Hidden structures: a driving factor to achieve low thermal conductivity and high thermoelectric performance.

The long-range periodic atomic arrangement or the lack thereof in solids typically dictates the magnitude and temperature dependence of their lattice thermal conductivity (κlat). Compared to crystalline materials, glasses exhibit a much-suppressed κlat across all temperatures as the phonon mean free path reaches parity with the interatomic distances therein. While the occurrence of such glass-like thermal transport in crystalline solids captivates the scientific community with its fundamental inquiry, it also holds the potential for profoundly impacting the field of thermoelectric energy conversion. Therefore, efficient manipulation of thermal transport and comprehension of the microscopic mechanisms dictating phonon scattering in crystalline solids are paramount. As quantized lattice vibrations (i.e., phonons) drive κlat, atomistic insights into the chemical bonding characteristics are crucial to have informed knowledge about their origins. Recently, it has been observed that within the highly symmetric 'averaged' crystal structures, often there are hidden locally asymmetric atomic motifs (within a few Å), which exert far-reaching influence on phonon transport. Phenomena such as local atomic off-centering, atomic rattling or tunneling, liquid-like atomic motion, site splitting, local ordering, etc., which arise within a few Å scales, are generally found to drastically disrupt the passage of heat carrying phonons. Despite their profound implication(s) for phonon dynamics, they are often overlooked by traditional crystallographic techniques. In this review, we provide a brief overview of the fundamental aspects of heat transport and explore the status quo of innately low thermally conductive crystalline solids, wherein the phonon dynamics is majorly governed by local structural phenomena. We also discuss advanced techniques capable of characterizing the crystal structure at the sub-atomic level. Subsequently, we delve into the emergent new ideas with examples linked to local crystal structure and lattice dynamics. While discussing the implications of the local structure for thermal conductivity, we provide the state-of-the-art examples of high-performance thermoelectric materials. Finally, we offer our viewpoint on the experimental and theoretical challenges, potential new paths, and the integration of novel strategies with material synthesis to achieve low κlat and realize high thermoelectric performance in crystalline solids via local structure designing.

Room-Temperature Synthesis and Low Thermal Conductivity in Nanocrystalline Ag3CuS2.

Noble-metal-based chalcogenide materials recently gained massive attention in the field of thermoelectrics. In most cases, materials are synthesized using (i) high-temperature solid-state reactions or (ii) soft chemical methods where temperature requirements are lower than those of solid-state reactions (generally below 400 °C). Herein, we present a simple, surfactant-free, room-temperature, and energy-efficient synthesis of Ag3CuS2 nanocrystals. The present synthesis technique is scalable and capable of gram-scale production. A spark plasma sintering (SPS) pressed sample exhibits ultralow thermal conductivity (∼0.31 W/mK at room temperature). We found that Ag3CuS2 exhibits low sound velocity, as well as a non-Debye-like behavior based on a low-temperature heat capacity measurement. A high degree of anharmonicity of bonding, soft vibrations modes, and nanoscale grain boundary scattering in Ag3CuS2 lead to ultralow thermal conductivity, which can be important for thermoelectrics, optoelectronics, and thermal barrier coating applications.

Chemically Transformed Ag2 Te Nanowires on Polyvinylidene Fluoride Membrane For Flexible Thermoelectric Applications.

Flexible thermoelectric devices of nanomaterials have shown a great potential for applications in wearable to remotely located electronics with desired shapes and geometries. Continuous powering up the low power flexible electronics is a major challenge. We are reporting a flexible thermoelectric module prepared from silver telluride (Ag2 Te) nanowires (NWs), which are chemically transformed from uniquely synthesized and scalable tellurium (Te) NWs. Conducting Ag2 Te NWs composites have shown an ultralow total thermal conductivity ~0.22 W/mK surpassing the bulk melt-grown Ag2 Te ~1.23 W/mK at ~300 K, which is attributed to the nanostructuring of the material. Flexible thermoelectric device consisting of 4 legs (n-type) of Ag2 Te NWs on polyvinylidene fluoride membrane displays a significant output voltage (Voc ) ~2.3 mV upon human touch and Voc ~18 mV at temperature gradient, ΔT ~50 K, which shows the importance of NWs based flexible thermoelectric devices to power up the low power wearable electronics.

