Phonon Scattering and Thermal Conductivity in p‐Type Nanostructured PbTe‐BaTe Bulk Thermoelectric Materials

Transmission electron microscopy studies show that a PbTe‐BaTe bulk thermoelectric system represents the coexistence of solid solution and nanoscale BaTe precipitates. The observed significant reduction in the thermal conductivity is attributed to the enhanced phonon scattering by the combination of substitutional point defects in the solid solution and the presence of high spatial density of nanoscale precipitates. In order to differentiate the role of nanoscale precipitates and point defects in reducing lattice thermal conductivity, a modified Callaway model is proposed, which highlights the contribution of point defect scattering due to solid solution in addition to that of other relevant microstructural constituents. Calculations indicate that in addition to a 60% reduction in lattice thermal conductivity by nanostructures, point defects are responsible for about 20% more reduction and the remaining reduction is contributed by the collective of dislocation and strain scattering. These results underscore the need for tailoring integrated length‐scales for enhanced heat‐carrying phonon scattering in high performance thermoelectrics.     

Multipoint Defect Synergy Realizing the Excellent Thermoelectric Performance of n‐Type Polycrystalline SnSe via Re Doping

SnSe has attracted much attention due to the excellent thermoelectric (TE) properties of both p‐ and n‐type single crystals. However, the TE performance of polycrystalline SnSe is still low, especially in n‐type materials, because SnSe is an intrinsic p‐type semiconductor. In this work, a three‐step doping process is employed on polycrystalline SnSe to make it n‐type and enhance its TE properties. It is found that the Sn_0.97Re_0.03Se_0.93Cl_0.02 sample achieves a peak ZT value of ≈1.5 at 798 K, which is the highest ZT reported, to date, in n‐type polycrystalline SnSe. This is attributed to the synergistic effects of a series of point defects: $V_{\mathrm{Se}}^{\mathrm{..}},{\mathrm{Cl}}_{\mathrm{Se}}^{.},V_{\mathrm{Sn}}^{,,},{\mathrm{Re}}_{\mathrm{Sn}}^{\times },{\mathrm{Re}}_{}^0$. In those defects, the $V_{\mathrm{Se}}^{\mathrm{..}}$ compensates for the intrinsic Sn vacancies in SnSe, the ${\mathrm{Cl}}_{\mathrm{Se}}^{.}$ acts as a donor, the $V_{\mathrm{Sn}}^{,,}$acts as an acceptor, all of which contribute to optimizing the carrier concentration. Rhenium (Re) doping surprisingly plays dual‐roles, in that it both significantly enhances the electrical transport properties and largely reduces the thermal conductivity by introducing the point defects, ${\mathrm{Re}}_{\mathrm{Sn}}^{\times },{\mathrm{Re}}_{}^0$. The method paves the way for obtaining high‐performance TE properties in SnSe crystals using multipoint‐defect synergy via a step‐by‐step multielement doping methodology.     

High Thermoelectric Performance in the Wide Band‐Gap AgGa1‐xTe2 Compounds: Directional Negative Thermal Expansion and Intrinsically Low Thermal Conductivity

A deficiency of Ga in wide band‐gap AgGa_1‐xTe₂ semiconductors (1.2 eV) can be used to optimize the electrical transport properties and reduce the thermal conductivity to achieve ZT > 1 at 873 K. First‐principles density functional theory calculations and a Boson peak observed in the low temperature heat capacity data indicate the presence of strong coupling between optical phonons with low frequency and heat carrying acoustical phonons, resulting in a depressed maximum of Debye frequency in the first Brillouin zone and low phonon velocities. Moreover, the Ag? Te bond lengths and Te? Ag? Te bond angles increase with rising temperature, leading to a significant distortion of the [AgTe₄]^7? tetrahedra, but an almost unmodified [GaTe₄]^5? tetrahedra. This behavior results in lattice expansion in the ab‐plane and contraction along the c‐axis, corresponding to the positive and negative Gruneisen parameters in the phonon spectral calculations. This effect gives rise to the large anharmonic behavior of the lattice. These factors together with the low frequency vibrations of Ag and Te atoms in the structure lead to an ultralow thermal conductivity of 0.18 W m^?1 K^?1 at 873 K.     

