattice fully occupied and are also metallic or half-metallic (see Thermoelectric Devices: Refrigeration and Power Generations With No Moving Parts) and exhibit interesting magnetic properties.01 and 8 Skutterudites are the next class of materials that have received a lot of attention within the TE community since the 1990s. first introduced by Slack. These values are comparable to that of Bi2Te3 alloys. kL.01. (2002) reported the effect of partial substitution of Ni by Pd on the thermoelectric (TE) properties in the ZrNiSn half-Heusler system. 2001). is corroborated by the large atomic displacement parameters (ADPs) . kLE3 W mÀ1KÀ1 in the high ZT sample identified above.99Sb0. Specifically. and Oak Ridge groups.5Hf0. JPL. Hf. with RE ¼ La. a sample of (CeyFe1-y)xCo4-xSb12 exhibited a ZTE1. Earlier results presented on reduction of grain boundary scattering on the lattice thermal conductivity appear to have observed these predicted results (Tritt et al. Shen and co-workers were able to achieve values of kLE2 W mÀ1KÀ1 at TE800 K in a sample of Zr0. This investigation yielded a thermoelectric figure of merit of ZT ¼ 0:7 at TE800 K in a sample of Zr0.5Ni0. The Sb doping leads to a relatively large power factor of 0. This is shown clearly by Nolas and co-workers in an investigation of the thermal conductivity of RECo4Sb9Ge3. However. Structure. forming three interpenetrating f.1–8 mO cm) both of which are necessary for a potential thermoelectric material.5Sn0. This is due in large part to the ability to greatly vary kL. The open square. indicates the presence of two voids in the structure which are typically filled by the rare earth atoms to produce the most pronounced effects on the thermal conductivity reduction. The halfHeusler alloys are intermetallic compounds with the general formula MNiSn where M is a group 4 transition metal (M ¼ Zr. Half-Heusler alloys.g. or ‘‘rattling’’ disorder of the void-filling ions that substantially affect the phonon propagation through the lattice. It contains 32 atoms per unit cell. Ti).

it is still much higher than the estimated minimum thermal conductivity of CoSb3. ADPs have been found to be very useful in thermoelectric materials research (Sales et al. Note that although the Yb0. Metallic variants of these compounds are most readily synthesized. Ba containing Si and Ge type I compounds have shown superconducting properties. thus allowing for a ‘‘rattling’’ mechanism with which to ‘‘tune’’ the thermal conductivity. 2001). kminE0. even higher ZT values may be forthcoming in skutterudite compounds. This study concluded that ‘‘tunneling states’’ as well as ‘‘rattling states’’ are necessary to produce a true glass-like thermal conductivity in these materials. or Sn. which is shown in Fig. The ‘‘rattling’’ motion of the small and massive Yb in the voids of CoSb3 substantially reduces kL in these compounds. or dip. including alkali metal. Ge. atoms that are encapsulated in two different polyhedra and E represents the group 14 elements such as Si. like the skutterudites are also cage-like structures. Room temperature structural refinements from single crystal and powder neutron scattering and x-ray diffraction reveal large atomic displacement parameters (ADPs) for atoms inside the structure of the type I clathrates. The thermal conductivity of the Yb. result in semiconducting behavior. and rare earth atoms. kLo1 W mÀ1KÀ1 (at TE300 K) and the Eu8Ga16Ge30 and Sr8Ga16Ge30 systems exhibited properties of a structural glass while the Ba8Ga16Ge30 system exhibited a temperature dependence consistent with a crystalline material. They are of fundamental interest from the perspective of both bonding and their physical properties. The very low glass-like thermal conductivity found in certain type I clathrate compounds has also attracted interest. with a relatively weak temperature dependence. These materials. Investigations of the TE properties of Yb partially filled skutterudites yielded a figure of merit. which predominantly scatters the highest frequency phonons. Similar results have also been observed in a series of Eu-doped Co-based skutterudites. 