Strained Lamellar Structures Leading to Improved Thermoelectric Performance in Mg3Sb1.5Bi0.5.

Mg3Sb2-xBix solid-solutions represent an important class of thermoelectric (TE) materials due to their high efficiency and variable operating temperature range. Of particular significance for midtemperature applications is the Mg3Sb1.5Bi0.5 composition whose superior thermoelectric (TE) performance is attributed to the complex conduction band edge in conjunction with alloy dominated phonon scattering. In this work, we show that microstructure also plays a significant role in lowering the lattice thermal conductivity which in turn affects the overall TE performance (change in peak zT values between 1.1 and 1.4 have been observed). Temperature dependent TE properties of Mg3+xSb1.5Bi0.5 compositions with varying nominal Mg content (x = 0.2, 0.3, 0.4) have been studied. A marked reduction of the lattice thermal conductivity (κL) is observed in compositions with low nominal Mg content (x = 0.2), which is due to the presence of lamellar structures within the grains. These lamellar regions are isostructural to the matrix with a low misfit angle and represent compositional fluctuations in the Bi to Sb ratio. Both the size (200 nm-500 nm) and the interfacial strain contribute to the enhanced phonon scattering. A quantitative estimate of κL reduction due to these structures have been carried out using a mean free path (MFP) spectrum analysis which reveal a good match with experiments at room temperature. Further, the electrical properties are not influenced by these lamellar structures as observed from the similar power-factor (S2σ) and weighted mobilities in all of the compositions. This is due to their similar orientation to the adjacent matrix region. Thus, the zT parameter in the various compositions with similar carrier concentration can be significantly altered (∼25%) by adjusting the nominal Mg content. The results demonstrate that preferential phonon scattering by microstructure modification can be a new route for property improvement in Mg3+xSb2-yBiy solid-solutions.

Chemical Bonding Tuned Lattice Anharmonicity Leads to a High Thermoelectric Performance in Cubic AgSnSbTe3.

Comprehension of chemical bonding and its intertwined relation with charge carriers and heat propagation through a crystal lattice is imperative to design compounds for thermoelectric energy conversion. Here, we report the synthesis of large single crystal of new p-type cubic AgSnSbTe3 which shows an innately ultra-low lattice thermal conductivity (κlat ) of 0.47-0.27 Wm-1  K-1 and a high electrical conductivity (1238 - 800 S cm-1 ) in the temperature range 294-723 K. We investigated the origin of the low κlat by analysing the nature of the chemical bonding and its crystal structure. The interaction between Sn(5 s)/Ag(4d) and Te(5p) orbitals was found to generate antibonding states just below the Fermi level in the electronic band structure, resulting in a softening of the lattice in AgSnSbTe3 . Furthermore, the compound exhibits metavalent bonding which provides highly polarizable bonds with a strong lattice anharmonicity while maintaining the superior electrical conductivity. The electronic band structure exhibits nearly degenerate valence-band maxima that help to achieve a high Seebeck coefficient throughout the measured temperature range and, as a result, the maximum thermoelectric figure of merit reaches to ≈1.2 at 661 K in pristine single crystal of AgSnSbTe3 .

Insights into Low Thermal Conductivity in Inorganic Materials for Thermoelectrics.

