The Criteria for Beneficial Disorder in Thermoelectric Solid Solutions

Forming solid solutions has long been considered an effective approach for good thermoelectrics because the lattice thermal conductivities are lower than those of the constituent compounds due to phonon scattering from disordered atoms. However, this effect could also be compensated by a reduction in carrier mobility due to electron scattering from the same disorder. Using a detailed study of n‐type (PbTe)_1–x (PbSe)_x solid solution (0 ≤ x ≤ 1) as a function of composition, temperature, and doping level, quantitative modeling of transport properties reveals the important parameters characterizing these effects. Based on this analysis, a general criterion for the improvement of zT due to atomic disorder in solid solutions is derived and can be applied to several thermoelectric solid solutions, allowing a convenient prediction of whether better thermoelectric performance could be achieved in a given solid solution. Alloying is shown to be most effective at low temperatures and in materials that are unfavorable for thermoelectrics in their unalloyed forms: high lattice thermal conductivity (stiff materials with low Grüneisen parameters) and high deformation potential.     

Improved Thermoelectric Properties in Ga2Te3-GaSb Vacancy Compounds

Thermoelectric materials with high figure of merit, which requires large Seebeck coefficient, large electrical conductivity, and low thermal conductivity, are of great importance in solid-state cooling and power generation. Solid-solution formation is one effective method to achieve low thermal conductivity by phonon scattering due to mass and strain field fluctuations. This type of scattering is maximized in structures containing vacancies. The thermoelectric properties of Ga₂Te₃-GaSb vacancy compounds were studied in this work. We find that the lattice thermal conductivity is reduced by over an order of magnitude with the addition of only very moderate amounts of Ga₂Te₃. Additionally, both the carrier type and concentration can be modified. While the vacancy structure induced by Ga₂Te₃ addition to GaSb can effectively reduce phonon conductivity, carrier mobility is also degraded, and optimized thermoelectric properties require careful control of the vacancy content in these solid solutions.     

Electrical and Thermal Transport Properties of Ge1–xPbxCuySbyTeSe2y

Balancing the contradictory relationship between thermoelectric parameters, such as effective mass and carrier mobility, is a challenge to optimize thermoelectric performance. Herein, the exceptional thermoelectric performance is realized in GeTe through collaboratively optimizing the carrier and phonon transport via stepwise alloying Pb and CuSbSe₂. The formation energy of Ge vacancy is efficiently bolstered by alloying Pb, which reduces carrier density and carrier scattering to maintain superior carrier mobility in GeTe. Additionally, CuSbSe₂, acting as an n-type dopant, further modulates carrier density and validly equilibrates carrier mobility and effective mass. Accordingly, the promising power factor of 45 µW cm⁻¹ K⁻² is achieved at 723 K. Meanwhile, point defects are found to significantly suppress phonons transport to descend lattice thermal conductivity by Pb and CuSbSe₂ alloying, which barely impacts the carrier mobility. A combination with superior carrier mobility and lower lattice thermal conductivity, a maximum ZT of 2.2 is attained in Ge_0.925Pb_0.075Cu_0.005Sb_0.005TeSe_0.01, which corresponds to a 100% promotion compared with that of intrinsic GeTe. This study provides a new indicator for optimizing carrier and phonon transport properties by balancing interrelated thermoelectric parameters.     

Analysis of Phase Separation in High Performance PbTe–PbS Thermoelectric Materials

