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.     

Enhancement of Thermopower of TAGS‐85 High‐Performance Thermoelectric Material by Doping with the Rare Earth Dy

Enhancement of thermopower is achieved by doping the narrow‐band semiconductor Ag_6.52Sb_6.52Ge_36.96Te₅₀ (acronym TAGS‐85), one of the best p‐type thermoelectric materials, with 1 or 2% of the rare earth dysprosium (Dy). Evidence for the incorporation of Dy into the lattice is provided by X‐ray diffraction and increased orientation‐dependent local fields detected by ¹²⁵Te NMR spectroscopy. Since Dy has a stable electronic configuration, the enhancement cannot be attributed to 4f‐electron states formed near the Fermi level. It is likely that the enhancement is due to a small reduction in the carrier concentration, detected by ¹²⁵Te NMR spectroscopy, but mostly due to energy filtering of the carriers by potential barriers formed in the lattice by Dy, which has large both atomic size and localized magnetic moment. The interplay between the thermopower, the electrical resistivity, and the thermal conductivity of TAGS‐85 doped with Dy results in an enhancement of the power factor (PF) and the thermoelectric figure of merit (ZT) at 730 K, from PF = 28 μW cm^?1 K^?2 and ZT ≤ 1.3 in TAGS‐85 to PF = 35 μW cm^?1 K^?2 and ZT ≥ 1.5 in TAGS‐85 doped with 1 or 2% Dy for Ge. This makes TAGS‐85 doped with Dy a promising material for thermoelectric power generation.     

High Thermoelectric Performance in Supersaturated Solid Solutions and Nanostructured n‐Type PbTe–GeTe

Sb‐doped and GeTe‐alloyed n‐type thermoelectric materials that show an excellent figure of merit ZT in the intermediate temperature range (400–800 K) are reported. The synergistic effect of favorable changes to the band structure resulting in high Seebeck coefficient and enhanced phonon scattering by point defects and nanoscale precipitates resulting in reduction of thermal conductivity are demonstrated. The samples can be tuned as single‐phase solid solution (SS) or two‐phase system with nanoscale precipitates (Nano) based on the annealing processes. The GeTe alloying results in band structure modification by widening the bandgap and increasing the density‐of‐states effective mass of PbTe, resulting in significantly enhanced Seebeck coefficients. The nanoscale precipitates can improve the power factor in the low temperature range and further reduce the lattice thermal conductivity (κ_lat). Specifically, the Seebeck coefficient of Pb_0.988Sb_0.012Te–13%GeTe–Nano approaches ?280 µV K^?1 at 673 K with a low κ_lat of 0.56 W m^?1 K^?1 at 573 K. Consequently, a peak ZT value of 1.38 is achieved at 623 K. Moreover, a high average ZT_avg value of ≈1.04 is obtained in the temperature range from 300 to 773 K for n‐type Pb_0.988Sb_0.012Te–13%GeTe–Nano.     

Cu Intercalation and Br Doping to Thermoelectric SnSe2 Lead to Ultrahigh Electron Mobility and Temperature‐Independent Power Factor

Due to its single conduction band nature, it is highly challenging to enhance the power factor of SnSe₂ by band convergence. Here, it is reported that simultaneous Cu intercalation and Br doping induce strong Cu–Br interaction to connect SnSe₂ layers, otherwise isolated, via “electrical bridges.” Atom probe tomography analysis confirms a strong attraction between Cu intercalants and Br dopants in the SnSe₂ lattice. Density functional theory calculations reveal that this interaction delocalizes electrons confined around Sn? Se covalent bonds and enhances charge transfer across the SnSe₂ slabs. These effects dramatically increase electron mobility and concentration. Polycrystalline SnCu_0.005Se_1.98Br_0.02 shows even higher electron mobility than pristine SnSe₂ single crystal and the theoretical expectation. This results in significantly improved electrical conductivity without reducing effective mass and Seebeck coefficient, thereby leading to the highest power factor of ≈12 µW cm^?1 K^?2 to date for polycrystalline SnSe₂ and SnSe. It even surpasses the value for the state‐of‐the‐art n‐type SnSe_0.985Br_0.015 single crystal at elevated temperatures. Surprisingly, the achieved power factor is nearly independent of temperature ranging from 300 to 773 K. The engineering thermoelectric figure of merit ZT_eng for SnCu_0.005Se_1.98Br_0.02 is ≈0.25 between 773 and 300 K, the highest ZT_eng ever reported for any form of SnSe₂‐based thermoelectric materials.     

