Ultralow thermal conductivity from transverse acoustic phonon suppression in distorted crystalline ?-MgAgSb.
ABSTRACT: Low thermal conductivity is favorable for preserving the temperature gradient between the two ends of a thermoelectric material, in order to ensure continuous electron current generation. In high-performance thermoelectric materials, there are two main low thermal conductivity mechanisms: the phonon anharmonic in PbTe and SnSe, and phonon scattering resulting from the dynamic disorder in AgCrSe2 and CuCrSe2, which have been successfully revealed by inelastic neutron scattering. Using neutron scattering and ab initio calculations, we report here a mechanism of static local structure distortion combined with phonon-anharmonic-induced ultralow lattice thermal conductivity in ?-MgAgSb. Since the transverse acoustic phonons are almost fully scattered by the compound's intrinsic distorted rocksalt sublattice, the heat is mainly transported by the longitudinal acoustic phonons. The ultralow thermal conductivity in ?-MgAgSb is attributed to its atomic dynamics being altered by the structure distortion, which presents a possible microscopic route to enhance the performance of similar thermoelectric materials.
Project description:Lead chalcogenides have exceptional thermoelectric properties and intriguing anharmonic lattice dynamics underlying their low thermal conductivities. An ideal material for thermoelectric efficiency is the phonon glass-electron crystal, which drives research on strategies to scatter or localize phonons while minimally disrupting electronic-transport. Anharmonicity can potentially do both, even in perfect crystals, and simulations suggest that PbSe is anharmonic enough to support intrinsic localized modes that halt transport. Here, we experimentally observe high-temperature localization in PbSe using neutron scattering but find that localization is not limited to isolated modes - zero group velocity develops for a significant section of the transverse optic phonon on heating above a transition in the anharmonic dynamics. Arrest of the optic phonon propagation coincides with unusual sharpening of the longitudinal acoustic mode due to a loss of phase space for scattering. Our study shows how nonlinear physics beyond conventional anharmonic perturbations can fundamentally alter vibrational transport properties.
Project description:The lattice dynamics and high-temperature structural transition in SnS and SnSe are investigated via inelastic neutron scattering, high-resolution Raman spectroscopy and anharmonic first-principles simulations. We uncover a spectacular, extreme softening and reconstruction of an entire manifold of low-energy acoustic and optic branches across a structural transition, reflecting strong directionality in bonding strength and anharmonicity. Further, our results solve a prior controversy by revealing the soft-mode mechanism of the phase transition that impacts thermal transport and thermoelectric efficiency. Our simulations of anharmonic phonon renormalization go beyond low-order perturbation theory and capture these striking effects, showing that the large phonon shifts directly affect the thermal conductivity by altering both the phonon scattering phase space and the group velocities. These results provide a detailed microscopic understanding of phase stability and thermal transport in technologically important materials, providing further insights on ways to control phonon propagation in thermoelectrics, photovoltaics, and other materials requiring thermal management.
Project description:A fundamental understanding of phonon transport in stanene is crucial to predict the thermal performance in potential stanene-based devices. By combining first-principle calculation and phonon Boltzmann transport equation, we obtain the lattice thermal conductivity of stanene. A much lower thermal conductivity (11.6 W/mK) is observed in stanene, which indicates higher thermoelectric efficiency over other 2D materials. The contributions of acoustic and optical phonons to the lattice thermal conductivity are evaluated. Detailed analysis of phase space for three-phonon processes shows that phonon scattering channels LA + LA/TA/ZA ↔ TA/ZA are restricted, leading to the dominant contributions of high-group-velocity LA phonons to the thermal conductivity. The size dependence of thermal conductivity is investigated as well for the purpose of the design of thermoelectric nanostructures.
Project description:In materials science, the substructure approach consists in imagining complex materials in which a particular property is associated with a distinct structural feature, so as to combine different chosen physical characteristics, which otherwise have little chance to coexist. Applied to thermoelectric materials, it has been used to achieve simultaneously phonon-glass and electron-crystal properties. Mostly studied for its superionic conductivity, AgCrSe2 is a naturally layered compound, which achieves very low thermal conductivity, ~0.4?W.K(-1).m(-1) at RT (room temperature), and is considered a promising thermoelectric. The Cr atoms of the [CrSe2]? layer bear a spin S?=?3/2, which orders below TN?=?55?K. Here we report low temperature inelastic neutron scattering experiments on AgCrSe2, alongside the magnetic field evolution of its thermal and electrical transport. We observe a very low frequency mode at 3?meV, ascribed to large anharmonic displacements of the Ag(+) ions in the [Ag]? layer, and 2D magnetic fluctuations up to 3 TN in the chromium layer. The low thermal conductivity of AgCrSe2 is attributed to acoustic phonon scattering by a regular lattice of Ag(+) oscillating in quasi-2D potential wells. These findings highlight a new way to achieve localised phonon modes in a perfectly crystalline solid.
Project description:Strain engineering is a practical method to tune and improve the physical characteristics and properties of two-dimensional materials, due to their large stretchability. Tensile strain dependence of electronic, phonon, and thermoelectric properties of InSe monolayer are systematically studied. We demonstrate that the lattice thermal conductivity can be effectively modulated by applying tensile strain. Tensile strain can enhance anharmonic phonon scattering, giving rise to the enhanced phonon scattering rate, reduced phonon group velocity and heat capacity, and therefore lattice thermal conductivity decreases from 25.9 to 13.1 W/mK when the strain of 6% is applied. The enhanced figure of merit indicates that tensile strain is an effective way to improve the thermoelectric performance of InSe monolayer.