Phase immiscibility in PbTe–based thermoelectric materials is an effective means of top‐down synthesis of nanostructured composites exhibiting low lattice thermal conductivities. PbTe_1‐x S_x thermoelectric materials can be synthesized as metastable solid solution alloys through rapid quenching. Subsequent post‐annealing induces phase separation at the nanometer scale, producing nanostructures that increase phonon scattering and reduce lattice thermal conductivity. However, there has yet to be any study investigating in detail the local chemical structure of both the solid solution and nanostructured variants of this material system. Herein, quenched and annealed (i.e., solid solution and phase‐separated) samples of PbTe–PbS are analyzed by in situ high‐resolution synchrotron powder X‐ray diffraction, solid‐state ¹²⁵Te nuclear magnetic resonance (NMR), and infrared (IR) spectroscopy analysis. For high concentrations of PbS in PbTe, e.g., x >16%, NMR and IR analyses reveal that rapidly quenched samples exhibit incipient phase separation that is not detected by state‐of‐the‐art synchrotron X‐ray diffraction, providing an example of a PbTe thermoelectric “alloy” that is in fact phase inhomogeneous. Thermally‐induced PbS phase separation in PbTe–PbS occurs close to 200 °C for all compositions studied, and the solubility of the PbS phase in PbTe at elevated temperatures >500 °C is reported. The findings of this study suggest that there may be a large number of thermoelectric alloy systems that are phase inhomogeneous or nanostructured despite adherence to Vegard's Law of alloys, highlighting the importance of careful chemical characterization to differentiate between thermoelectric alloys and composites.     

Enhancement of Thermoelectric Figure‐of‐Merit by a Bulk Nanostructuring Approach

Recently a significant figure‐of‐merit (ZT) improvement in the most‐studied existing thermoelectric materials has been achieved by creating nanograins and nanostructures in the grains using the combination of high‐energy ball milling and a direct‐current‐induced hot‐press process. Thermoelectric transport measurements, coupled with microstructure studies and theoretical modeling, show that the ZT improvement is the result of low lattice thermal conductivity due to the increased phonon scattering by grain boundaries and structural defects. In this article, the synthesis process and the relationship between the microstructures and the thermoelectric properties of the nanostructured thermoelectric bulk materials with an enhanced ZT value are reviewed. It is expected that the nanostructured materials described here will be useful for a variety of applications such as waste heat recovery, solar energy conversion, and environmentally friendly refrigeration.     

The effects of quaternary additions on thermoelectric properties of TiNiSn-based half-heusler alloys

Half-Heusler-type compounds have gained increasing attention as promising thermoelectric materials. In the present work, a focus is placed on TiNiSn with additions of Hf, Zr, Si, or Pt. Nominally stoichiometric TiNiSn alloys were prepared using arc melting and subsequent annealing at 1,073 K for 2 weeks. The thermoelectric properties, such as thermoelectric power, electrical resistivity, and thermal conductivity, were measured in a temperature range from 300 K to 1,000 K. As-cast materials show metallic transport properties, while annealed ones exhibit semiconductor behavior. Microstructures of TiNiSn alloys basically consist of nonequilibrium four-phase; half-Heusler TiNiSn, Heusler TiNi₂Sn, metallic Ti₆Sn₅, and Sn solid solution. The volume fraction of the half-Heusler TiNiSn phase significantly increases by annealing. It is revealed that coexisting metallic phases degrade the thermoelectric properties of half-Heusler TiNiSn. Alloy additions strongly affect not only thermoelectric properties but also phase stability. The thermal conductivity of TiNiSn alloys with alloy additions decreases because of the point-defect phonon scattering.     

High-Density Frenkel Defects as Origin of N-Type Thermoelectric Performance and Low Thermal Conductivity in Mg3Sb2-Based Materials

Mg₃Sb₂-based intermetallic compounds with exceptionally high thermoelectric performance exhibit unconventional n-type dopability and anomalously low thermal conductivity, attracting much attention to the underlying mechanisms. To date, investigations have been limited to first-principle calculations and thermodynamic analysis of defect formation, and detailed experimental analysis on crystal structure and phonon modes has not been achieved. Here, a synchrotron X-ray diffraction study clarifies that, against a previous view of a simple crystal structure with a small unit cell, Mg₃Sb₂ is inherently a heavily disordered material with Frenkel defects, charge-neutral defect complexes of cation vacancies and interstitials. Ionic charge neutrality preserved in Mg₃Sb₂ is responsible for exotic n-type dopability, which is unachievable for other Zintl phase materials. The thermal conductivity of Mg₃Sb₂ exhibits deviation from the standard T⁻¹ temperature dependency with strongly limited phonon transport due to a strain field. Inelastic X-ray scattering measurement reveals enhanced phonon scattering induced by disorder. The results will draw renewed attention to crystal defects and disorder as means to explore new high-performance thermoelectric materials.     

