Effect of Ca Doping on the Thermoelectric Performance of Yb<Subscript>14</Subscript>MnSb<Subscript>11</Subscript>

Complex Zintl phases possess low thermal conductivity and can be easily doped to modify the transport properties. Therefore, these phases have the potential to be good thermoelectric materials by simply controlling carrier concentration. Yb₁₄MnSb₁₁ is a Zintl phase that has shown promise as a p-type thermoelectric material for high-temperature power generation. A Sn-flux synthetic route was used to make the new phase, Yb₁₃CaMnSb₁₁. The high-temperature thermoelectric properties were measured on polycrystalline hot-pressed pellets and compared with Yb₁₄MnSb₁₁. Substitution of the lighter isovalent Ca for Yb should reduce the lattice thermal conductivity by mass disorder scattering, and a noticeable reduction is seen in thermal diffusivity measurements at high temperature. There may also be a carrier concentration effect by employing the more electropositive Ca.     

Zintl Phases as Thermoelectric Materials: Tuned Transport Properties of the Compounds CaxYb1–xZn2Sb2

Zintl phases are ideal candidates for efficient thermoelectric materials, because they are typically small‐bandgap semiconductors with complex structures. Furthermore, such phases allow fine adjustment of dopant concentration without disrupting electronic mobility, which is essential for optimizing thermoelectric material efficiency. The tunability of Zintl phases is demonstrated with the series Ca_xYb_1–xZn₂Sb₂ (0 ≤ x ≤ 1). Measurements of the electrical conductivity, Hall mobility, Seebeck coefficient, and thermal conductivity (in the 300–800 K temperature range) show the compounds to behave as heavily doped semiconductors, with transport properties that can be systematically regulated by varying x. Within this series, x = 0 is the most metallic (lowest electrical resistivity, lowest Seebeck coefficient, and highest carrier concentration), and x = 1 is the most semiconducting (highest electrical resistivity, highest Seebeck coefficient, and lowest carrier concentration), while the mobility is largely independent of x. In addition, the structural disorder generated by the incorporation of multiple cations lowers the overall thermal conductivity significantly at intermediate compositions, increasing the thermoelectric figure of merit, zT. Thus, both zT and the thermoelectric compatibility factor (like zT, a composite function of the transport properties) can be finely tuned to allow optimization of efficiency in a thermoelectric device.     

In?Situ Growth of a Yb2O3 Layer for Sublimation Suppression for Yb14MnSb11 Thermoelectric Material for Space Power Applications

The compound Yb₁₄MnSb₁₁ is a p-type thermoelectric material of interest to the National Aeronautics and Space Administration (NASA) as a candidate replacement for the state-of-the-art Si-Ge used in current radioisotope thermoelectric generators (RTGs). Ideally, the hot end of this leg would operate at 1000°C in the vacuum of space. Although Yb₁₄MnSb₁₁ shows the potential to double the value of the thermoelectric figure of merit (zT) over that of Si-Ge at 1000°C, it suffers from a high sublimation rate at elevated temperatures and would require a coating in order to survive the required RTG lifetime of 14?years. The purpose of the present work is to measure the sublimation rate of Yb₁₄MnSb₁₁ and to investigate sublimation suppression for this material. This paper reports on the sublimation rate of Yb₁₄MnSb₁₁ at 1000°C (??3?×?10^?3?g/cm²?h) and efforts to reduce the sublimation rate with an in?situ grown Yb₂O₃ layer. Despite the success in forming thin, dense, continuous, and adherent oxide scales on Yb₁₄MnSb₁₁, the scales did not prove to be sublimation barriers.     

Crystal Structure and High-Temperature Thermoelectric Properties of the Mo<Subscript>3−<Emphasis Type="Italic">x</Emphasis></Subscript>Ru<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Sb<Subscript>7</Subscript> Compounds

Zintl phases are currently receiving great attention for their thermoelectric potential typified by the discovery of a high ZT value in Yb₁₄MnSb₁₁-based compounds. Herein, we report on the crystallographic characterization via neutron and x-ray diffraction experiments, and on the thermoelectric properties measured in the 300 K to 1000 K temperature range, of Mo₃Sb₇ and its isostructural compounds Mo_3−x Ru _x Sb₇. Even though Mo₃Sb₇ displays rather high ZT values given its metallic character, the partial substitution of Mo by Ru substantially improves its thermoelectric properties, resulting in a ZT value of ∼0.45 at 1000 K for x = 0.8.     