The Impact of Nanostructuring on the Thermal Conductivity of Thermoelectric CoSb3

The high concentration of grain boundaries provided by nanostructuring is expected to lower the thermal conductivity of thermoelectric materials, which favors an increase in their thermoelectric figure‐of‐merit, ZT. A novel chemical alloying method has been used for the synthesis of nanoengineered‐skutterudite CoSb₃. The CoSb₃ powders were annealed for different durations to obtain a set of samples with different particle sizes. The samples were then compacted into pellets by uniaxial pressing under various conditions and used for the thermoelectric characterization. The transport properties were investigated by measuring the Seebeck coefficient and the electrical and thermal conductivities in the temperature range 300 K to 650 K. A substantial reduction in the thermal conductivity of CoSb₃ was observed with decreasing grain size in the nanometer region. For an average grain size of 140 nm, the thermal conductivity was reduced by almost an order of magnitude compared to that of a single crystalline or highly annealed polycrystalline material. The highest ZT value obtained was 0.17 at 611 K for a sample with an average grain size of 220 nm. The observed decrease in the thermal conductivity with decreasing grain size is quantified using a model that combines the macroscopic effective medium approaches with the concept of the Kapitza resistance. The compacted samples exhibit Kapitza resistances typical of semiconductors and comparable to those of Si–Ge alloys.     

High‐Performance N‐type Mg3Sb2 towards Thermoelectric Application near Room Temperature

Se‐doped Mg_3.2Sb_1.5Bi_0.5‐based thermoelectric materials are revisited in this study. An increased ZT value ≈ 1.4 at about 723 K is obtained in Mg_3.2Sb_1.5Bi_0.49Se_0.01 with optimized carrier concentration ≈ 1.9 × 10¹⁹ cm^?3. Based on this composition, Co and Mn are incorporated for the manipulation of the carrier scattering mechanism, which are beneficial to the dramatically enhanced electrical conductivity and power factor around room temperature range. Combined with the lowered lattice thermal conductivity due to the introduction of effective phonon scattering centers in Se&Mn‐codoped sample, a highest room temperature ZT value ≈ 0.63 and a peak ZT value ≈ 1.70 at 623 K are achieved for Mg_3.15Mn_0.05Sb_1.5Bi_0.49Se_0.01, leading to a high average ZT ≈ 1.33 from 323 to 673 K. In particular, a remarkable average ZT ≈ 1.18 between the temperature of 323 and 523 K is achieved, suggesting the competitive substitution for the commercialized n‐type Bi₂Te₃‐based thermoelectric materials.     

Understanding of the Extremely Low Thermal Conductivity in High‐Performance Polycrystalline SnSe through Potassium Doping

P‐type polycrystalline SnSe and K_0.01Sn_0.99Se are prepared by combining mechanical alloying (MA) and spark plasma sintering (SPS). The highest ZT of ≈0.65 is obtained at 773 K for undoped SnSe by optimizing the MA time. To enhance the electrical transport properties of SnSe, K is selected as an effective dopant. It is found that the maximal power factor can be enhanced significantly from ≈280 μW m^?1 K^?2 for undoped SnSe to ≈350 μW m^?1 K^?2 for K‐doped SnSe. It is also observed that the thermal conductivity of polycrystalline SnSe can be enhanced if the SnSe powders are slightly oxidized. Surprisingly, after K doping, the absence of Sn oxides at grain boundaries and the presence of coherent nanoprecipitates in the SnSe matrix contribute to an impressively low lattice thermal conductivity of ≈0.20 W m^?1 K^?1 at 773 K along the sample section perpendicular to pressing direction of SPS. This extremely low lattice thermal conductivity coupled with the enhanced power factor results in a record high ZT of ≈1.1 at 773 K along this direction in polycrystalline SnSe.     

