Band Modification and Localized Lattice Engineering Leads to High Thermoelectric Performance in Ge and Bi Codoped SnTe–AgBiTe2 Alloys

SnTe, emerging as an environment-friendly alternative to conventional PbTe thermoelectrics, has drawn significant attention for clean energy conversion. Here, a high peak figure of merit (ZT) of 1.45 at 873 K in Ge/Bi codoped SnTe–AgBiTe₂ alloys is reported. It is demonstrated that the existence of Ge, Bi, and Ag facilitate band convergence in SnTe, resulting in remarkable enhancement of Seebeck coefficient and power factor. Simultaneously, localized lattice imperfections including dislocations, point defects, and micro/nanopore structures are caused by incorporation of Ge, Bi, and Ag, which can effectively scatter heat carrying phonons with different wavelengths and contribute to an extremely low κ_L of 0.61 W m⁻¹ K⁻¹ in Sn_0.92Ge_0.04Bi_0.04Te–10%AgBiTe₂. Such high peak ZT is achieved by decouples electron and phonon transport through band modification and localized lattice engineering, highlighting promising solutions for advancing thermoelectrics.     

Anomalous Defect Dependence of Thermal Conductivity in Epitaxial WO3 Thin Films

Lattice defects typically reduce lattice thermal conductivity, which has been widely exploited in applications such as thermoelectric energy conversion. Here, an anomalous dependence of the lattice thermal conductivity on point defects is demonstrated in epitaxial WO₃ thin films. Depending on the substrate, the lattice of epitaxial WO₃ expands or contracts as protons are intercalated by electrolyte gating or oxygen vacancies are introduced by adjusting growth conditions. Surprisingly, the observed lattice volume, instead of the defect concentration, plays the dominant role in determining the thermal conductivity. In particular, the thermal conductivity increases significantly with proton intercalation, which is contrary to the expectation that point defects typically lower the lattice thermal conductivity. The thermal conductivity can be dynamically varied by a factor of ≈ 1.7 via electrolyte gating, and tuned over a larger range, from 7.8 to 1.1 W m^?1 K^?1, by adjusting the oxygen pressure during film growth. The electrolyte‐gating‐induced changes in thermal conductivity and lattice dimensions are reversible through multiple cycles. These findings not only expand the basic understanding of thermal transport in complex oxides, but also provide a path to dynamically control the thermal conductivity.     

Melt‐Centrifuged (Bi,Sb)2Te3: Engineering Microstructure toward High Thermoelectric Efficiency

Microstructure engineering is an effective strategy to reduce lattice thermal conductivity (κ_l) and enhance the thermoelectric figure of merit (zT). Through a new process based on melt‐centrifugation to squeeze out excess eutectic liquid, microstructure modulation is realized to manipulate the formation of dislocations and clean grain boundaries, resulting in a porous network with a platelet structure. In this way, phonon transport is strongly disrupted by a combination of porosity, pore surfaces/junctions, grain boundaries, and lattice dislocations. These collectively result in a ≈60% reduction of κ_l compared to zone melted ingot, while the charge carriers remain relatively mobile across the liquid‐fused grains. This porous material displays a zT value of 1.2, which is higher than fully dense conventional zone melted ingots and hot pressed (Bi,Sb)₂Te₃ alloys. A segmented leg of melt‐centrifuged Bi_0.5Sb_1.5Te₃ and Bi_0.3Sb_1.7Te₃ could produce a high device ZT exceeding 1.0 over the whole temperature range of 323–523 K and an efficiency up to 9%. The present work demonstrates a method for synthesizing high‐efficiency porous thermoelectric materials through an unconventional melt‐centrifugation technique.     

Lattice Distortions and Multiple Valence Band Convergence Contributing to High Thermoelectric Performance in MnTe

Here, a new route is proposed for the minimization of lattice thermal conductivity in MnTe through considerable increasing phonon scattering by introducing dense lattice distortions. Dense lattice distortions can be induced by Cu and Ag dopants possessing large differences in atom radius with host elements, which causes strong phonon scattering and results in extremely low lattice thermal conductivity. Density functional theory (DFT) calculations reveal that Cu and Ag codoping enables multiple valence band convergence and produces a high density of state values in the electronic structure of MnTe, contributing to the large Seebeck coefficient. Cu and Ag codoping not only optimizes the Seebeck coefficient but also substantially increases the carrier concentration and electrical conductivity, resulting in the significant enhancement of power factor. The maximum power factor reaches 11.36 µW cm⁻¹K⁻² in Mn_0.98Cu_0.04Ag_0.04Te. Consequently, an outstanding ZT of 1.3 is achieved for Mn_0.98Cu_0.04Ag_0.04Te by these synergistic effects. This study provides guidelines for developing high-performance thermoelectric materials through the rational design of effective dopants.     