Enhanced Thermoelectric Performance in 18‐Electron Nb0.8CoSb Half‐Heusler Compound with Intrinsic Nb Vacancies

Typical 18‐electron half‐Heusler compounds, ZrNiSn and NbFeSb, are identified as promising high‐temperature thermoelectric materials. NbCoSb with nominal 19 valence electrons, which is supposed to be metallic, is recently reported to also exhibit thermoelectric properties of a heavily doped n‐type semiconductor. Here for the first time, it is experimentally demonstrated that the nominal 19‐electron NbCoSb is actually the composite of 18‐electron Nb_0.8+δCoSb (0 ≤ δ < 0.05) and impurity phases. Single‐phase Nb_0.8+δCoSb with intrinsic Nb vacancies, following the 18‐electron rule, possesses improved thermoelectric performance, and the slight change in the content of Nb vacancies has a profound effect on the thermoelectric properties. The carrier concentration can be controlled by varying the Nb deficiency, and the optimization of the thermoelectric properties can be realized within the narrow pure phase region. Benefiting from the elimination of impurity phases and the optimization of carrier concentration, thermoelectric performance is remarkably enhanced by ≈100% and a maximum zT of 0.9 is achieved in Nb_0.83CoSb at 1123 K. This work expands the family of half‐Heusler thermoelectric materials and opens a new avenue for searching for nominal 19‐electron half‐Heusler compounds with intrinsic vacancies as promising thermoelectric materials.     

High Thermoelectric Performance in Sulfide‐Type Argyrodites Compound Ag8Sn(S1−xSex)6 Enabled by Ultralow Lattice Thermal Conductivity and Extended Cubic Phase Regime

Argyrodites with a general chemical formula of A₈BC₆ are known for complex phase transitions, ultralow lattice thermal conductivity, and mixed electronic and ionic conduction. The coexistence of ionic conduction and promising thermoelectric performance have recently been reported in selenide and telluride argyrodites, but scarcely in sulfide argyrodites. Here, the thermoelectric properties of Ag₈Sn(S_1?xSe_x)₆ are reported. Specifically, Ag₈SnS₆ exhibits intrinsically ultralow lattice thermal conductivities of 0.61–0.31 W m^?1 K^?1 over the whole temperature range from 32 to 773 K due to distorted local crystal structure, relatively weak chemical bonding, rattler‐like Ag atoms, low‐lying optical modes, and dynamic disorder of Ag ions at high temperatures. Se doping shifts the orthorhombic–cubic phase transition from 457 K at x = 0 to 430 K at x = 0.10, thereby expanding the temperature range of the thermoelectrically favored cubic phase. A figure of merit zT value ≈ 0.80 is achieved at 773 K in Ag₈Sn(S_1?xSe_x)₆ (x = 0.03), the highest zT value reported in sulfide argyrodites. These results fill a knowledge gap of the thermoelectric study of argyrodites and contribute to a comprehensive understanding of the chemical bonding, lattice dynamics, and thermal transport of argyrodites.     

The Zintl Compound Ca5Al2Sb6 for Low‐Cost Thermoelectric Power Generation

Understanding transport in Zintl compounds is important due to their unusual chemistry, structural complexity, and potential for good thermoelectric performance. Resistivity measurements indicate that undoped Ca₅Al₂Sb₆ is a charge‐balanced semiconductor with a bandgap of 0.5 eV, consistent with Zintl–Klemm charge counting rules. Substituting divalent calcium with monovalent sodium leads to the formation of free holes, and a transition from insulating to metallic electronic behavior is observed. Seebeck measurements yield a hole mass of ～2m_e, consistent with a structure containing both ionic and covalent bonding. The structural complexity of Zintl compounds is implicated in their unusually low thermal conductivity values. Indeed, Ca₅Al₂Sb₆ possesses an extremely low lattice thermal conductivity (0.6 W mK^?1 at 850 K), which approaches the minimum thermal conductivity limit at high temperature. A single parabolic band model is developed and predicts that Ca_4.75Na_0.25Al₂Sb₆ possesses a near‐optimal carrier concentration for thermoelectric power generation. A maximum zT > 0.6 is obtained at 1000 K.Beyond thermoelectric applications, the semiconductor Ca₅Al₂Sb₆ possesses a 1D covalent structure which should be amenable to interesting magnetic interactions when appropriately doped.     