Hierarchical Chemical Bonds Contributing to the Intrinsically Low Thermal Conductivity in α‐MgAgSb Thermoelectric Materials

Understanding the lattice dynamics and phonon transport from the perspective of chemical bonds is essential for improving and finding high‐efficiency thermoelectric materials and for many applications. Here, the coexistence of global and local weak chemical bonds is elucidated as the origin of the intrinsically low lattice thermal conductivity of non‐caged structure Nowotny–Juza compound, α‐MgAgSb, which is identified as a new type of promising thermoelectric material in the temperature range of 300–550 K. The global weak bonds of the compound lead to a low sound velocity. The unique three‐centered Mg? Ag? Sb bonds in α‐MgAgSb vibrate locally and induce low‐frequency optical phonons, resulting in “rattling‐like” thermal damping to further reduce the lattice thermal conductivity. The hierarchical chemical bonds originate from the low valence electron count of α‐MgAgSb, with the feature shared by Nowotny–Juza compounds. Low lattice thermal conductivities are therefore highly possible in this series of compounds, which is verified by phonon and bulk modulus calculations on some of the compositions.     

Analysis of Nanostructuring in High Figure‐of‐Merit Ag1–xPbmSbTe2+m Thermoelectric Materials

Thermoelectric materials based on quaternary compounds Ag_1?xPb_mSbTe_2+m exhibit high dimensionless figure‐of‐merit values, ranging from 1.5 to 1.7 at 700 K. The primary factor contributing to the high figure of merit is a low lattice thermal conductivity, achieved through nanostructuring during melt solidification. As a consequence of nucleation and growth of a second phase, coherent nanoscale inclusions form throughout the material, which are believed to result in scattering of acoustic phonons while causing only minimal scattering of charge carriers. Here, characterization of the nanosized inclusions in Ag_0.53Pb₁₈Sb_1.2Te₂₀ that shows a strong tendency for crystallographic orientation along the {001} planes, with a high degree of lattice strain at the interface, consistent with a coherent interfacial boundary is reported. The inclusions are enriched in Ag relative to the matrix, and seem to adopt a cubic, 96 atom per unit cell Ag₂Te phase based on the Ti₂Ni type structure. In‐situ high‐temperature synchrotron radiation diffraction studies indicated that the inclusions remain thermally stable to at least 800 K.     

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.     

Anomalous Low Thermal Conductivity of Atomically Thin InSe Probed by Scanning Thermal Microscopy

The ability of a material to conduct heat influences many physical phenomena, ranging from thermal management in nanoscale devices to thermoelectrics. Van der Waals 2D materials offer a versatile platform to tailor heat transfer due to their high surface-to-volume ratio and mechanical flexibility. Here, the nanoscale thermal properties of 2D indium selenide (InSe) are studied by scanning thermal microscopy. The high electrical conductivity, broad-band optical absorption, and mechanical flexibility of 2D InSe are accompanied by an anomalous low thermal conductivity (κ). This can be smaller than that of low-κ dielectrics, such as silicon oxide, and it decreases with reducing the lateral size and/or thickness of InSe. The thermal response is probed in free-standing InSe layers as well as layers supported by a substrate, revealing the role of interfacial thermal resistance, phonon scattering, and strain. These thermal properties are critical for future emerging technologies, such as field-effect transistors that require efficient heat dissipation or thermoelectric energy conversion with low-κ, high electron mobility 2D materials, such as InSe.     

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.     

Design of High‐Performance Disordered Half‐Heusler Thermoelectric Materials Using 18‐Electron Rule

Ternary half‐Heusler (HH) alloys display intriguing functionalities ranging from thermoelectric to magnetic and topological properties. For thermoelectric applications, stable HH alloys with a nominal valence electron count (VEC) of 18 per formula or defective HH alloys with a VEC of 17 or 19 are assumed to be promising candidates. Inspired by the pioneering efforts to design a TiFe_0.5Ni_0.5Sb double HH alloy by combining 17‐electron TiFeSb and 19‐electron TiNiSb HH alloys, both high‐performance n‐type and p‐type materials based on the same parent TiFe_0.5Ni_0.5Sb are developed. First‐principles calculation results demonstrate their beneficial band structure having a high band degeneracy that contributes to their large effective mass and thereby maintains their high Seebeck coefficient values. Due to the strong Fe/Ni disorder effect, TiFe_0.5Ni_0.5Sb exhibits a much lower lattice thermal conductivity than does TiCoSb, consistent with very recently reported results. Furthermore, tuning the ratio of Fe and Ni leads to achieving both p‐ and n‐types, and alloying Ti by Hf further enhances the thermoelectric performance significantly. A peak ZT of ≈1 and ≈0.7 at 973 K are achieved in the p‐type and n‐type based on the same parent, respectively, which are beneficial and promising for real applications.     