Engineering Multiple Microstructural Defects for Record-Breaking Thermoelectric Properties of Chalcopyrite Cu1-xAgxGaTe2

Defect engineering for vacancies, holes, nano precipitates, dislocations, and strain are efficient means of suppressing lattice thermal conductivity. Multiple microstructural defects are successfully designed in Cu_1-xAg_xGaTe₂ (0 ≤ x ≤ 0.5) solid solutions through high-ratio alloying and vibratory ball milling, to achieve ultra-low thermal conductivity and record-breaking thermoelectric performance. Extremely low total thermal conductivities of 1.28 W m⁻¹ K⁻¹ at 300 K and 0.40 W m⁻¹ K⁻¹ at 873 K for the Cu_0.5Ag_0.5GaTe₂ are observed, which are ≈79% and ≈58% lower than that of the CuGaTe₂ matrix. Multiple phonon scattering mechanisms are collectively responsible for the reduction of thermal conductivity in this work. On one hand, large amounts of nano precipitates and dislocations are formed via vibrating ball milling followed by the low-temperature hot press, which can enhance phonon scattering. On the other hand, the difference in atomic sizes, distorted chemical bonds, elements fluctuation, and strained domains are caused by the high substitution ratio of Ag and also function as a center for the strong phonon scattering. As a result, the Cu_0.7Ag_0.3GaTe₂ exhibits a record high ZT_max of ≈1.73 at 873 K and ZT_ave of ≈0.69 between 300–873 K, which are the highest values of CuGaTe₂-based thermoelectric materials.     

Realizing zT of 2.3 in Ge1−x−ySbxInyTe via Reducing the Phase‐Transition Temperature and Introducing Resonant Energy Doping

GeTe with rhombohedral‐to‐cubic phase transition is a promising lead‐free thermoelectric candidate. Herein, theoretical studies reveal that cubic GeTe has superior thermoelectric behavior, which is linked to (1) the two valence bands to enhance the electronic transport coefficients and (2) stronger enharmonic phonon–phonon interactions to ensure a lower intrinsic thermal conductivity. Experimentally, based on Ge_1?xSb_xTe with optimized carrier concentration, a record‐high figure‐of‐merit of 2.3 is achieved via further doping with In, which induces the distortion of the density of states near the Fermi level. Moreover, Sb and In codoping reduces the phase‐transition temperature to extend the better thermoelectric behavior of cubic GeTe to low temperature. Additionally, electronic microscopy characterization demonstrates grain boundaries, a high‐density of stacking faults, and nanoscale precipitates, which together with the inevitable point defects result in a dramatically decreased thermal conductivity. The fundamental investigation and experimental demonstration provide an important direction for the development of high‐performance Pb‐free thermoelectric materials.     

Lattice Softening Significantly Reduces Thermal Conductivity and Leads to High Thermoelectric Efficiency

The influence of micro/nanostructure on thermal conductivity is a topic of great scientific interest, particularly to thermoelectrics. The current understanding is that structural defects decrease thermal conductivity through phonon scattering where the phonon dispersion and speed of sound are assumed to remain constant. Experimental work on a PbTe model system is presented, which shows that the speed of sound linearly decreases with increased internal strain. This softening of the materials lattice completely accounts for the reduction in lattice thermal conductivity, without the introduction of additional phonon scattering mechanisms. Additionally, it is shown that a major contribution to the improvement in the thermoelectric figure of merit (zT > 2) of high‐efficiency Na‐doped PbTe can be attributed to lattice softening. While inhomogeneous internal strain fields are known to introduce phonon scattering centers, this study demonstrates that internal strain can modify phonon propagation speed as well. This presents new avenues to control lattice thermal conductivity, beyond phonon scattering. In practice, many engineering materials will exhibit both softening and scattering effects, as is shown in silicon. This work shines new light on studies of thermal conductivity in fields of energy materials, microelectronics, and nanoscale heat transfer.     

