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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. [ABSTRACT FROM AUTHOR]

Thermal conductivity, which measures the ease at which heat passes through a crystalline solid, is controlled by the nature of the chemical bonding and periodicity in the solid. This necessitates an in‐depth understanding of the crystal structure and chemical bonding to tailor materials with notable lattice thermal conductivity (κL). Herein, the nature of chemical bonding and its influence on the thermal transport properties (2–523 K) of all‐inorganic halide perovskite Cs3Bi2I9 are studied. The κL exhibits an ultralow value of ≈0.20 W m−1K−1 in 30–523 K temperature range. The antibonding states just below the Fermi level in the electronic structure arising from the interaction between bismuth 6s and iodine 5p orbitals, weakens the bond and causes soft elasticity in Cs3Bi2I9. First‐principles density functional theory (DFT) calculations reveal highly localized soft optical phonon modes originating from Cs‐rattling and dynamic double octahedral distortion of 0D [Bi2I9]3− in Cs3Bi2I9. These low energy nearly flat optical phonons strongly interact with transverse acoustic modes creating an ultrashort phonon lifetime of ≈1 ps. While the presence of extended antibonding states gives rise to soft anharmonic lattice; Cs rattling provides sharp localized optical phonon modes, which altogether result in strong lattice anharmonicity and ultralow κL. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

As the periodic atomic arrangement of a crystal is made to a disorder or glassy-amorphous system by destroying the long-range order, lattice thermal conductivity, κL, decreases, and its fundamental characteristics changes. The realization of ultralow and unusual glass-like κL in a crystalline material is challenging but crucial to many applications like thermoelectrics and thermal barrier coatings. Herein, we demonstrate an ultralow (~0.20 W/m·K at room temperature) and glass-like temperature dependence (2–400 K) of κL in a single crystal of layered halide perovskite, Cs3Bi2I6Cl3. Acoustic phonons with low cut-off frequency (20 cm−1) are responsible for the low sound velocity in Cs3Bi2I6Cl3 and make the structure elastically soft. While a strong anharmonicity originates from the low energy and localized rattling-like vibration of Cs atoms, synchrotron X-ray pair-distribution function evidence a local structural distortion in the Bi-halide octahedra and Cl vacancy. The hierarchical chemical bonding and soft vibrations from selective sublattice leading to low κL is intriguing from lattice dynamical perspective as well as have potential applications. The investigation of thermal conductivity is crucial to the success of many modern technologies. Here the authors have reported an unusual glass-like thermal conductivity in a single crystal of layered halide perovskite, Cs3Bi2I6Cl3. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

A remarkable decrease in the lattice thermal conductivity and enhancement of thermoelectric figure of merit were recently observed in rock-salt cubic SnTe, when doped with germanium (Ge). Primarily, based on theoretical analysis, the decrease in lattice thermal conductivity was attributed to local ferroelectric fluctuations induced softening of the optical phonons which may strongly scatter the heat carrying acoustic phonons. Although the previous structural analysis indicated that the local ferroelectric transition temperature would be near room temperature in Sn 0.7 Ge 0.3 Te , a direct evidence of local ferroelectricity remained elusive. Here we report a direct evidence of local nanoscale ferroelectric domains and their switching in Sn 0.7 Ge 0.3 Te using piezoeresponse force microscopy(PFM) and switching spectroscopy over a range of temperatures near the room temperature. From temperature dependent (250–300 K) synchrotron X-ray pair distribution function (PDF) analysis, we show the presence of local off-centering distortion of Ge along the rhombohedral direction in global cubic Sn 0.7 Ge 0.3 Te . The length scale of the Ge 2 + off-centering is 0.25–0.10 Å near the room temperatures (250–300 K). This local emphatic behaviour of cation is the cause for the observed local ferroelectric instability, thereby low lattice thermal conductivity in Sn 0.7 Ge 0.3 Te . [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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 InTe2n-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 InTe2n-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. [ABSTRACT FROM AUTHOR]

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 InTe2n-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 InTe2n-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. [ABSTRACT FROM AUTHOR]

Thermoelectric energy conversion from waste heat sources is expected to play a crucial role in determining the world energy landscape through efficient thermal energy utilization and management. The thermoelectric performance of a material critically depends on its electrical conductivity and Seebeck coefficient. The electronic structure plays a pivotal role in determining both these parameters, electrical conductivity and Seebeck coefficient, in a material and, therefore, in turn, dominantly controls the material's thermoelectric performance. For example, a common feature among most of the known high-performance thermoelectric materials is that they are heavily doped degenerate semiconductors and have large band degeneracy. Therefore, it is essential to improve our understanding and manipulation capabilities of the electronic structure in a material. Intensive research on thermoelectric materials has led to various novel electronic structure modulation strategies, such as valence band convergence, resonant level, and employment of various low dimensional electronic features. These strategies play a critical role in the recent developments of various high-performance thermoelectric materials, such as PbTe, SnTe, SnSe, and GeTe. In this Perspective, we have discussed various electronic structure modulation strategies and their recent developments with a brief background of the underlying ideas. [ABSTRACT FROM AUTHOR]

With the apparent burgeoning energy crisis, alternative sources of energies are in a greater need for a sustainable future. Thermoelectrics which can convert waste heat arising from industries, power plants and automobiles into a usable form, electricity; have the potential to be a game-changer in this critical energy shortage. The efficiency of thermoelectric materials which is given by the figure of merit is tricky to manipulate due to the complicated interrelationships of its parameters. But with proper understanding of a material and with the aid of periodic table, one can manoeuvre the shortcomings which hinder its efficiency. In this perspective, we discuss how the properties of materials can be manipulated just by understanding the elements of the periodic table and how each element in their respective position in the periodic table influences the outcome of high performing thermoelectric material. Thermoelectrics being an alternative clean energy solution is important in mitigating the looming energy crisis by converting waste heat into electricity. Here, we show how the periodicity of elements influences the physical properties that govern the efficiency of thermoelectric materials and help us to achieve high-performance thermoelectrics. [ABSTRACT FROM AUTHOR]

Tailoring the electronic structure of topological crystalline insulators (TCIs) is necessary to enhance their thermoelectric (TE) performance. p-Type chemical doping in a TCI such as Pb0.6Sn0.4Te exhibited a significantly high TE figure of merit (zT), but the n-type Pb0.6Sn0.4Te is still elusive and is urgently needed for thermoelectric applications. Herein, we report enhanced thermoelectric performance in n-type iodine (I) doped Pb0.6Sn0.4Te. Aliovalent I− doping in the Te2− sublattice of Pb0.6Sn0.4Te widens the band gap via breaking of local crystal mirror symmetry, which decreases the bipolar conduction and pushes the Seebeck maxima towards high temperatures. Iodine doping in Pb0.6Sn0.4Te significantly increases the n-type carrier concentration and shifts the chemical potential (Fermi level) inside the conduction band of Pb0.6Sn0.4Te, thus improving the electrical transport properties. We report a maximum zT of 1.05 in the n-type Pb0.60Sn0.40Te0.995I0.005 sample at 620 K, which is 483% higher than pristine Pb0.6Sn0.4Te. [ABSTRACT FROM AUTHOR]