Nanostructure and High Thermoelectric Performance in Nonstoichiometric AgPbSbTe Compounds: the Role of Ag

High-performance nanostructured Ag_1−x Pb_22.5SbTe₂₀ thermoelectric materials have been fabricated using mechanical alloying and spark plasma sintering. A decrease in Ag content causes a great reduction in thermal conductivity and a prominent increase in ZT value. A minimum thermal conductivity of 0.86 W/m K and a high ZT value of 1.5 (700 K) have been obtained for the Ag_0.4Pb_22.5SbTe₂₀ sample. The smaller and denser nanoscopic regions with reduced Ag content are thought to enhance phonon scattering, resulting in decreased thermal conductivity and enhanced thermoelectric performance.     

Hydride Anion Substitution Boosts Thermoelectric Performance of Polycrystalline SrTiO3 via Simultaneous Realization of Reduced Thermal Conductivity and High Electronic Conductivity

The development of environmentally benign thermoelectric materials with high energy conversion efficiency (ZT) continues to be a long-standing challenge. So far, high ZT has been achieved using heavy elements to reduce lattice thermal conductivity (κ_lat). However, it is not preferred to use such elements because of their environmental load and high material cost. Here a new approach utilizing hydride anion (H⁻) substitution to oxide ion is proposed for ZT enhancement in thermoelectric oxide SrTiO₃ bulk polycrystals. Light element H⁻ substitution largely reduces κ_lat from 8.2 W/(mK) of SrTiO₃ to 3.5 W/(mK) for SrTiO_3−xH_x with x = 0.216. The mass difference effect on phonon scattering is small in the SrTiO_3−xH_x, while local structure distortion arising from the distributed Ti−(O,H) bond lengths strongly enhances phonon scattering. The polycrystalline SrTiO_3−xH_x shows high electronic conductivity comparable to La-doped SrTiO₃ single crystal because the H⁻ substitution does not form a grain boundary potential barrier and thus suppresses electron scattering. As a consequence, SrTiO_3−xH_x bulk exhibits maximum ZT = 0.11 at room temperature and the ZT value increases continuously up to 0.22 at T = 657 K. The H⁻ substitution idea offers a new approach for ZT enhancement in thermoelectric materials without utilizing heavy elements.     

Rational Electronic and Structural Designs Advance BiCuSeO Thermoelectrics

In this work, a record high thermoelectric figure-of-merit ZT of 1.6 ± 0.2 at 873 K in p-type polycrystalline Bi_0.94Pb_0.06CuSe_1.01O_0.99 by a synergy of rational band manipulation and novel nanostructural design is reported. First-principles density functional theory calculation results indicate that the density of state at the Fermi level that crosses the valence band can be significantly reduced and the measured optical bandgap can be enlarged from 0.70 to 0.74 eV by simply replacing 1% O with 1% Se, both indicating a potentially reduced carrier concentration and in turn, an improved carrier mobility and a boosted power factor up to 9.0 µW cm⁻¹ K⁻². Meanwhile, comprehensive characterizations reveal that under Se-rich condition, Cu₂Se secondary microphases and significant lattice distortions triggered by Pb-doping and Se-substitution can be simultaneously achieved, contributing to a reduced lattice thermal conductivity of 0.4 W m⁻¹ K⁻¹. Furthermore, a unique shear exfoliation technique enables an effective grain refinement with higher anisotropy of the polycrystalline pellet, leading to a further improved power factor up to 10.9 µW cm⁻¹ K⁻² and a further reduced lattice thermal conductivity of 0.30 W m⁻¹ K⁻¹, which gives rise to record high ZT.     