Vacancy Manipulation Induced Optimal Carrier Concentration,Band Convergence and Low Lattice Thermal Conductivity in Nano-Crystalline SnTe Yielding Superior Thermoelectric Performance

Synergetic optimization of electrical and thermal transport properties is achieved for SnTe-based nano-crystalline materials. Gd doping is able to suppress the Sn vacancy, which is confirmed by positron annihilation measurements and corresponding theoretical calculations. Hence, the optimal hole carrier concentration is obtained, leading to the improvement of electrical transport performance and simultaneous decrease of electronic thermal conductivity. In addition, the incremental density of states effective mass m* in SnTe is realized by the promotion of the band convergence via Gd doping, which is further confirmed by the band structure calculation. Hence, the enhancement of the Seebeck coefficient is also achieved, leading to a high power factor of 2922 µW m⁻¹ K⁻² for Sn_0.96Gd_0.04Te at 900 K. Meanwhile, substantial suppression of the lattice thermal conductivity is observed in Gd-doped SnTe, which is originated from enhanced phonon scattering by multiple processes including mass and strain fluctuations due to the Gd doping, scattering of grain boundaries, nano-pores, and secondary phases induced by Gd doping. With the decreased phonon mean free path and reduced average phonon group velocity, a rather low lattice thermal conductivity is achieved. As a result, the synergetic optimization of the electric and thermal transport properties contributes to a rather high ZT value of ≈1.5 at 900 K, leading to the superior thermoelectric performance of SnTe-based nanoscale polycrystalline materials.     

Oxide Thermoelectric Materials: A Structure–Property Relationship

Recent demand for thermoelectric materials for power harvesting from automobile and industrial waste heat requires oxide materials because of their potential advantages over intermetallic alloys in terms of chemical and thermal stability at high temperatures. Achievement of thermoelectric figure of merit equivalent to unity (ZT ≈ 1) for transition-metal oxides necessitates a second look at the fundamental theory on the basis of the structure–property relationship giving rise to electron correlation accompanied by spin fluctuation. Promising transition-metal oxides based on wide-bandgap semiconductors, perovskite and layered oxides have been studied as potential candidate n- and p-type materials. This paper reviews the correlation between the crystal structure and thermoelectric properties of transition-metal oxides. The crystal-site-dependent electronic configuration and spin degeneracy to control the thermopower and electron–phonon interaction leading to polaron hopping to control electrical conductivity is discussed. Crystal structure tailoring leading to phonon scattering at interfaces and nanograin domains to achieve low thermal conductivity is also highlighted.     

Graphene/Strontium Titanate: Approaching Single Crystal–Like Charge Transport in Polycrystalline Oxide Perovskite Nanocomposites through Grain Boundary Engineering

Grain boundaries critically limit the electronic performance of oxide perovskites. These interfaces lower the carrier mobilities of polycrystalline materials by several orders of magnitude compared to single crystals. Despite extensive effort, improving the mobility of polycrystalline materials (to meet the performance of single crystals) is still a severe challenge. In this work, the grain boundary effect is eliminated in perovskite strontium titanate (STO) by incorporating graphene into the polycrystalline microstructure. An effective mass model provides strong evidence that polycrystalline graphene/strontium titanate (G/STO) nanocomposites approach single crystal‐like charge transport. This phenomenological model reduces the complexity of analyzing charge transport properties so that a quantitative comparison can be made between the nanocomposites and STO single crystals. In other related works, graphene composites also optimize the thermal transport properties of thermoelectric materials. Therefore, decorating grain boundaries with graphene appears to be a robust strategy to achieve “phonon glass–electron crystal” behavior in oxide perovskites.     