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.     

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.     

XBi4S7 (X = Mn,Fe): New Cost‐Efficient Layered n‐Type Thermoelectric Sulfides with Ultralow Thermal Conductivity

A new class of cost‐efficient n‐type thermoelectric sulfides with a layered structure is reported, namely MnBi₄S₇ and FeBi₄S₇. Theoretical calculations combined with synchrotron X‐ray/neutron diffraction analyses reveal the origin of their electronic and thermal properties. The complex low‐symmetry monoclinic crystal structure generates an electronic band structure with a mixture of heavy and light bands near the conduction band edge, as well as vibrational properties favorable for high thermoelectric performance. The low thermal conductivity can be attributed to the complex layered crystal structure and to the existence of the lone pair of electrons in Bi³⁺. This feature combined with the relatively high power factor lead to a figure of merit as high as 0.21 (700 K) in undoped MnBi₄S₇, making this material a promising n‐type candidate for low‐ and intermediate‐temperature thermoelectric applications.     

In‐Plane Liquid Crystalline Texture of High‐Performance Thienothiophene Copolymer Thin Films

Poly(2,5‐Bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]thiophenes (pBTTTs) are a new class of solution‐processable polymer semiconductors with high charge carrier mobilities that rival amorphous silicon. This exceptional performance is thought to originate in the microstructure of pBTTT films, which exhibit high crystallinity and a surface topography of wide terraces. However, the true lateral grain size has not been determined, despite the critical impact grain boundaries can have on the charge transport of polymer semiconductors. Here a strategy for determining the lateral grain structure of pBTTT using dark‐field transmission electron microscopy (DF‐TEM) and subsequent image analysis is presented. For the first time, it is revealed that the in‐plain pBTTT crystal orientation varies smoothly across a length scale significantly less than one micrometer (e.g., with only small angles between adjacent diffracting regions). The pBTTT polymers thus exhibit an in‐plane liquid crystalline texture. This microstructure is different from what has been reported for small molecule semiconductors or polymer semiconductors such as poly(3‐hexyl thiophene) (P3HT). Even though films processed differently exhibit different apparent domain sizes, they exhibit similar charge carrier hopping activation energies because they possess similar low densities of abrupt grain boundaries.     

Ultralow Thermal Conductivity of Single‐Crystalline Porous Silicon Nanowires

Porous materials provide a large surface‐to‐volume ratio, thereby providing a knob to alter fundamental properties in unprecedented ways. In thermal transport, porous nanomaterials can reduce thermal conductivity by not only enhancing phonon scattering from the boundaries of the pores and therefore decreasing the phonon mean free path, but also by reducing the phonon group velocity. Herein, a structure–property relationship is established by measuring the porosity and thermal conductivity of individual electrolessly etched single‐crystalline silicon nanowires using a novel electron‐beam heating technique. Such porous silicon nanowires exhibit extremely low diffusive thermal conductivity (as low as 0.33 W m^?1 K^?1 at 300 K for 43% porosity), even lower than that of amorphous silicon. The origin of such ultralow thermal conductivity is understood as a reduction in the phonon group velocity, experimentally verified by measuring the Young's modulus, as well as the smallest structural size ever reported in crystalline silicon (<5 nm). Molecular dynamics simulations support the observation of a drastic reduction in thermal conductivity of silicon nanowires as a function of porosity. Such porous materials provide an intriguing platform to tune phonon transport, which can be useful in the design of functional materials toward electronics and nanoelectromechanical systems.     