Intrinsically Low Thermal Conductivity in BiSbSe3: A Promising Thermoelectric Material with Multiple Conduction Bands

Bi₂Se₃, as a Te‐free alternative of room‐temperature state‐of‐the‐art thermoelectric (TE) Bi₂Te₃, has attracted little attention due to its poor electrical transport properties and high thermal conductivity. Interestingly, BiSbSe₃, a product of alloying 50% Sb on Bi sites, shows outstanding electron and phonon transports. BiSbSe₃ possesses orthorhombic structure and exhibits multiple conduction bands, which can be activated when the carrier density is increased as high as ≈3.7 × 10²⁰ cm^?3 through heavily Br doping, resulting in simultaneously enhancing the electrical conductivities and Seebeck coefficients. Meanwhile, an extremely low thermal conductivity (≈0.6–0.4 W m^?1 K^?1 at 300–800 K) is found in BiSbSe₃. Both first‐principles calculations and elastic properties measurements show the strong anharmonicity and support the ultra‐low thermal conductivity of BiSbSe₃. Finally, a maximum dimensionless figure of merit ZT ～ 1.4 at 800 K is achieved in BiSb(Se_0.94Br_0.06)₃, which is comparable to the most n‐type Te‐free TE materials. The present results indicate that BiSbSe₃ is a new and a robust candidate for TE power generation in medium‐temperature range.     

Magnetic Field‐Enhanced Thermoelectric Performance in Dirac Semimetal Cd3As2 Crystals with Different Carrier Concentrations

The magneto‐thermoelectric figure of merit (ZT) in crystals of the topological Dirac semimetal Cd₃As₂ with different carrier concentrations is studied. The ZTs for all the crystals increase with the temperature and show maxima at high temperatures. Meanwhile, the temperatures corresponding to the ZT maxima increase with the carrier concentration. The limit to the improvement in ZT(T) at high temperature could be related to the unusual large enhancement in thermal conductivity at elevated temperatures. The bipolar effect and Dirac liquid behavior are presented as processes possibly responsible for the peculiar behavior of the thermal conductivity. Applying a transverse magnetic field initially leads to a dramatic enhancement and, subsequently, to a slight reduction in ZT for all the crystals. The maximum ZT achieved in a magnetic field increases with the carrier concentration and reaches 1.24 at 450 K in a magnetic field of 9 T for the crystal with the highest carrier concentration. It is expected that this work will be beneficial to the current interests in optimizing the thermoelectric properties of quantum topological materials.     

Thermal Cycling, Mechanical Degradation, and the Effective Figure of Merit of a Thermoelectric Module

Thermoelectric modules experience performance reduction and mechanical failure due to thermomechanical stresses induced by thermal cycling. The present study subjects a thermoelectric module to thermal cycling and evaluates the evolution of its thermoelectric performance through measurements of the thermoelectric figure of merit, ZT, and its individual components. The Seebeck coefficient and thermal conductivity are measured using steady-state infrared microscopy, and the electrical conductivity and ZT are evaluated using the Harman technique. These properties are tracked over many cycles until device failure after 45,000 thermal cycles. The mechanical failure of the TE module is analyzed using high-resolution infrared microscopy and scanning electron microscopy. A reduction in electrical conductivity is the primary mechanism of performance reduction and is likely associated with defects observed during cycling. The effective figure of merit is reduced by 20% through 40,000 cycles and drops by 97% at 45,000 cycles. These results quantify the effect of thermal cycling on a commercial TE module and provide insight into the packaging of a complete TE module for reliable operation.     

Strongly Anisotropic Thermal Conductivity of Free‐Standing Reduced Graphene Oxide Films Annealed at High Temperature

Thermal conductivity of free‐standing reduced graphene oxide films subjected to a high‐temperature treatment of up to 1000 °C is investigated. It is found that the high‐temperature annealing dramatically increases the in‐plane thermal conductivity, K, of the films from ≈3 to ≈61 W m^?1 K^?1 at room temperature. The cross‐plane thermal conductivity, K_⊥, reveals an interesting opposite trend of decreasing to a very small value of ≈0.09 W m^?1 K^?1 in the reduced graphene oxide films annealed at 1000 °C. The obtained films demonstrate an exceptionally strong anisotropy of the thermal conductivity, K/K_⊥ ≈ 675, which is substantially larger even than in the high‐quality graphite. The electrical resistivity of the annealed films reduces to 1–19 Ω □^?1. The observed modifications of the in‐plane and cross‐plane thermal conductivity components resulting in an unusual K/K_⊥ anisotropy are explained theoretically. The theoretical analysis suggests that K can reach as high as ≈500 W m^?1 K^?1 with the increase in the sp² domain size and further reduction of the oxygen content. The strongly anisotropic heat conduction properties of these films can be useful for applications in thermal management.     