Efficient manipulation of thermal conductivity and fundamental understanding of the microscopic mechanisms of phonon scattering in crystalline solids are crucial to achieve high thermoelectric performance. Thermoelectric energy conversion directly and reversibly converts between heat and electricity and is a promising renewable technology to generate electricity by recovering waste heat and improve solid-state refrigeration. However, a unique challenge in thermal transport needs to be addressed to achieve high thermoelectric performance: the requirement of crystalline materials with ultralow lattice thermal conductivity (κL). A plethora of strategies have been developed to lower κL in crystalline solids by means of nanostructural modifications, introduction of intrinsic or extrinsic phonon scattering centers with tailored shape and dimension, and manipulation of defects and disorder. Recently, intrinsic local lattice distortion and lattice anharmonicity originating from various mechanisms such as rattling, bonding heterogeneity, and ferroelectric instability have found popularity. In this Perspective, we outline the role of manipulation of chemical bonding and structural chemistry on thermal transport in various high-performance thermoelectric materials. We first briefly outline the fundamental aspects of κL and discuss the current status of the popular phonon scattering mechanisms in brief. Then we discuss emerging new ideas with examples of crystal structure and lattice dynamics in exemplary materials. Finally, we present an outlook for focus areas of experimental and theoretical challenges, possible new directions, and integrations of novel techniques to achieve low κL in order to realize high-performance thermoelectric materials.

Enhanced Band Convergence and Ultra-Low Thermal Conductivity Lead to High Thermoelectric Performance in SnTe.

SnTe, a structural analogue of champion thermoelectric (TE) material PbTe, has recently attracted wide attention for TE energy conversion. Herein, we demonstrate a co-doping strategy to improve the TE performance of SnTe via simultaneous modulation of electronic structure and phonon transport. The electrical transport is optimized by 3 mol % Ag doping in self-compensated SnTe (i.e., Sn1.03 Te). Further, Mg doping in SnAg0.03 Te resulted in highly converged valence bands, which enhanced the Seebeck coefficient markedly. The energy gap between two uppermost valence bands (ΔEv ) decreases to 0.10 eV in Sn0.92 Ag0.03 Mg0.08 Te compared to 0.35 eV in pristine SnTe. The optimized p-type carrier concentration and highly converged valence bands gave a high power factor of ca. 27 µW cm-1 K-2 at 865 K in Sn0.92 Ag0.03 Mg0.08 Te. The lattice thermal conductivity of Sn0.92 Ag0.03 Mg0.08 Te reached to an ultra-low value of ≈0.23 W m-1 K-1 at 865 K due to the formation of MgTe nanoprecipitates in SnTe matrix. These combined effects resulted in a high TE figure of merit, zT≈1.55 at 865 K in Sn0.92 Ag0.03 Mg0.08 Te.

Intrinsically ultralow thermal conductive inorganic solids for high thermoelectric performance.

Thermoelectric materials which can convert heat energy to electricity rely on crystalline inorganic solid state compounds exhibiting low phonon transport (i.e. low thermal conductivity) without much inhibiting the electrical transport. Suppression of phonons traditionally has been carried out via extrinsic pathways, involving formation of point defects, foreign nanostructures, and meso-scale grains, but the incorporation of extrinsic substituents also influences the electrical properties. Crystalline materials with intrinsically low lattice thermal conductivity (κlat) provide an attractive paradigm as it helps in simplifying the complex interrelated thermoelectric parameters and allows us to focus largely on improving the electronic properties. In this feature article, we have discussed the chemical bonding and structural aspects in determining phonon transport through a crystalline material. We have outlined how the inherent material properties like lone pair, bonding anharmonicity, presence of intrinsic rattlers, ferroelectric instability, weak and rigid substructures, etc. influence in effectively suppressing the heat transport. The strategies summarized in this feature article should serve as a general guide to rationally design and predict materials with low κlat for potential thermoelectric applications.

Metavalent Bonding in GeSe Leads to High Thermoelectric Performance.