Significantly Enhanced Thermoelectric Performance in n‐type Heterogeneous BiAgSeS Composites

High performance n‐type bulk BiAgSeS is successfully synthesized to construct heterogeneous composites which consist of mesoscale grains of both pristine BiAgSeS and doped BiAgSeS_1‐xCl_x ( x = 0.03 or 0.05). Without perceptibly deteriorating the Seebeck coefficient, a significant enhancement on electrical conductivity is obtained due to an anomalous increase of both carrier mobility and concentration; the enhanced carrier mobility is proven to be a direct result of modulation doping which relates to the band alignments, while the increased carrier concentration is attributed to the possible charge transfer from Cl rich nanoscale precipitates at the heterogeneous BiAgSeS/BiAgSeS_1‐xCl_x grain boundaries. Eventually, an enhanced figure of merit ZT ≈ 1.23 at 773 K in the composite (BiAgSeS)_0.5(BiAgSeS_0.97Cl_0.03)_0.5 is achieved, indicating that heterogeneous composites ultilizing the mechanism of modulation doping shall be a promising means of boosting the performance of thermoelectric materials. This strategy should be very likely applicable to other thermoelectrics.     

Enhancing the Thermoelectric Properties via Modulation of Defects in P-Type MNiSn-Based (M = Hf,Zr, Ti) Half-Heusler Materials

The thermoelectric figure-of-merit (zT) of p-type MNiSn (M = Ti, Zr, or Hf) half-Heusler compounds is lower than their n-type counterparts due to the presence of a donor in-gap state caused by Ni occupying tetrahedral interstitials. While ZrNiSn and TiNiSn, have been extensively studied, HfNiSn remains unexplored. Herein, this study reports an improved thermoelectric property in p-type HfNi_1−xCo_xSn. By doping 5 at% Co at the Ni sites, the Seebeck coefficient becomes reaching a peak value exceeding 200 µV K⁻¹ that breaks the record of previous reports. A maximum power factor of ≈2.2 mW m⁻¹ K⁻² at 973 K is achieved by optimizing the carrier concentration. The enhanced p-type transport is ascribed to the reduced content of Ni defects, supported by first principle calculations and diffraction pattern refinement. Concomitantly, Co doping also softens the lattice and scatters phonons, resulting in a minimum lattice thermal conductivity of ≈1.8 W m⁻¹ K⁻¹. This leads to a peak zT of 0.55 at 973 K is realized, surpassing the best performing p-type MNiSn by 100%. This approach offers a new method to manipulate the intrinsic atomic disorder in half-Heusler materials, facilitating further optimization of their electronic and thermal properties.     

Thermoelectric Properties of Mn-Doped Ca<Subscript>5</Subscript>Al<Subscript>2</Subscript>Sb<Subscript>6</Subscript>

Ca₅Al₂Sb₆ is a relatively inexpensive Zintl compound exhibiting promising thermoelectric efficiency at temperatures suitable for waste heat recovery. Motivated by our previous studies of Ca₅Al₂Sb₆ doped with Na and Zn, this study focuses on doping with Mn²⁺ at the Al³⁺ site. While Mn is a successful p-type dopant in Ca₅Al₂Sb₆, we find that incomplete dopant activation yields lower hole concentrations than obtained with either previously investigated dopant. High-temperature Hall effect and Seebeck coefficient measurements show a transition from nondegenerate to degenerate semiconducting behavior in Ca₅Al_2−x Mn _x Sb₆ samples (x = 0.05, 0.1, 0.2, 0.3, 0.4) with increasing Mn content. Ultimately, no improvement in zT is achieved via Mn doping, due in part to the limited carrier concentration range achieved.     

Rate of Sublimation of Yb14MnSb11, a Thermoelectric Material for Space Power Applications

The compound Yb₁₄MnSb₁₁ is a p-type thermoelectric material of interest for space power applications. However, average rates of sublimation previously measured at 1000°C were unacceptably high. In at least one study, Yb₂O₃ was observed on the surface after testing. In this study, the rate of sublimation of Yb₁₄MnSb₁₁ was measured at 1000°C by use of a vacuum thermogravimetric analyzer (TGA) which continuously measures weight loss as a result of sublimation. This experiment revealed that the rate of sublimation decreased with time, but also resulted in formation of Yb₂O₃ on the surface, even though the base pressure at the start of the test was 1.9 × 10^?4 Pa (1.4 × 10^?6 torr). Subsequently, the effect of the Yb₂O₃ on the rate of sublimation was evaluated by performing interrupted vacuum furnace tests in which the sample was weighed after exposure at 1000°C for different times. During the weighing periods, the accumulated oxide scale was either completely removed or left to accumulate further on the surface. The interrupted furnace tests showed that formation of Yb₂O₃ on the surface was the likely cause of the reduction in the rate of sublimation of the Yb₁₄MnSb₁₁ when measured by use of the vacuum TGA, at least for the measured test duration. Therefore, uncoated material in the vacuum of space, where oxygen is absent, would be likely to sublime at a continuous rate in excess of 5 × 10^?3 g/cm²/h.     

