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.

Metavalent Bonding-Mediated Dual 6s2 Lone Pair Expression Leads to Intrinsic Lattice Shearing in n-Type TlBiSe2.

Metavalent bonding has attracted immense interest owing to its capacity to impart a distinct property portfolio to materials for advanced functionality. Coupling metavalent bonding to lone pair expression can be an innovative way to propagate lattice anharmonicity from lone pair-induced local symmetry-breaking via the soft p-bonding electrons to achieve long-range phonon dampening in crystalline solids. Motivated by the shared chemical design pool for topological quantum materials and thermoelectrics, we based our studies on a three-dimensional (3D) topological insulator TlBiSe2 that held prospects for 6s2 dual-cation lone pair expression and metavalent bonding to investigate if the proposed hypothesis can deliver a novel thermoelectric material. Herein, we trace the inherent phononic origin of low thermal conductivity in n-type TlBiSe2 to dual 6s2 lone pair-induced intrinsic lattice shearing that strongly suppresses the lattice thermal conductivity to a low value of 1.1-0.4 Wm-1 K-1 between 300 and 715 K. Through synchrotron X-ray pair distribution function and first-principles studies, we have established that TlBiSe2 exists not in a monomorphous R-3m structure but as a distribution of distorted configurations. Via a cooperative movement of the constituent atoms akin to a transverse shearing mode facilitated by metavalent bonding in TlBiSe2, the structure shuttles between various energetically accessible low-symmetry structures. The orbital interactions and ensuing multicentric bonding visualized through Wannier functions augment the long-range transmission of atomic displacement effects in TlBiSe2. With additional point-defect scattering, a κlatt of 0.3 Wm-1 K-1 was achieved in TlBiSeS with a maximum n-type thermoelectric figure of merit (zT) of ∼0.8 at 715 K.

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.

Local Symmetry Breaking Suppresses Thermal Conductivity in Crystalline Solids.

Understanding the correlations of both the local and global structures with lattice dynamics is critical for achieving low lattice thermal conductivity (κlat ) in crystalline materials. Herein, we demonstrate local cationic off-centring within the global rock-salt structure of AgSbSe2 by using synchrotron X-ray pair distribution function analysis and unravel the origin of its ultralow κlat ≈0.4 W mK-1 at 300 K. The cations are locally off-centered along the crystallographic ⟨ 100 ⟩ direction by about ≈0.2 Å, which averages out as the rock-salt structure on the global scale. Phonon dispersion obtained by density functional theory (DFT) shows weak instabilities that cause local off-centering distortions within an anharmonic double-well potential. The local structural distortion arises from the stereochemically active 5s2 lone pairs of Sb. Our findings open an avenue for understanding how the local structure influences the phonon transport and facilitates the design of next-generation crystalline materials with tailored thermal properties.

Emphanisis in Cubic (SnSe)0.5(AgSbSe2)0.5: Dynamical Off-Centering of Anion Leads to Low Thermal Conductivity and High Thermoelectric Performance.

The structural transformation generally occurs from lower symmetric to higher symmetric structure on heating. However, the formation of locally broken asymmetric phases upon warming has been evidenced in PbQ (Q = S, Se, Te), a rare phenomenon called emphanisis, which has significant effect on their thermal transport and thermoelectric properties. (SnSe)0.5(AgSbSe2)0.5 crystallizes in rock-salt cubic average structure, with the three cations occupying the same Wycoff site (4a) and Se in the anion position (Wycoff site, 4b). Using synchrotron X-ray pair distribution function (X-PDF) analysis, herein, we show the gradual deviation of the local structure of (SnSe)0.5(AgSbSe2)0.5 from the overall cubic rock-salt structure with warming, resembling emphanisis. The local structural analysis indicates that Se atoms remain in off-centered position by a magnitude of ∼0.25 Å at 300 K along the [111] direction and the magnitude of this distortion is found to increase with temperature resulting in three short and three long M-Se bonds (M = Sn/Ag/Sb) within the average rock-salt lattice. This hinders phonon propagation and lowers the lattice thermal conductivity (κlat) to 0.49-0.39 W/(m·K) in the 295-725 K range. Analysis of phonons based on density functional theory (DFT) reveals significant soft modes with high anharmonicity which involve localized Ag and Se vibrations primarily. Emphanisis induced low κlat and favorable electronic structure with multiple valence band extrema within close energy concurrently give rise to a promising thermoelectric figure of merit (zT) of 1.05 at 706 K in p-type carrier optimized Ge doped new rock-salt phase of (SnSe)0.5(AgSbSe2)0.5.

Evidence of Highly Anharmonic Soft Lattice Vibrations in a Zintl Rattler.