Nanoscale FeS2 (Pyrite) as a Sustainable Thermoelectric Material

We have synthesized undoped, Co-doped (up to 5%), and Se-doped (up to 4%) FeS₂ materials by mechanical alloying in a planetary ball mill and investigated their thermoelectric properties from room temperature (RT) to 600 K. With decreasing particle size, the undoped FeS₂ samples showed higher electrical conductivity, from 0.02 S cm^?1 for particles with 70 nm grain size up to 3.1 S cm^?1 for the sample with grain size of 16 nm. The Seebeck coefficient of the undoped samples showed a decrease with further grinding, from 128 μV K^?1 at RT for the sample with 70-nm grains down to 101 μV K^?1 for the sample with grain size of 16 nm. The thermal conductivity of the 16-nm undoped sample lay within the range from 1.3 W m^?1 K^?1 at RT to a minimal value of 1.2 W m^?1 K^?1 at 600 K. All doped samples showed improved thermoelectric behavior at 600 K compared with the undoped sample with 16 nm particle size. Cobalt doping modified the p-type semiconducting behavior to n-type and increased the thermal conductivity (2.1 W m^?1 K^?1) but improved the electrical conductivity (41 S cm^?1) and Seebeck coefficient (-129 μV K^?1). Isovalent selenium doping led to a slightly higher thermal conductivity (1.7 W m^?1 K^?1) as well as to an improved electrical conductivity (26 S cm^?1) and Seebeck coefficient (110 μV K^?1). The ZT value of FeS₂ was increased by a factor of five by Co doping and by a factor of three by Se doping.     

Point Defect Engineering of High‐Performance Bismuth‐Telluride‐Based Thermoelectric Materials

Developing high‐performance thermoelectric materials is one of the crucial aspects for direct thermal‐to‐electric energy conversion. Herein, atomic scale point defect engineering is introduced as a new strategy to simultaneously optimize the electrical properties and lattice thermal conductivity of thermoelectric materials, and (Bi,Sb)₂(Te,Se)₃ thermoelectric solid solutions are selected as a paradigm to demonstrate the applicability of this new approach. Intrinsic point defects play an important role in enhancing the thermoelectric properties. Antisite defects and donor‐like effects are engineered in this system by tuning the formation energy of point defects and hot deformation. As a result, a record value of the figure of merit ZT of ≈1.2 at 445 K is obtained for n‐type polycrystalline Bi₂Te_2.3Se_0.7 alloys, and a high ZT value of ≈1.3 at 380 K is achieved for p‐type polycrystalline Bi_0.3Sb_1.7Te₃ alloys, both values being higher than those of commercial zone‐melted ingots. These results demonstrate the promise of point defect engineering as a new strategy to optimize thermoelectric properties.     

Manipulation of Band Structure and Interstitial Defects for Improving Thermoelectric SnTe

Many efforts are recently devoted on improving thermoelectric SnTe as an environment—friendly alternative to conventional PbTe and successful approaches include valence band convergence, nanostructuring, and substantial/interstitial defects. Among these strategies, alloying SnTe with MnTe enables the most effective reduction in the valence band offset (between L and Σ) for a convergence due to its high solubility of ≈15%, yet there is no indication that the solubility of MnTe is high enough for fully optimizing the valence band structure and thus for maximizing the electronic performance. Here, a strategy is shown to increase the MnTe solubility up to ≈25% by alloying with 5% GeTe, which successfully locates the composition (20% MnTe) to optimize the valence band structure by converging a more degenerated Λ (as compared with band L) and Σ valence bands. Through a further alloying with Cu₂Te, the resultant Cu‐interstitial defects enable a sufficient reduction in lattice thermal conductivity to its amorphous limit (0.4 W m⁻¹ K⁻¹). These electronic and thermal effects successfully realize a record‐high thermoelectric figure of merit, zT of 1.8, strongly competing with that of PbTe. This work demonstrates the validity of band manipulation and interstitial defects for realizing extraordinary thermoelectric performance in SnTe.     