Origin of Phonon Glass–Electron Crystal Behavior in Thermoelectric Layered Cobaltate

Measurement of local disorder and lattice vibrations is of great importance for understanding the mechanisms whereby thermoelectric materials efficiently convert heat to electricity. Attaining high thermoelectric power requires minimizing thermal conductivity while keeping electric conductivity high. This situation is achievable by enhancing phonon scattering through specific structural disorder (phonon glass) that also retains sufficient electron mobility (electron crystal). It is demonstrated that the quantitative acquisition of multiple annular‐dark‐field images via scanning transmission electron microscopy at different scattering‐angles simultaneously allows not only the separation but also the accurate determination of static and thermal atomic displacements in crystals. Applying the unique method to the layered thermoelectric material (Ca₂CoO₃)_0.62CoO₂ discloses the presence of large incommensurate displacive modulation and enhanced local vibration of atoms, largely confined within its Ca₂CoO₃ sublayers. Relating the refined disorder to ab initio calculations of scattering rates is a tremendeous challenge. Based on an approximate calculation of scattering rates, it is suggested that this well‐defined deterministic disorder engenders static displacement‐induced scattering and vibrational‐induced resonance scattering of phonons as the origin of the phonon glass. Concurrently, the crystalline CoO₂ sublayers provide pathways for highly conducting electrons and large thermal voltages.     

Inorganic Colloidal Solution-Based Approach to Nanocrystal Synthesis of (Bi,Sb)2Te3

There is an interest in higher-ZT thermoelectric materials for high-watt-density cooling of electronics. Reducing thermal conductivity through increased phonon scattering in nanomaterials has been shown to be effective and is being investigated by many groups. Solution-based synthesis is a method for making thermoelectric nanomaterials that can provide particle sizes <20?nm and can be scaled to production quantities of materials. We are exploring an approach that proceeds through formation of an ??ink?? that contains inorganic colloidal nanocrystals of thermoelectric materials. This approach has the advantage that, by adjustments within the basic synthesis process, the size, shape, and composition of the nanocrystals can be tightly controlled to study changes in the transport properties. Currently we are making materials from inks that contain Bi₂Te₃ nanocrystals with Sb₂Te₃ ligands, suspended in a solvent. Powders formed by curing the inks are made into solid pellets by hot pressing, and the pellets are used for characterization and transport property measurements. The best result from our thermoelectric property measurements is ZT?=?0.9 with power factor of 27???W/cm?K², which to our knowledge is the best value for solution-based synthesis.     

Bulk Nanostructured Thermoelectric Materials: Preparation,Structure and Properties

Bulk nanostructured materials have recently emerged as a new paradigm for improving the performance of existing thermoelectric materials. Here, we fabricated two kinds of bulk nanostructured thermoelectric materials by a bottom-up strategy and an in situ precipitation method, respectively. Binary PbTe was fabricated by a combination of chemical synthesis and hot pressing. The grain sizes of the hot pressed bulk samples varied from 200 nm to 400 nm, which significantly contributed to the reduction of thermal conductivity due to the enhanced boundary phonon scattering. The highest figure of merit ZT of the binary PbTe sample reached 0.8 at 580 K. Mg₂(Si,Sn) solid solutions have shown great promise for thermoelectric application, due to good thermoelectric properties, non-toxicity, and abundantly available constituent elements. The nanoscale microstructure observation of the compounds showed the existence of nanophases formed in situ, which is believed to be related to the relatively low lattice thermal conductivity in this material system. The highest ZT of Sb-doped Mg₂(Si,Sn) samples reached 1.1 at 770 K.     

Thermal Conductivity and Phonon Scattering Processes of ALD Grown PbTe–PbSe Thermoelectric Thin Films