2001b. Structure. indicative of resonance scattering.and Eu-filled skutterudites is much lower. A variety of different elements have been encapsulated inside the polyhedra of these structure types.6 Clathrates Another class of materials that is very interesting for thermoelectrics comprises materials called clathrates (e. in that they were low. Sr. Ba) have been performed (Sales et al. 2000). has been replaced by one or more much lower frequency scattering mechanisms. especially for potential thermoelectric applications. These materials have crystal structures closely related to those of type-I and type-II clathrate hydrates such as (Cl2)8(H2O)46 and (CO2)24(H2O)136.. there has been a substantial amount of work on compounds with the type I crystal structure. the semiconductor Sr8Ga16Ge30 exhibits a thermal conductivity of similar magnitude and temperature dependence as that of amorphous materials. but these are relatively new TE materials and much work is ahead.g. The low-temperature (To1K) data indicate a T2 temperature dependence. 2002).19Co4Sb12 specimen has a low thermal conductivity. A similar framework can therefore be built up from elements such as Si. ZT41 at TE600 K (Nolas et al. as compared to that of CoSb3. Nolas et al. where charge compensation is established by substitutionally doping the tetravalent framework atoms with trivalent atoms such as gallium. Ge. For example. alkaline earth. 9 4. or rare earth metal ‘‘guest’’ . The type II structure is represented by the general formula X8Y16E136. and Applications that have been observed in alkaline earth and lanthanide-filled skutterudites.Thermoelectric Materials: Principles. The bonding scheme in the clathrate hydrates is somewhat similar to that of diamond-structured group 14 elements. This was the approach used by Nolas and co-workers in synthesizing polycrystalline semiconducting type I clathrates in order to investigate their transport properties for possible TE applications. Large single crystals have been synthesized by the Oak Ridge group (Sales and co-workers) and extensive investigations of X8Ga16Ge30 (where X ¼ Eu. It is suggested that low-frequency vibrational modes of the ‘‘guest’’ atoms inside their oversized polyhedra are responsible for the large reduction in thermal conductivity in these clathrates. Many different compositions with these two structures are possible. alkaline earth. where it can be lower than that of vitreous silica and very close to that of amorphous germanium. or Sn. Only a 19% Yb in CoSb3 dramatically decreases kL as compared to the ‘‘unfilled’’ compound. 2000b). The scattering of the low-frequency acoustic phonons by the ‘‘rattle’’ modes of the encapsulated Sr atoms results in the low thermal conductivity. The thermal conductivity properties were consistent with those observed earlier. Properties. One of the more interesting properties of the type I clathrates is the very distinct thermal conductivity. It is clear from these results that in the Sr8Ga16Ge30 compound the traditional alloy phonon scattering. where X and Y are alkalimetal. Although these results are encouraging.3 W mÀ1KÀ1. Sr8Ga16Ge30) (Nolas et al. 4 (Lamberton et al. Thus far. This is an indication of localized disorder within these polyhedra beyond typical thermal vibration. The type I structure can then be represented by the general formula X2Y6E46. Ternary type I clathrates. 2000a). Higher temperature data show a minimum. Clathrates with frameworks built up from group 14 atoms have been known since the 1970s based on Na8Si46 and NaxSi136 structures. These materials have yet to exhibit a ZTE1.

Sharp J. at Lincoln Labs on PbTe/PbTeSe quantum dot structures that yield a ZTE0. Rev. Pion. Johnson D. Appl. Wiley-VCH. Kaeser M A. Warrendale. in terms of band structure calculations and modeling. Certainly theoretical guidance. Tritt T M. Tritt T M 1999 Skutterudites: a phonon-glass-electron-crystal approach to advanced thermoelectrics energy conversion applications. not easily found in nature. 12727–31 Kim S-G. Littleton IV R T. Only a small fraction of 10 . Nolas G S 2002 High figure of merit in Eu-filled CoSb3-based skutterudites. pp. New York Nolas G S. Yang J. 1024–8 Goldsmid H J 1986 Electronic Refrigeration. Goldsmid H J 2001a Thermoelectrics: Basic Principles and New Materials Developments. Kolis J W 2001 Effect of Sb substitution on the thermoelectric properties of the Group IV pentatelluride materials M1ÀXYXTe5 (M ¼ Hf. Mater. Dresselhaus M S 1993 Effect of quantum-well structures on the thermoelectric figure of merit.) Organic Superconductors. will be essential to the identification of the most promising materials and compositions. as high as 700 W cmÀ2. 64. 