Record High Power Factor and Low Thermal Conductivity in Amorphous/PbTe/Amorphous Multiple Quantum Wells

Quantum well (QW) superlattice is one of the proposals to improve the thermoelectric properties and provide a rich platform for the next generation of thermoelectric device. Previous QW have two main challenges that need to be addressed: i) decrease the electron tunneling across the layers in the semiconductor-based multiple QWs (MQW), and ii) decrease the thermal conductivity in the oxide-based MQW. Herein, the study demonstrates amorphous based PbTe/amorphous-STO MQWs with ultrahigh power factor of 40.9 µW cm⁻¹ K⁻² and record low thermal conductivity of ≈0.49 W m⁻¹ K⁻¹ at room temperature. The high performance of PbTe/amorphous-STO MQWs is attributed to strong quantum confine effect and its intrinsic low thermal conductivity of amorphous superlattice structure. The results open up a new avenue toward modulating thermoelectric properties beyond traditional MQWs of thermoelectric materials.     

Designing and Understanding the Superior Potassium Storage Performance of Nitrogen/Phosphorus Co-Doped Hollow Porous Bowl-Like Carbon Anodes

Potassium-ion batteries (PIBs) are promising alternatives to lithium-ion batteries because of the advantage of abundant, low-cost potassium resources. However, PIBs are facing a pivotal challenge to develop suitable electrode materials for efficient insertion/extraction of large-radius potassium ions (K⁺). Here, a viable anode material composed of uniform, hollow porous bowl-like hard carbon dual doped with nitrogen (N) and phosphorus (P) (denoted as N/P-HPCB) is developed for high-performance PIBs. With prominent merits in structure, the as-fabricated N/P-HPCB electrode manifests extraordinary potassium storage performance in terms of high reversible capacity (458.3 mAh g⁻¹ after 100 cycles at 0.1 A g⁻¹), superior rate performance (213.6 mAh g⁻¹ at 4 A g⁻¹), and long-term cyclability (205.2 mAh g⁻¹ after 1000 cycles at 2 A g⁻¹). Density-functional theory calculations reveal the merits of N/P dual doping in favor of facilitating the adsorption/diffusion of K⁺ and enhancing the electronic conductivity, guaranteeing improved capacity, and rate capability. Moreover, in situ transmission electron microscopy in conjunction with ex situ microscopy and Raman spectroscopy confirms the exceptional cycling stability originating from the excellent phase reversibility and robust structure integrity of N/P-HPCB electrode during cycling. Overall, the findings shed light on the development of high-performance, durable carbon anodes for advanced PIBs.     

Covalently Bonded Graphene–Carbon Nanotube Hybrid for High‐Performance Thermal Interfaces

The remarkable thermal properties of graphene and carbon nanotubes (CNTs) have been the subject of intensive investigations for the thermal management of integrated circuits. However, the small contact area of CNTs and the large anisotropic heat conduction of graphene have hindered their applications as effective thermal interface materials (TIMs). Here, a covalently bonded graphene–CNT (G‐CNT) hybrid is presented that multiplies the axial heat transfer capability of individual CNTs through their parallel arrangement, while at the same time it provides a large contact area for efficient heat extraction. Through computer simulations, it is demonstrated that the G‐CNT outperforms few‐layer graphene by more than 2 orders of magnitude for the c‐axis heat transfer, while its thermal resistance is 3 orders of magnitude lower than the state‐of‐the‐art TIMs. We show that heat can be removed from the G‐CNT by immersing it in a liquid. The heat transfer characteristics of G‐CNT suggest that it has the potential to revolutionize the design of high‐performance TIMs.     

Direct Synthesis of Large‐Scale WTe2 Thin Films with Low Thermal Conductivity

Large‐scale, polycrystalline WTe₂ thin films are synthesized by atmospheric chemical vapor reaction of W metal films with Te vapor catalyzed by H₂Te intermediates, paving a way to understanding the synthesis mechanism for low bonding energy tellurides and toward synthesis of single‐crystalline telluride nanoflakes. Through‐plane and in‐plane thermal conductivities of single‐crystal WTe₂ flakes and polycrystalline WTe₂ thin films are measured for the first time. Nanoscale grains and disorder in WTe₂ thin films suppress the in‐plane thermal conductivity of WTe₂ greatly, which is at least 7.5 times lower than that of the single‐crystalline flakes.     

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.