BiSbTe‐Based Nanocomposites with High ZT: The Effect of SiC Nanodispersion on Thermoelectric Properties

Thermoelectric materials have potential applications in energy harvesting and electronic cooling devices, and bismuth antimony telluride (BiSbTe) alloys are the state‐of‐the‐art thermoelectric materials that have been widely used for several decades. It is demonstrated that mixing SiC nanoparticles into the BiSbTe matrix effectively enhances its thermoelectric properties; a high dimensionless figure of merit (ZT) value of up to 1.33 at 373 K is obtained in Bi_0.3Sb_1.7Te₃ incorporated with only 0.4 vol% SiC nanoparticles. SiC nanoinclusions possessing coherent interfaces with the Bi_0.3Sb_1.7Te₃ matrix can increase the Seebeck coefficient while increasing the electrical conductivity, in addition to its effect of reducing lattice thermal conductivity by enhancing phonon scattering. Nano‐SiC dispersion further endows the BiSbTe alloys with better mechanical properties, which are favorable for practical applications and device fabrication.     

Anisotropic and Ultralow Phonon Thermal Transport in Organic–Inorganic Hybrid Perovskites: Atomistic Insights into Solar Cell Thermal Management and Thermoelectric Energy Conversion Efficiency

Energy‐related functionality and performance of organic–inorganic hybrid perovskites, such as methylammonium lead iodide (MAPbI₃), highly depend on their thermal transport behavior. Using equilibrium molecular dynamics simulations, it is discovered that the thermal conductivities of MAPbI₃ under different phases (cubic, tetragonal, and orthorhombic) are less than 1 W m^?1 K^?1, and as low as 0.31 W m^?1 K^?1 at room temperature. Such ultralow thermal conductivity can be attributed to the small phonon group velocities due to their low elastic stiffness, in addition to their short phonon lifetimes (<100 ps) and mean‐free‐paths (<10 nm) due to the enhanced phonon–phonon scattering from highly‐overlapped phonon branches. The anisotropy in thermal conductivity at lower temperatures is found to associate with preferential orientations of organic CH₃NH₃⁺ cations. Among all atomistic interactions, electrostatic interactions dominate thermal conductivities in ionic MAPbI₃ crystals. Furthermore, thermal conductivities of general hybrid perovskites MABX₃ (B = Pb, Sn; X = I, Br) have been qualitatively estimated and found that Sn‐ or Br‐based perovskites possess higher thermal conductivities than Pb‐ or I‐based ones due to their much higher elastic stiffness. This study inspires optimal selections and rational designs of ionic components for hybrid perovskites with desired thermal conductivity for thermally‐stable photovoltaic or highly‐efficient thermoelectric energy harvesting/conversion applications.     

Microstructure‐Lattice Thermal Conductivity Correlation in Nanostructured PbTe0.7S0.3 Thermoelectric Materials

The reduction of thermal conductivity, and a comprehensive understanding of the microstructural constituents that cause this reduction, represent some of the important challenges for the further development of thermoelectric materials with improved figure of merit. Model PbTe‐based thermoelectric materials that exhibit very low lattice thermal conductivity have been chosen for this microstructure–thermal conductivity correlation study. The nominal PbTe_0.7S_0.3 composition spinodally decomposes into two phases: PbTe and PbS. Orderly misfit dislocations, incomplete relaxed strain, and structure‐modulated contrast rather than composition‐modulated contrast are observed at the boundaries between the two phases. Furthermore, the samples also contain regularly shaped nanometer‐scale precipitates. The theoretical calculations of the lattice thermal conductivity of the PbTe_0.7S_0.3 material, based on transmission electron microscopy observations, closely aligns with experimental measurements of the thermal conductivity of a very low value, ～0.8 W m^?1 K^?1 at room temperature, approximately 35% and 30% of the value of the lattice thermal conductivity of either PbTe and PbS, respectively. It is shown that phase boundaries, interfacial dislocations, and nanometer‐scale precipitates play an important role in enhancing phonon scattering and, therefore, in reducing the lattice thermal conductivity.