Project description:A fundamental understanding of the phonon transport mechanism is important for optimizing the efficiency of thermoelectric devices. In this study, we investigate the thermal transport properties of the oxidized form of phosphorene called phosphorene oxide (PO) by solving phonon Boltzmann transport equation based on first-principles density functional theory. We reveal that PO exhibits a much lower thermal conductivity (2.42-7.08?W/mK at 300?K) than its pristine counterpart as well as other two-dimensional materials. To comprehend the physical origin of such low thermal conductivity, we scrutinize the contribution of each phonon branch to the thermal conductivity by evaluating various mode-dependent quantities including Grüneisen parameters, anharmonic three-phonon scattering rate, and phase space of three-phonon scattering processes. Our results show that its flexible puckered structure of PO leads to smaller sound velocities; its broken-mirror symmetry allows more ZA phonon scattering; and the relatively-free vibration of dangling oxygen atoms in PO gives rise to additional scattering resulting in further reduction in the phonon lifetime. These results can be verified by the fact that PO has larger phase space for three-phonon processes than phosphorene. Furthermore we show that the thermal conductivity of PO can be optimized by controlling its size or its phonon mean free path, indicating that PO can be a promising candidate for low-dimensional thermoelectric devices.
Project description:Phonons in condensed matter materials transmit energy through atomic lattices as coherent vibrational waves. Like electronic and photonic properties, an improved understanding of phononic properties is essential for the development of functional materials, including thermoelectric materials. Recently, an Einstein rattling mode was found in thermoelectric material Na0.8CoO2, due to the large displacement of Na between the [CoO2] layers. In this work, we have realized a different type of rattler in another thermoelectric material Ca3Co4O9 by chemical doping, which possesses the same [CoO2] layer as Na0.8CoO2. It remarkably suppressed the thermal conductivity while enhancing its electrical conductivity. This new type of rattler was investigated by inelastic neutron scattering experiments in conjunction with ab-initio molecular dynamics simulations. We found that the large mass of dopant rather than the large displacement is responsible for such rattling in present study, which is fundamentally different from skutterudites, clathrates as well as Na analogue. We have also tentatively studied the phonon band structure of this material by DFT lattice dynamics simulation, showing the relative contribution to phonons in the distinct layers of Ca3Co4O9.
Project description:Crystalline solids exhibiting glass-like thermal conductivity have attracted substantial attention both for fundamental interest and applications such as thermoelectrics. In most crystals, the competition of phonon scattering by anharmonic interactions and crystalline imperfections leads to a non-monotonic trend of thermal conductivity with temperature. Defect-free crystals that exhibit the glassy trend of low thermal conductivity with a monotonic increase with temperature are desirable because they are intrinsically thermally insulating while retaining useful properties of perfect crystals. However, this behavior is rare, and its microscopic origin remains unclear. Here, we report the observation of ultralow and glass-like thermal conductivity in a hexagonal perovskite chalcogenide single crystal, BaTiS<sub>3</sub>, despite its highly symmetric and simple primitive cell. Elastic and inelastic scattering measurements reveal the quantum mechanical origin of this unusual trend. A two-level atomic tunneling system exists in a shallow double-well potential of the Ti atom and is of sufficiently high frequency to scatter heat-carrying phonons up to room temperature. While atomic tunneling has been invoked to explain the low-temperature thermal conductivity of solids for decades, our study establishes the presence of sub-THz frequency tunneling systems even in high-quality, electrically insulating single crystals, leading to anomalous transport properties well above cryogenic temperatures.
Project description:Engineering lattice thermal conductivity requires to control the heat carried by atomic vibration waves, the phonons. The key parameter for quantifying it is the phonon lifetime, limiting the travelling distance, whose determination is however at the limits of instrumental capabilities. Here, we show the achievement of a direct quantitative measurement of phonon lifetimes in a single crystal of the clathrate Ba<sub>7.81</sub>Ge<sub>40.67</sub>Au<sub>5.33</sub>, renowned for its puzzling 'glass-like' thermal conductivity. Surprisingly, thermal transport is dominated by acoustic phonons with long lifetimes, travelling over distances of 10 to 100?nm as their wave-vector goes from 0.3 to 0.1?Å<sup>-1</sup>. Considering only low-energy acoustic phonons, and their observed lifetime, leads to a calculated thermal conductivity very close to the experimental one. Our results challenge the current picture of thermal transport in clathrates, underlining the inability of state-of-the-art simulations to reproduce the experimental data, thus representing a crucial experimental input for theoretical developments.Phonon lifetime is a fundamental parameter of thermal transport however its determination is challenging. Using inelastic neutron scattering and the neutron resonant spin-echo technique, Lory et al. determine the acoustic phonon lifetime in a single crystal of clathrate Ba7.81Ge40.67Au5.33.
Project description:Which sizes of nanoparticles embedded in a crystalline solid yield the lowest thermal conductivity? Nanoparticles have long been demonstrated to reduce the thermal conductivity of crystals by scattering phonons, but most previous works assumed the nanoparticles to have a single size. Here, we use optimization methods to show that the best nanoparticle size distribution to scatter the broad thermal phonon spectrum is not a similarly broad distribution but rather several discrete peaks at well-chosen nanoparticle radii. For SiGe, the best size distribution yields a thermal conductivity below that of amorphous silicon. Further, we demonstrate that a simplified distribution yields nearly the same low thermal conductivity and can be readily fabricated. Our work provides important insights into how to manipulate the full spectrum of phonons and will guide the design of more efficient thermoelectric materials.