Here, we present lattice dynamics associated with the local chemical bonding hierarchy in Zintl compound TlInTe2 , which cause intriguing phonon excitations and strongly suppress the lattice thermal conductivity to an ultralow value (0.46-0.31 W m-1 K-1 ) in the 300-673 K. We established an intrinsic rattling nature in TlInTe2 by studying the local structure and phonon vibrations using synchrotron X-ray pair distribution function (PDF) (100-503 K) and inelastic neutron scattering (INS) (5-450 K), respectively. We showed that while 1D chain of covalently bonded I n T e 2 n - n transport heat with Debye type phonon excitation, ionically bonded Tl rattles with a frequency ca. 30 cm-1 inside distorted Thompson cage formed by I n T e 2 n - n . This highly anharmonic Tl rattling causes strong phonon scattering and consequently phonon lifetime reduces to ultralow value of ca. 0.66(6) ps, resulting in ultralow thermal conductivity in TlInTe2 .

Ultralow Thermal Conductivity in Chain-like TlSe Due to Inherent Tl+ Rattling.

Understanding the mechanism that correlates phonon transport with chemical bonding and solid-state structure is the key to envisage and develop materials with ultralow thermal conductivity, which are essential for efficient thermoelectrics and thermal barrier coatings. We synthesized thallium selenide (TlSe), which is comprised of intertwined stiff and weakly bonded substructures and exhibits intrinsically ultralow lattice thermal conductivity (κL) of 0.62-0.4 W/mK in the range 295-525 K. Ultralow κL of TlSe is a result of its low energy optical phonon modes which strongly interact with the heat carrying acoustic phonons. Low energy optical phonons of TlSe are associated with the intrinsic rattler-like vibration of Tl+ cations in the cage constructed by the chains of (TlSe2)nn-, as evident in low temperature heat capacity, terahertz time-domain spectroscopy, and temperature dependent Raman spectroscopy. Density functional theoretical analysis reveals the bonding hierarchy in TlSe which involves ionic interaction in Tl+-Se while Tl3+-Se bonds are covalent, which causes significant lattice anharmonicity and intrinsic rattler-like low energy vibrations of Tl+, resulting in ultralow κL.

Local Structure and Influence of Sb Substitution on the Structure-Transport Properties in AgBiSe2.

Owing to their intrinsically low thermal conductivity and chemical diversity, materials within the I-V-VI2 family, and especially AgBiSe2, have recently attracted interest as promising thermoelectric materials. However, further investigations are needed in order to develop a more fundamental understanding of the origin of the low thermal conductivity in AgBiSe2, to evaluate possible stereochemical activity of the 6s2 lone pair of Bi3+, and to further elaborate on chemical design approaches for influencing the occurring phase transitions. In this work, a combination of temperature-dependent X-ray diffraction, Rietveld refinements of laboratory X-ray diffraction data, and pair distribution function analyses of synchrotron X-ray diffraction data is used to tackle the influence of Sb substitution within AgBi1-xSbxSe2 (0 ⩽ x ⩽ 0.15) on the phase transitions, local distortions, and off-centering of the structure. This work shows that, similar to other lone-pair-containing materials, local off-centering and distortions can be found in AgBiSe2. Furthermore, electronic and thermal transport measurements, in combination with the modeling of point-defect scattering, highlight the importance of structural characterizations toward understanding changes induced by elemental substitutions. This work provides new insights into the structure-transport correlations of the thermoelectric AgBiSe2.

Tuning of p-n-p-Type Conduction in AgCuS through Cation Vacancy: Thermopower and Positron Annihilation Spectroscopy Investigations.

Understanding the complex phenomenon behind the structural transformations is a key requisite to developing important solid-state materials with better efficacy such as transistors, resistive switches, thermoelectrics, etc. AgCuS, a superionic semiconductor, exhibits temperature-dependent p-n-p-type conduction switching and a colossal jump in thermopower during an orthorhombic to hexagonal superionic transition. Tuning of p-n-p-type conduction switching in superionic compounds is fundamentally important to realize the correlation between electronic/phonon dispersion modulation with changes in the crystal structure and bonding, which might contribute to the design of better thermoelectric materials. Herein, we have created extrinsic Ag/Cu nonstoichiometry in AgCuS, which resulted in the vanishing of p-n-p-type conduction switching and improved its thermoelectric properties. We have performed the selective removal of cations and measured their temperature-dependent thermopower and Hall coefficient, which demonstrates only p-type conduction in the Ag1- xCuS and AgCu1- xS samples. The removal of Cu is much more efficient in arresting conduction switching, whereas in the case of Ag vacancy, p-n-p-type conduction switching vanishes at higher vacant concentrations. Positron annihilation spectroscopy measurements have been done to shed further light on the mechanisms behind this structural transition-dependent conduction switching. Cation (Ag+/Cu+) nonstoichiometry in AgCuS significantly increases the vacancy concentration, hence, the p-type carriers, which is confirmed by positron annihilation spectroscopy and Hall measurement. The Ag1- xCuS and AgCu1- xS samples exhibit ultralow thermal conductivity (∼0.3-0.5 W/m·K) in the 290-623 K temperature range because of the low-energy cationic sublattice vibration that arises as a result of the movement of loosely bound Ag/Cu within the stiff S sublattice.