Enhanced Thermoelectric Performance in GeTe by Synergy of Midgap state and Band Convergence

The good co-existence of midgap state and valence band degeneracy is realized in Bi-alloyed GeTe through the In-Cd codoping to play different but complementary roles in the valence band structure modification. In doping induces midgap state and results in a considerably improved Seebeck coefficient near room temperature, while Cd doping significantly increases the Seebeck coefficient in the mid-high temperature region by promoting the valence band convergence. The synergistic effects obviously increase the density of state effective mass from 1.39 to 2.65 m₀, and the corresponding carrier mobility still reaches 34.3 cm² V⁻¹ s⁻¹ at room temperature. Moreover, the Bi-In-Cd co-alloying introduces various phonon scattering centers including nanoprecipitates and strain field fluctuations and suppresses the lattice thermal conductivity to a rather low value of 0.56 W m⁻¹ K⁻¹ at 600 K. As a result, the Ge_0.89Bi_0.06In_0.01Cd_0.04Te sample obtains excellent thermoelectric properties of zT_max ≈2.12 at 650 K and zT_avg ≈1.43 between 300 and 773 K. This study illustrates that the thermoelectric performance of GeTe can be optimized in a wide temperature range through the synergy of midgap state and valence band convergence.     

Suppression of phonon‐mediated hot carrier relaxation in type‐II InAs/AlAsxSb1 − x quantum wells: a practical route to hot carrier solar cells

InAs/AlAs_xSb_{1 − x} quantum wells are investigated for their potential as hot carrier solar cells. Continuous wave power and temperature‐dependent photoluminescence indicate a transition in the dominant hot carrier relaxation process from conventional phonon‐mediated carrier relaxation below 90 K to a regime where inhibited radiative recombination dominates the hot carrier relaxation at elevated temperatures. At temperatures below 90 K, photoluminescence measurements are consistent with type‐I quantum wells that exhibit hole localization associated with alloy/interface fluctuations. At elevated temperatures, hole delocalization reveals the true type‐II band alignment, where it is observed that inhibited radiative recombination due to the spatial separation of the charge carriers dominates hot carrier relaxation. This decoupling of phonon‐mediated relaxation results in robust hot carriers at higher temperatures, even at lower excitation powers. These results indicate type‐II quantum wells offer potential as practical hot carrier systems. Copyright © 2016 John Wiley & Sons, Ltd.     

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.     

Enhanced Thermoelectric Performance and Service Stability of Cu2Se Via Tailoring Chemical Compositions at Multiple Atomic Positions

Liquid‐like thermoelectric (TE) materials have the advantages of ultrahigh performance, low cost, and environment friendly, but their stability is greatly limited by the possible Cu/Ag deposition under a large current and/or temperature gradient. The pratical application based on liquid‐like TE materials requires both a high TE figure of merit (zT) for high energy conversion efficiency and large critical voltage for good stability, but they are very difficult to be simultaneously achieved in one material. In this work, both the zT and critical voltage are simultaneously optimized in Cu₂Se via tailoring chemical compositions at multiple atomic positions, i.e., introducing Cu deficiency at the Cu‐sites to lower Cu ion chemical potential and alloying sulfur at the Se‐sites to reduce carrier concentrations. A maximum zT of 2.0 at 1000 K has been successfully achieved for Cu_1.96Se_0.8S_0.2, about a 30% improvement over that for Cu₂Se. More importantly, Cu_1.96Se_0.8S_0.2 demonstrates a much higher critical voltage than Cu₂Se, yielding a greatly enhanced service stability under the conditions with/without a temperature gradient. An Ni/Mo/Cu_1.96Se_0.8S_0.2 TE unileg is successfully fabricated with a stable power output even after 400 thermal cycles between 473 and 873 K. This study greatly accelerates the real application of Cu₂Se‐based liquid‐like materials.     