Orthorhombic GeSe is a promising thermoelectric material. However, large band gap and strong covalent bonding result in a low thermoelectric figure of merit, zT≈0.2. Here, we demonstrate a maximum zT≈1.35 at 627 K in p-type polycrystalline rhombohedral (GeSe)0.9 (AgBiTe2 )0.1 , which is the highest value reported among GeSe based materials. The rhombohedral phase is stable in ambient conditions for x=0.8-0.29 in (GeSe)1-x (AgBiTe2 )x . The structural transformation accompanies change from covalent bonding in orthorhombic GeSe to metavalent bonding in rhombohedral (GeSe)1-x (AgBiTe2 )x . (GeSe)0.9 (AgBiTe2 )0.1 has closely lying primary and secondary valence bands (within 0.25-0.30 eV), which results in high power factor 12.8 µW cm-1 K-2 at 627 K. It also exhibits intrinsically low lattice thermal conductivity (0.38 Wm-1 K-1 at 578 K). Theoretical phonon dispersion calculations reveal vicinity of a ferroelectric instability, with large anomalous Born effective charges and high optical dielectric constant, which, in concurrence with high effective coordination number, low band gap and moderate electrical conductivity, corroborate metavalent bonding in (GeSe)0.9 (AgBiTe2 )0.1 . We confirmed the presence of low energy phonon modes and local ferroelectric domains using heat capacity measurement (3-30 K) and switching spectroscopy in piezoresponse force microscopy, respectively.

Ferroelectric Instability Induced Ultralow Thermal Conductivity and High Thermoelectric Performance in Rhombohedral p-Type GeSe Crystal.

The orthorhombic phase of GeSe, a structural analogue of layered SnSe (space group: Pnma), has recently attracted attention after a theoretical prediction of high thermoelectric figure of merit, zT > 2. The experimental realization of such high performance in orthorhombic GeSe, however, is still elusive (zT ≈ 0.2). The rhombohedral phase of GeSe, a structural analogue of GeTe (space group: R3m), previously stabilized at high pressure (2 GPa) and high temperature (1600 K), is promising due to its theoretically predicted ferroelectric instability and the higher earth abundance of Se compared to Te. Here, we demonstrate high thermoelectric performance in the rhombohedral crystals of GeSe, which is stabilized at ambient conditions by alloying with 10 mol % AgBiSe2. We show ultralow lattice thermal conductivity (κL) of 0.74-0.47 W/mK in the 300-723 K range and high zT ≈ 1.25 at 723 K in the p-type rhombohedral (GeSe)0.9(AgBiSe2)0.1 crystals grown using Bridgman method. First-principles density functional theoretical analysis reveals its vicinity to a ferroelectric instability which generates large anomalous Born effective charges and strong coupling of low energy polar optical phonons with acoustic phonons. The presence of soft optical phonons and incipient ferroelectric instability in (GeSe)0.9(AgBiSe2)0.1 are directly evident in the low temperature heat capacity (Cp) and switching spectroscopy piezoresponse force microscopy (SS-PFM) experiments, respectively. Effective scattering of heat carrying acoustic phonons by ferroelectric instability induced soft transverse optical phonons significantly reduces the κL and enhances the thermoelectric performance in rhombohedral (GeSe)0.9(AgBiSe2)0.1 crystals.

Highly Converged Valence Bands and Ultralow Lattice Thermal Conductivity for High-Performance SnTe Thermoelectrics.

A two-step optimization strategy is used to improve the thermoelectric performance of SnTe via modulating the electronic structure and phonon transport. The electrical transport of self-compensated SnTe (that is, Sn1.03 Te) was first optimized by Ag doping, which resulted in an optimized carrier concentration. Subsequently, Mn doping in Sn1.03-x Agx Te resulted in highly converged valence bands, which improved the Seebeck coefficient. The energy gap between the light and heavy hole bands, i.e. ΔEv decreases to 0.10 eV in Sn0.83 Ag0.03 Mn0.17 Te compared to the value of 0.35 eV in pristine SnTe. As a result, a high power factor of ca. 24.8 µW cm-1 K-2 at 816 K in Sn0.83 Ag0.03 Mn0.17 Te was attained. The lattice thermal conductivity of Sn0.83 Ag0.03 Mn0.17 Te reached to an ultralow value (ca. 0.3 W m-1 K-1 ) at 865 K, owing to the formation of Ag7 Te4 nanoprecipitates in SnTe matrix. A high thermoelectric figure of merit (z T≈1.45 at 865 K) was obtained in Sn0.83 Ag0.03 Mn0.17 Te.