6199–203 Lamberton G A Jr. Mazin II. 77. J. Lett. 136–41 5. Chem. Brazis P. See also: Intermetallic Compounds: Electrical Resistivity. In addition. Thermoelectric Devices: Refrigeration and Power Generations With No Moving Parts. Mater. and speed can lead to enormous applications in a gamut of different technologies. Bibliography Caillat T. Structure. Kanatzidis MG 2000 CsBi4Te6. New York. 4. Magnetocaloric Effect: From Theory to Practice Researchers at the Research Triangle Institute (RTI) have demonstrated a significant enhancement in the thermoelectric figure-of-merit overcoming a major hurdle since the 1960s (Venkatasubramanian et al. However. Uher C. Am. Ketchum D. and Applications 4. Science 287. Vol. Rocci-Lane M. which have been ‘‘floated off’’ the substrate to yield free-standing films. London Harman T. Lett. these thin-film devices are extremely fast acting. Also. Tedstrom R H. 29. Intermediate Valence Systems. To address large-scale refrigeration (home refrigerators) or power generation (automotive or industrial applications) requirements. Phys. there have been reports by Harman et al. 2002). 89. 21. a highperformance thermoelectric material for low-temperature applications.) Encyclopedia of Applied Physics. Korzenski M. PA. Rev. Tritt T M 2000a High figure of merit in ytterbium-filled skutterudite materials. New York. B 57. Phys. rapid yet accurate characterization of materials is also essential to effectively advance this field of research. Sci. Phys. While the thin film results are very exciting they may be most appropriate for small-scale electronic and opto-electronics applications where small heat loads or low levels of power generation are more appropriate. Morelli D T. 101–5 Chung D Y.7 Thin Films Materials Approach these ternary materials have been attempted. These materials exhibited a ZTE2. Sci. as well as the ongoing research on the most promising new materials. Properties. 89–116 Nolas G S. Conclusion From these discussions it is apparent that there are many strategies towards investigating materials in the hope of identifying the next generation TE materials. power density. In: Proc. 691 Nolas G S. Little W A (eds. Appl. 29. 2002 Materials Research Society. Spinger.8 at TE300 K and ZTE2 at TE550 K (Harman et al. Rev. 598–600 Littleton IV R T. 47. B. The combination of performance. Borshchevsky A 1997 Preparation and thermoelectric properties of semiconducting Zn4Sb3. In: Trigg G L. 121104–7 Morelli D T 1997 Thermoelectric devices. Zr and Ti). Bhattacharya S.4. Annu. Vol. within B10 ms. Kannewurf C. given the many materials that are yet to be investigated. 80. 339–54 Nolas G S. Conservative estimates of the thermal conductivity were used in these calculations. there is certainly much more work ahead. These nano-engineered TE devices would offer a high coefficient of performance in solid-state refrigeration as well as allow high cooling power densities to be achieved. 1855–7 Nolas G S. Hogan T. then higher performance bulk materials will have to be developed. Rapid Comm. These materials have been grown as thick films. Singh D J 1998 First-principles study of Zn–Sb thermoelectrics. L1–4 Hicks L D. Rev. Spears D L. The existing bulk TE materials are based on binary compounds and the ternary systems are just beginning to be investigated. Solids 58. 1119–25 Chaiken P M 1990 An introduction to thermopower for those who might want to use it to study organic conductors and superconductors. which were measured to yield these results. Immergut E H (eds. Littleton IV R T. Phys. Bastea M. Kaeser M. Electron. A number of potential materials have been identified and discussed in Sect.Thermoelectric Materials: Principles. 2000). Fleurial J-P. The enhancement is attributed to creating a ‘‘nanoengineered’’ material that is efficient in thermal insulation while remaining a good electrical conductor. Phys. which is a factor of 23 000 better than state-of-the art bulk TE technology. Tritt T M. pp. The thermal insulation arises from a complex localization-like behavior for phonons while the electron transmission is facilitated by optimal choice of band-offsets in these semiconductor heterostructures. In addition. In: Kresin V Z. B. Phys. Plenum Press. Mandrus D G 2002 Thermoelectric materials and devices. Slack G A 2001b Thermoelectric clathrates. Taylor P J. Walsh M P 2000 Thermoelectric quantum-dot superlattices with high ZT. In 2002 none of these materials have as yet displaced the current state-of-the-art materials (Bi2Te3 and SiGe) which have held that distinction since the 1970s. J.