This work studies the thermal conductivity and phonon scattering processes in a series of n‐type lead telluride‐lead selenide (PbTe–PbSe) nanostructured thin films grown by atomic layer deposition (ALD). The ALD growth of the PbTe–PbSe samples in this work results in nonepitaxial films grown directly on native oxide/Si substrates, where the Volmer–Weber mode of growth promotes grains with a preferred columnar orientation. The ALD growth of these lead‐rich PbTe, PbSe, and PbTe–PbSe thin films results in secondary oxide phases, along with an increase microstructural quality with increased film thickness. The compositional variation and resulting point and planar defects in the PbTe–PbSe nanostructures give rise to additional phonon scattering events that reduce the thermal conductivity below that of the corresponding ALD‐grown control PbTe and PbSe films. Temperature‐dependent thermal conductivity measurements show that the phonon scattering in these ALD‐grown PbTe–PbSe nanostructured materials, along with ALD‐grown PbTe and PbSe thin films, are driven by extrinsic defect scattering processes as opposed to phonon–phonon scattering processes intrinsic to the PbTe or PbSe phonon spectra. The implication of this work is that polycrystalline, nanostructured ALD composites of thermoelectric PbTe–PbSe films are effective in reducing the phonon thermal conductivity, and represent a pathway for further improvement of the figure of merit (ZT), enhancing their thermoelectric application potential.     

Thermoelectric Properties of <Emphasis Type="Italic">n</Emphasis>-Type Multiple-Filled Skutterudites

Filled skutterudites are prospective intermediate temperature materials for␣thermoelectric power generation. CoSb₃-based n-type filled skutterudites have good electrical transport properties with power factor values over 40 μW/cm K² at elevated temperatures. Filling multiple fillers into the crystallographic voids of skutterudites would help scatter a broad range of lattice phonons, thus resulting in lower lattice thermal conductivity values. We report the thermoelectric properties of n-type multiple-filled skutterudites between 5 K and 800 K. The combination of different fillers inside the voids of the skutterudite structure shows enhanced phonon scattering, and consequently a strong suppression of the lattice thermal conductivity. Very good power factor values are achieved in multiple-filled skutterudite compared with single-element-filled materials. The dimensionless thermoelectric figure of merit for n-type filled skutterudites is improved through multiple-filling in a wide temperature range.     

Electron mobility in an AlGaN/GaN two-dimensional electron gas. I. Carrier concentration dependent mobility

The transport properties of two-dimensional electron gas (2-DEG) at the AlGaN/GaN interface were studied by characterizing the 2-DEG mobility dependence on carrier concentration, n/sub s/, and temperature. High-quality AlGaN/GaN heterostructures were grown, and heterostructure field effect transistors (HFETs) using a Fat FET geometry were fabricated. Measurements of 2-DEG mobility were performed by magnetoresistance and capacitance-conductance. In order to understand the dominant transport factors, the mobility was modeled using different scattering mechanisms and compared to our results. It is found that mobility dependence on n/sub s/ shows a bell-shape behavior over the whole temperature range. For low n/sub s/ the mobility is dominated by Coulomb interaction from interface charge, and at high n/sub s/ the mobility is dominated by interface roughness. Using previously reported experimental values of interface charge and interface roughness in our modeling, we show good agreement with mobility measurement results. Scattering from interface states in AlGaN/GaN heterostructures, seems to be related to the high polarization field in the heterointerface. At temperatures higher than 200K polar optical phonon scattering dominates the transport, yet both interface charge and roughness affect the mobility at the low and high n/sub s/, respectively.     

Thermoelectric Properties of Scaled Silicon Nanowires Using the sp3d?5s*-SO Atomistic Tight-Binding Model and Boltzmann Transport

As a result of suppressed phonon conduction, large improvements of the thermoelectric figure of merit, ZT, have been recently reported for nanostructures compared with the raw materials’ ZT values. It has also been suggested that low dimensionality can improve a device’s power factor as well, offering a further enhancement. In this work the atomistic sp ³ d ⁵ s*-spin–orbit-coupled tight-binding model is used to calculate the electronic structure of silicon nanowires (NWs). Linearized Boltzmann transport theory is applied, including all relevant scattering mechanisms, to calculate the electrical conductivity, the Seebeck coefficient, and the thermoelectric power factor. We examine n-type NWs of diameter 3 nm and 12 nm, in [100], [110], and [111] transport orientations, at different carrier concentrations. Using experimental values for the lattice thermal conductivity in NWs, the expected ZT value is computed. We find that, at room temperature, although scaling the diameter below 7 nm can be beneficial to the power factor due to band structure changes alone, at those dimensions enhanced phonon and surface roughness scattering (SRS) degrade the conductivity and reduce the power factor.     