Thermally insulative thermoelectric argyrodites

Ag/Cu-based argyrodites have recently received extensive attention as promising thermoelectric materials. This can be largely understood by the hierarchical chemical bonding structure that allows the existence of high-concentration and highly mobile Ag⁺/Cu⁺ ions distributed in the rigid polyanionic framework, since the diffusive cations enable an effective phonon scattering for phononically insulating as that in woods while the rigid framework ensures an electronic charge transport as that in trivial thermoelectric semiconductors. This review focused firstly on the synthesis of both single-crystalline and poly-crystalline argyrodites as well as the chemical compositions, phases and crystallographic features; secondly on the origins of the low lattice thermal conductivity including crystal structure complexity, weak bonded ions, strong lattice anharmonicity and low sound velocity; and thirdly on the electronic band structure characteristics including effective mass and band degeneracy for an evaluation on the electronic transport properties, as well as performance stability. These together lead a perspective on future development of thermoelectric argyrodites to emphasize the enhancement of electronic performance such as by carrier concentration and by manipulating the electronic band structure.     

Unprecedented Enhancement of Thermoelectric Power Factor Induced by Pressure in Small‐Molecule Organic Semiconductors

Establishing the relationship between pressure and heat–electricity interconversion in van der Waals bonded small‐molecule organic semiconductors is critical not only in designing flexible thermoelectric materials, but also in developing organic electronics. Here, based on first‐principles calculations and using naphthalene as a case study, an unprecedented elevation of p‐type thermoelectric power factor induced by pressure is demonstrated; and the power factor increases by 267% from 159.5 µW m^?1 K^?2 under ambient conditions to 585.8 µW m^?1 K^?2 at 2.1 GPa. The underlying mechanism is attributed to the dramatic inhibition of lattice‐vibration‐caused electronic scattering. Furthermore, it is revealed that both restraining low‐frequency intermolecular vibrational modes and increasing intermolecular electronic coupling are two essential factors that effectively suppress the electron–phonon scattering. From the standpoint of molecular design, these two conditions can be achieved by extending the π‐conjugated backbones, introducing long alkyl sidechains to the π‐cores, and substituting heteroatoms in the π‐cores.     

Influence of Structure Defects on Thermal Conductivity in Solid p-H2 and p-H2 - o-D2 Solid Solutions

The formation of structure defects induced by thermal stress in pure H₂ and H₂-D₂ solutions has been investigated. The thermal conductivity of p-H₂ crystals and p-H₂ - o-D₂ solutions is measured by the steady-state method from 1.5 K to the melting point. Crystals with different numbers of structure defects were prepared by varying the growth rate and parameters of subsequent annealing, and thermal shock. The value of thermal conductivity and the character of the temperature dependence are observed to change, depending on the number of defects present. The experimental results are analyzed within the Callaway model taking into account the phonon scattering processes such as phononphonon scattering, boundary scattering, scattering on D₂ impurities, and scattering on structure defects (dislocations and low-angle boundaries). The contribution of isolated dislocations into the total relaxation rate is distinct only for the pure parahydrogen sample subjected to thermal shock. In the p-H₂ - o-D₂ solutions this contribution is not, detectable against the background of the strong frequency-independent scattering by low-angle boundaries. It is shown that the density of the dislocations that form low-angle grain boundaries is proportional to the concentration of impurity molecules.     

Simultaneous Boost of Power Factor and Figure‐of‐Merit in In–Cu Codoped SnTe

Significantly enhanced thermoelectric performance is achieved for eco‐friendly SnTe by a coorperative effect between a dopant resonant energy level and interstitial defects. By manipulating the band structure through indium doping, the Seebeck coefficient is remarkably improved, leading to an enhanced power factor, with a high level of ≈29 µW cm^?1 K^?2 at 873 K. Lattice thermal conductivity is sharply reduced, approaching the amorphous limit, through the strong phonon scattering induced by multiple scales of Cu₂Te nanoprecipitates, as well as Cu interstitials, leading to a high ZT value of ≈1.55 at 873 K.     

Direct Observation of Inherent Atomic‐Scale Defect Disorders responsible for High‐Performance Ti1−xHfxNiSn1−ySby Half‐Heusler Thermoelectric Alloys