Intrinsically Low Lattice Thermal Conductivity and Anisotropic Thermoelectric Performance in In-doped GeSb2Te4 Single Crystals

Layer-structured GeSb₂Te₄ is a promising thermoelectric candidate, while its anisotropy of thermal and electrical transport properties is still not clear. In this study, Ge_1–xIn_xSb₂Te₄ single crystals are grown by Bridgman method, and their anisotropic thermoelectric properties are systematically investigated. Lower electrical conductivity and higher Seebeck coefficient are observed in the c-axis due to the higher effective mass in this direction. Intrinsically low lattice thermal conductivity is also observed in the c-axis due to the weak chemical bonding and the strong lattice anharmonicity proved by density functional theory calculation. Indium doping introduces an impurity band in the bandgap of GeSb₂Te₄ and leads to the locally distorted density of states near the Fermi level, which contributes to enhanced Seebeck coefficient and improved power factor. Ultimately, a peak zT value of 1 at 673 K and an average zT value of 0.68 within 323–773 K are obtained in Ge_0.93In_0.07Sb₂Te₄ along the c-axis direction, which are 54% and 79% higher than that of the pristine GeSb₂Te₄ single crystal, respectively. This study clarified the origin of intrinsic low lattice thermal conductivity and anisotropy transport properties in GeSb₂Te₄, and shed light on the performance optimization of other layered thermoelectric materials.     

Effect of Excess Na on the Morphology and Thermoelectric Properties of Na x Pb1−x Te0.85Se0.15

The thermoelectric properties of p-Na _x Pb_1?x Te_0.85Se_0.15, which possesses a high thermoelectric figure of merit due to band convergence, have been systematically investigated for increasing Na concentration (x = 0.01, 0.02, 0.03, 0.05, and 0.07) from room temperature to 773 K. For x values up to 0.03, the hole concentration increases with the Na concentration; however, for x ≥ 0.03, excess Na forms separate microstructures with needle- and plate-like shapes. At high concentrations (x = 0.05 and 0.07) both the number and size of these structures increase (over 10 μm). Differential scanning calorimetry identifies a phase change near 660 K in samples with x = 0.05 and 0.07, confirming the formation of microstructures; this phase change leads to a decrease in electrical resistivity. However, these microstructures do not significantly affect thermal transport, probably because they are too large to scatter phonons. The highest thermoelectric figure of merit, zT, value is 1.6, which is obtained at 760 K for x = 0.05, due to the low thermal conductivity and electrical resistivity.     

Thermoelectric Properties of <Emphasis Type="Italic">p</Emphasis>-Type Mg<Subscript>2.00</Subscript>Si<Subscript>0.25</Subscript>Sn<Subscript>0.75</Subscript> with Li and Ag Double Doping

Mg₂Si_1−x Sn _x -system solid solutions are ecofriendly semiconductors that are promising materials for thermoelectric generators in the middle temperature range. To produce a thermoelectric device, high-performance p- and n-type materials must be balanced. In this paper, p-type Mg_2.00Si_0.25Sn_0.75 with Li and Ag double doping was prepared by the liquid–solid reaction method and hot-pressing. Effects of Li and Ag double doping on thermoelectric properties were investigated in the temperature range from room temperature to 850 K. All sintered compacts were identified as single-phase solid solutions with anti-fluorite structure. The carrier concentration increased with the double doping. The temperature dependence of resistivity of the double-doped samples was similar to that of a metal. The seebeck coefficient increased with temperature to a maximum value and then decreased in the intrinsic region. Thermal conductivity decreased linearly with increasing temperature, reaching a minimum near the intrinsic region, and then increased rapidly because of the contribution of the bipolar component. The dimensionless figure of merit reached 0.32 at 610 K for Mg_2.00Si_0.25Sn_0.75 double-doped with Li-5000 ppm and Ag-20000 ppm.     

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.     

Synergistic Compositional–Mechanical–Thermal Effects Leading to a Record High zT in n‐Type V2VI3 Alloys Through Progressive Hot Deformation

Here a progressive hot deformation procedure that endows the benchmark n‐type V₂VI₃ thermoelectric materials with short range disorder (multiple defects), long range order (crystallinity), and strong texture (nearly orientation order) is reported. Not only it is rare for these structural features to coexist but also these structural features elicit the synergistic compositional–mechanical–thermal effects, i.e., a profound interplay among the counts, magnitude, and temperature of hot deformation in relation to the as formed point defects, dislocations, textures, strain clusters, and distortions. Using progressively larger die sets and relatively low hot deformation temperature, rich multiscale microstructures concurrently with a high level of texture comparable to that of zone melted ingot are obtained. The strong donor‐like effect significantly increases the majority carrier concentration, suppressing the detrimental bipolar effect. In addition, the multiscale microstructures yield an ultralow lattice thermal conductivity ≈0.31 W m⁻¹ K⁻¹ at 405 K. A record zT ≈ 1.3 at 450 K are attained in progressively hot deformed n‐type Bi_1.95Sb_0.05Te_2.3Se_0.7 through the synergistic effects. These results not only promise a better pairing between n‐type and p‐type legs in device fabrication but also bring our understanding of n‐type V₂VI₃ alloys and hot deformation technique to a new level.