Mahan G D.) 2000a Semiconductors and Semimetals. Phys. San Diego. Poon S J. magnetic tape.) Semiconductors and Semimetals. In: Tritt T M (ed. 1–36 Sharp J W. Mahan G D (eds. magnetic. Proc. Ehrenreich H (eds. 7–12 Tritt T M. Chap. CRC Press. Chap. Proc. Encyclopedia of Materials: Science and Technology ISBN: 0-08-043152-6 pp. Poon S J. 20th Int. Vol. 79. B 63. Lyon H B. No part of this publication may be reproduced. 1–71 Slack G A 1995 New materials and performance limits for thermoelectric cooling. Thermoelectrics. In: Seitz F. 626. pp. Phys. 6. Academic Press. 76. In: Tritt T M (ed. pp. Yang J. 2000 Materials Research Society. 139–254. CRC Press. 478. 1–11 11 . 1276–7 Tritt. Recent Trends in Thermoelectric Materials Research. All rights reserved. 74. Boca Raton. Vol.) Semiconductors and Semimetals. Sasago Y. Appl. 37–76 Rowe D M. Chakoumakos B 1999 Thermoelectric properties of Tl2SnTe5 and Tl2GeTe5. Goldsmid H J 2001 Boundary scattering of phonons and thermoelectric figure of merit.Thermoelectric Materials: Principles. Xia Y. 5. 407–40 Slack G A. Academic Press. pp. Jin R. without permission in writing from the publishers. Academic Press. Uher C 2002 Effects of partial substitution of Ni by Pd on the thermoelectric properties of ZrNiSn-based half-Heusler compounds. Beijing. and transport properties of X8Ga16Ge30 (X ¼ Eu. Phys. Mandrus D 2001 Structural. Warrendale PA Tritt T M. Recent Trends in Thermoelectric Materials Research. B 56. Chap. FL Sales B C. Vol. Bhattacharya S. M. In: Rowe D M (ed. Academic Press. Siivola E. San Diego Venkatasubramanian R. Schujman S B 2000b Semiconducting clathrates: a phonon electron crystal material with potential for thermoelectric applications glass. Hirai T. Colpitts T. 2.) 1998 New material for small-scale thermoelectric refrigeration and power generation applications. Sales B C. IEEE Press. Vol. Warrendale PA Tritt T M. Uchinokura K 1997 Large thermoelectric power in NaCo2O4 single crystals.) Semiconductors and Semimetals. Lett. 69. Recent Trends in Thermoelectric Materials Research. Goto T. Phys. J. Meissner G P. Nature 413. Chap. thermal. stored in any retrieval system or transmitted in any form or by any means: electronic. (eds. 1998 Materials Research Society. Tritt Copyright r 2002 Elsevier Science Ltd. 1665–71 Terasaki I. 4165–7 Slack G A 1979 The thermal conductivity of non-metallic crystals. 34. pp. 69–71 Tritt T M. Vol. electrostatic. 70. Tsoukala V G 1994 Some properties of semiconducting IrSb3. Conf. 1997 Materials Research Society. San Diego. Rev. Turnbull D.) Semiconductors and Semimetals. pp. Vol. R82685–9 Tritt T M 1996 Thermoelectric materials beat the heat. (ed. photocopying. New York. pp. 545. 597–602 T. Ba) single crystals. Phys. Mandrus D G. Appl. Thadhani N 2001 Effect of various grain structures and sizes on the thermal conductivity of Ti-based half-Heusler alloys. mechanical. Ponnambalam V. 255–300 Poon S J 2000 Electronic and thermoelectric properties of halfHeusler alloys. San Diego. Rev. China. Thompson J R. Appl. Proc. FL. Vol. Recent Trends in Thermoelectric Materials Research. PA Uher C 2000 Skutterudites: prospective novel thermoelectrics. Slack G A. Sr. ICT 2001. Boca Raton. Structure. In: Tritt T M (ed. Lett. Mandras D. Academic Press. Chakoumakos B C. San Diego. Kanatzidis M G. Recent Trends in Thermoelectric Materials Research. Chakoumakos B C 2000 Use of atomic displacement parameters in thermoelectric materials research. Warrendale. Mahan G.) 1997 Thermoelectric materials—new directions and approaches. 69. Science 272. In: Tritt T M (ed. Vol. Physica Status Solidi (a) 187. 70. Academic Press. Vol. Chen L. pp. Mandrus D G. 1. and Applications Nolas G S. Properties. Kanatzidis M G. recording or otherwise.) 1995 CRC Handbook of Thermoelectrics.) Solid State Physics. Lyon H B. T M (ed.) CRC Handbook of Thermoelectrics. O’Quinn B C 2002 Thin-film thermoelectric devices with high room temperature figures of merit. Kanatzidis M G (eds. Nolas G S. 507–16 Shen Q. 245113–21 Sales B C. Proc. 3794–6 Sharp J W.) 2000b New materials for small-scale thermoelectric refrigeration and power generation applications.