Structural defects often dominate the electronic‐ and thermal‐transport properties of thermoelectric (TE) materials and are thus a central ingredient for improving their performance. However, understanding the relationship between TE performance and the disordered atomic defects that are generally inherent in nanostructured alloys remains a challenge. Herein, the use of scanning transmission electron microscopy to visualize atomic defects directly is described and disordered atomic‐scale defects are demonstrated to be responsible for the enhancement of TE performance in nanostructured Ti_1?x Hf_x NiSn_1?y Sb_y half‐Heusler alloys. The disordered defects at all atomic sites induce a local composition fluctuation, effectively scattering phonons and improving the power factor. It is observed that the Ni interstitial and Ti,Hf/Sn antisite defects are collectively formed, leading to significant atomic disorder that causes the additional reduction of lattice thermal conductivity. The Ti_1?x Hf_x NiSn_1?y Sb_y alloys containing inherent atomic‐scale defect disorders are produced in one hour by a newly developed process of temperature‐regulated rapid solidification followed by sintering. The collective atomic‐scale defect disorder improves the zT to 1.09 ± 0.12 at 800 K for the Ti_0.5Hf_0.5NiSn_0.98Sb_0.02 alloy. These results provide a promising avenue for improving the TE performance of state‐of‐the‐art materials.     

Ag_2Te掺杂对p型Bi_(0.5)Sb_(1.5)Te_3块状合金热电性能的影响

采用真空熔炼、机械球磨及放电等离子烧结技术(SPS)制备得到了(Ag2Te)x(Bi0.5Sb1.5Te3)1-x(x=0,0.025,0.05,0.1)系列样品,性能测试表明,Ag2Te的掺入可以显著改变材料的热电性能变化趋势,掺杂样品在温度为450~550K范围内具有较未掺杂样品更优的热电性能.适当量的Ag2Te掺入能够有效地提高材料的声子散射,降低材料的热导率.在测试温度范围内,(Ag2Te)0.05(Bi0.5Sb1.5Te3)0.95具有最低的晶格热导,室温至575K范围内保持在0.2~0.3W/(m·K)之间,在575K时,(Ag2Te)0.05(Bi0.5Sb1.5Te3)0.95试样具有最大热电优值ZT=0.84,相较于未掺杂样品提高了约20%.     

Breaking the Minimum Limit of Thermal Conductivity of Mg3Sb2 Thermoelectric Mediated by Chemical Alloying Induced Lattice Instability

Thermal properties strongly affect the applications of functional materials, such as thermal management, thermal barrier coatings, and thermoelectrics. Thermoelectric (TE) materials must have a low lattice thermal conductivity to maintain a temperature gradient to generate the voltage. Traditional strategies for minimizing the lattice thermal conductivity mainly rely on introduced multiscale defects to suppress the propagation of phonons. Here, the origin of the anomalously low lattice thermal conductivity is uncovered in Cd-alloyed Mg₃Sb₂ Zintl compounds through complementary bonding analysis. First, the weakened chemical bonds and the lattice instability induced by the antibonding states of 5p-4d levels between Sb and Cd triggered giant anharmonicity and consequently increased the phonon scattering. Moreover, the bond heterogeneity also augmented Umklapp phonon scatterings. Second, the weakened bonds and heavy element alloying softened the phonon mode and significantly decreased the group velocity. Thus, an ultralow lattice thermal conductivity of ≈0.33 W m⁻¹ K⁻¹ at 773 K is obtained, which is even lower than the predicated minimum value. Eventually, Na_0.01Mg_1.7Cd_1.25Sb₂ displays a high ZT of ≈0.76 at 773 K, competitive with most of the reported values. Based on the complementary bonding analysis, the work provides new means to control thermal transport properties through balancing the lattice stability and instability.     

Thermal Conductivity of Pb1 – x Mn x Te Single Crystals

The thermal conductivity of Pb_{1 – x} Mn _x Te single crystals is measured in the range 80–300 K. The electronic and lattice components of thermal conductivity in the crystals are evaluated for a parabolic conduction band, arbitrary degeneracy, and elastic scattering of charge carriers. The total thermal conductivity and lattice component are found to decrease with increasing temperature. Increasing the Mn content of the solid solutions also reduces the total and lattice thermal conductivities, while annealing increases them. The density of point defects in the crystals is evaluated. The heat conduction in Pb_{1 – x} Mn _x Te is shown to be dominated by phonons.     

Influence of the cation sublattice defectness on the electronic thermoelectric power of Li x Cu(2−x)−δ (x ≤ 0.25)

This paper presents an experimental study of the electronic thermoelectric power as a function of copper content for Li _x Cu_(2?x)?δS (x ≤ 0.25) electronic-ionic mixed conductors. Using a vacancy model for lattice defects, we calculate their electronic thermoelectric power as a function of x. By adjusting the hole effective mass, we reach satisfactory agreement with experimental data.     