In Situ Design of High-Performance Dual-Phase GeSe Thermoelectrics by Tailoring Chemical Bonds

Composite engineering favors high thermoelectric performance by tuning the carrier and phonon transport. Herein, orthorhombic and rhombohedral dual-phase GeSe are designed in situ by tailoring chemical bonds. Atom probe tomography verifies the coexistence of a covalently bonded orthorhombic phase and a metavalently bonded rhombohedral phase in GeSe-InTe alloys. The production of the rhombohedral phase simultaneously increases the carrier concentration, the carrier mobility, the band degeneracy, and the density-of-states effective mass due to the reduced formation energy of cation vacancies and the improved crystal symmetry. These attributes are beneficial to a high-power factor. In addition, the thermal conductivity can be significantly reduced due to the intrinsically strong lattice anharmonicity of the metavalently bonded phase, the interfacial acoustic phonon mismatch across different bonding mechanisms, and the phonon scattering at vacancy-solute clusters. Moreover, the metavalently bonded phase embraces higher solubility of dopants that enables the further optimization of properties by Cd-Ag doping, resulting in a zT of 0.95 at 773 K as well as enhanced strength and ductility in dual-phase Ge_0.94Cd_0.03Ag_0.03Se(InTe)_0.15. This work indicates that in situ design of dual-phase composites by tailoring chemical bonds is an effective method for enhancing the thermoelectric and mechanical properties of GeSe and other p-bonded chalcogenides.     

On Intensifying Carrier Impurity Scattering to Enhance Thermoelectric Performance in Cr‐Doped CeyCo4Sb12

The beneficial effect of impurity scattering on thermoelectric properties has long been disregarded even though possible improvements in power factor have been suggested by Ioffe more than a half century ago. Here it is theoretically and experimentally demonstrated that proper intensification of ionized impurity scattering to charge carriers can benefit the thermoelectric figure of merit (ZT) by increasing the Seebeck coefficient and decreasing the electronic thermal conductivity. The optimal strength of ionized impurity scattering for maximum ZT depends on the Fermi level and the density of states effective mass. Cr‐doping in Ce_yCo₄Sb₁₂ progressively increases the strength of ionized impurity scattering, and significantly improves the Seebeck coefficient, resulting in high power factors of 45 μW cm^?1 K^?2 with relatively low electrical conductivity. This effect, combined with the increased Ce‐filling fraction and thus decreased lattice thermal conductivity by charge compensation of Cr‐dopant, gives rise to a maximum ZT of 1.3 at 800 K and a large average ZT of 1.1 between 500 and 850 K, ≈30% and ≈20% enhancements as compared with those of Cr‐free sample, respectively. Furthermore, this study also reveals that carrier scattering parameter can be another fundamental degree of freedom to optimize electrical properties and improve thermal‐to‐electricity conversion efficiencies of thermoelectric materials.     

Tin telluride based thermoelectrical alloys

The effect on the Hall hole concentration and the thermoelectric coefficient of various elemental impurities in SnTe containing excess Te and in some solid solutions based on it is investigated in the temperature interval 300–900 K. The variation of the kinetic parameters is treated on the basis of the concept of resonance states bound to cation vacancies and to the impurities determining the hole concentration. The low values of the thermoelectric coefficient in SnTe is explained by selectivity of scattering of charge carriers with more probable transition of the holes to the resonance states and vice versa. In isomorphic solid solutions based on SnTe, because of a shift in the energy position of the resonance states relative to the band edges and the Fermi level, it is possible to alter the nature of the resonance scattering and raise the thermoelectric coefficient to values which are optimal from the standpoint of obtaining maximum thermoelectric efficiency. In solid solutions of chalcogenides of group-IV elements with SnTe content about 40 mol% of the dimensionless parameter of thermoelectric efficiency ZT=1 at temperatures above 700 K. Fiz. Tekh. Poluprovodn. 32, 268–271 (March 1998)