Thermoelectric SnTe with Band Convergence,Dense Dislocations,and Interstitials through Sn Self‐Compensation and Mn Alloying

SnTe is known as an eco‐friendly analogue of PbTe without toxic elements. However, the application potentials of pure SnTe are limited because of its high hole carrier concentration derived from intrinsic Sn vacancies, which lead to a high electrical thermal conductivity and low Seebeck coefficient. In this study, Sn self‐compensation and Mn alloying could significantly improve the Seebeck coefficients in the whole temperature range through simultaneous carrier concentration optimization and band engineering, thereby leading to a large improvement of the power factors. Combining precipitates and atomic‐scale interstitials due to Mn alloying with dense dislocations induced by long time annealing, the lattice thermal conductivity is drastically reduced. As a result, an enhanced figure of merit (ZT) of 1.35 is achieved for the composition of Sn_0.94Mn_0.09Te at 873 K and the ZT_ave from 300 to 873 K is boosted to 0.78, which is of great significance for practical application. Hitherto, the ZT_max and ZT_ave of this work are the highest values among all single‐element‐doped SnTe systems.     

Thermal conductivity of niobium in the purely superconducting and normal states

The thermal conductivity λ of four niobium samples has been measured between 1 and 10 K, both in the superconducting and normal states. The specimens differed in their crystal defect structures due to annealing at different temperatures (dislocations, grain boundaries) and, in one case, to subsequent fast neutron irradiation (dislocation loops). A procedure has been developed with which the electron and phonon contributions to the thermal conductivity can be separated with an accuracy not hitherto obtainable. All the samples proved to have the same energy gap at 0K:δ(0)=(1.95±0.02)kT _c . The phonon conductivity in the superconducting stateλ _p ^s has been compared with the formula of Bardeen, Rickayzen, and Tewordt extended for scattering mechanisms other than phonon-electron interaction. For the unirradiated samples at \({\text{T}} \lesssim 0.15T_{\text{c}} \) , λ _p ^s is proportional toT ², showing that dislocations are mainly responsible for the phonon scattering. The results are qualitatively in agreement with the theory of Klemens, giving a rough indication that the grain boundaries may be considered as arrays of line dislocations. Dislocation loops introduced by the neutron irradiation turn out to behave like clusters of point defects. A second consequence of the irradiation is an enhancement of the original dislocation scattering term.     

Manipulating the Ge Vacancies and Ge Precipitates through Cr Doping for Realizing the High‐Performance GeTe Thermoelectric Material

GeTe alloy is a promising medium‐temperature thermoelectric material but with highly intrinsic hole carrier concentration by thermodynamics, making this system to be intrinsically off‐stoichiometric with Ge vacancies and Ge precipitations. Generally, an intentional increase of formation energy of Ge vacancy by element substitution will lead to an effective dissolution of Ge precipitates for reduction in hole concentration. Here, an opposite direction of decreasing the formation energy of Ge vacancies is demonstrated by substituting Cr at Ge site. This strategy produces more but nearly homogenously distributed Ge precipitations and Ge vacancies, which provides enhanced phonon scattering and effectively reduces the lattice thermal conductivity. Furthermore, Cr atom carries one more electron than Ge and serves as an electron donor for decreasing the hole carrier concentrations. Further optimization incorporates the effect of Bi substitution for facilitating band convergence. A maximum figure of merit (ZT) of 2.0 at 600 K with average ZT of over 1.2 is achieved in the sample of Ge_0.92Cr_0.03Bi_0.05Te, making it one of the best thermoelectric materials for medium‐temperature application.     

Ge掺杂MnTe材料的热电输运性能

MnTe作为一种新型的无铅p型热电材料, 在中温区热电领域具有广阔的应用前景, 但其本身的热电性能不足以与高性能n型热电材料相匹配。本研究通过真空熔炼-淬火和放电等离子烧结的方法制备不同Ge掺杂量的致密且均匀的Mn_1.06-xGe_xTe(x=0, 0.01, 0.02, 0.03, 0.04)多晶块体样品。过量的Mn可以有效抑制MnTe₂相, 提高基体相的热电性能。通过掺杂4%Ge粉末, 材料的载流子浓度提高到7.328×10¹⁸ cm^-3, 电导率在873 K增大到7×10³ S∙cm^-1, 功率因子提升至620 μW∙m^-1∙K^-2。同时, 通过点缺陷增强声子散射使材料的热导率降低到0.62 W∙m^-1∙K^-1, 实现了对材料电声输运性能的有效调控。Mn_1.02Ge_0.04Te在873 K获得了0.86的热电优值ZT, 较纯MnTe材料提高了43%。