Anharmonic Phonon Research Articles

Tailoring Ni/Fe Doping for Superior Thermoelectric Performance of Zr2Ni2−xFexSnSb (x = 0.30, 0.35, 0.40) High‐Entropy Alloys

Half‐Heusler (hH) compounds are emerging as promising materials for thermoelectric applications, owing to their exceptional mechanical and thermal stability, combined with the absence of toxic elements. These characteristics make hH compounds an attractive subject for detailed study and potential use in advanced thermoelectric systems. However, its thermoelectric applicability is limited because of high lattice thermal conductivity (κl). Various strategies, such as phase separation, grain‐boundary scatterings, and electron–phonon interactions, have been used to reduce κl, which enhances phonon scatterings. Recently, high‐entropy hH alloys have gained significant attention due to their distorted structure that inherently incorporates high phonon scattering features, addressing the key issue of hH. Herein, hH high‐entropy alloys (Zr2Ni2−xFexSnSb; x = 0.30, 0.35, 0.40) have been synthesized by arc melting and heat treatment. A significantly reduced lattice thermal conductivities (<2.25 W mK−1 at 985 K) are obtained due to the presence of multicomponents, which scatter phonon significantly. Experimental observation is very well complimented with density functional theory findings by analyzing phonon dispersions, chemical bonding, group velocities, and anharmonicity. Thereby, it is demonstrated that a high thermoelectric figure of merit is achieved in the proposed hH high‐entropy alloys by strengthening the phonon scatterings.

H$_{3}$Se in the $Im\overline{3}m$ Phase: A High-Pressure Superconductor with $T_{\text{c}}$ Reaching 200 K at 64 GPa Mediated by Anharmonic Phonons

Abstract Hydrogen-based compounds have attracted significant attention in recent years due to the discovery of conventional superconductivity with high critical temperature under high pressure, rekindling hopes for searching room temperature superconductor. In this work, we investigated systematically the vibrational and superconducting properties of H$_{3}$Se in $Im\overline{3}m$ phase under pressures ranging from 50 to 200 GPa. Our approach combines the stochastic self-consistent harmonic approximation with first-principles calculations to address effects from the quantum and anharmonic vibrations of ions. It turns out that these effects significantly modify the crystal structure, increasing the inner pressure by about 8 GPa compared to situations where they are ignored. The phonon spectra suggest that with these effects included, the crystal can be stabilized at pressures as low as about 61 GPa, much lower than the previously predicted value of over 100 GPa. Our calculations also highlight the critical role of quantum and anharmonic effects on the electron-phonon coupling properties. Neglecting these factors could result in a substantial overestimation of the superconducting critical temperature $T_{\text{c}}$, by approximately 25 K at 125 GPa, for example. With anharmonic phonons, the $T_{\text{c}}$ derived from the Migdal-Eliashberg equations, reaches 200 K ($\mu^\star=0.1, \lambda$=4.1) as the pressure decreases to 64 GPa, making the crystal a rare high-$T_{\text{c}}$ superconductor at moderate pressures.

Electric Structure and Thermoelectric Performance in Cs2O Crystal

In this work, first principles DFT calculations has been employed with anharmonic phonon scatter theory and Boltzmann transport method to perform a exhaustive study on the thermoelectric properties as electronic and phonon transport of layered Cs2O crystal. The results indicate that Cs2O crystal represents a flat-and-dispersive type band structure, which returns a high power factor. In the other hand, low lattice thermal conductivity is discovered in Cs2O semiconductor, combined with its high power factor, the Cs2O crystal is considered a promising thermoelectric material. It is demonstrated that p-type Cs2O could be optimized to exhibit outstanding thermoelectric performance with a maximum ZT value of 0.71 at 500K. Explored by density functional theory calculations, the high ZT value is due to its high Seebeck coefficient S, high electrical conductivity , and low lattice thermal conductivity .

Significantly Enhanced Interfacial Thermal Conductance across GaN/Diamond Interfaces Utilizing AlxGa1-xN as a Phonon Bridge.

Improving the thermal conductance at the GaN/diamond interface is crucial for boosting GaN-based device performance and reliability. In this study, first-principles calculations and molecular dynamics simulations were employed to explore the interfacial thermal conductance of GaN/diamond interfaces with AlxGa1-xN transition layers. The AlxGa1-xN alloy exhibits a lower thermal conductivity than GaN, primarily due to enhanced anharmonic phonon scattering. However, for the interfacial thermal conductance at the GaN/diamond interface, we discovered that introducing an AlxGa1-xN with a high Al concentration (x > 0.5) as a phonon bridge between GaN and diamond can significantly enhance the interfacial thermal conductance. In particular, it increases from 4.79 MW·m-2 K-1 to a maximum of 158 MW·m-2 K-1 at x = 0.75, surpassing the 152 MW·m-2 K-1 achieved by AlN. The AlxGa1-xN alloy has been confirmed computationally as a more efficient phonon bridge, which can provide a valuable theoretical reference for experimentally investigating the thermal management and thermal design of high-power electronic devices based on the GaN/diamond interface.

Phase transition investigation of ferroelectric and dielectric properties of (NH 2 CH 2 COOH)3 H2SO4 crystal using green function method and two sublattice PLCM model Hamiltonian

The Greens function technique and extended two sublattice pseudospin lattice coupled-mode (PLCM) model Hamiltonian have been applied to study the phase transition mechanism in (NH2CH2COOH)3H2SO4 compound. The two sublattice PLCM model Hamiltonian is modified by considering anharmonic phonon interactions, extra spin-lattice interactions, and an external applied electric field term. By using the double-time thermal-dependent Green function technique, the theoretical equations for the total shift, total width, normal mode frequency, transition temperature, relative permittivity, dielectric tangent loss, acoustic attenuation and spontaneous polarization are derived. By fitting the distinct model parameters in the theoretical equations, we calculated the temperature dependence of normal mode frequency, relative permittivity, tangent loss, acoustic attenuation and spontaneous polarization. The numerically obtained results are hold well and correlated with experimental data.

Phonon-Lithium Ion Interactions: A Case Study of LiM(SeO3)2 (M = Al, Ga, In, Sc, Y, and La).

Li ion diffusion is fundamentally a thermally activated ion hopping process. Recently, soft lattice, anharmonic phonon, and paddlewheel mechanism have been proposed to potentially benefit the ion transport, while the understanding of vibrational couplings of mobile ions and anions is still very limited but essential. Herein, we accessed the ionic conductivity, stability, and especially, lattice dynamics in LiM(SeO3)2 (M = Al, Ga, In, Sc, Y, and La) with two different types of oxygen anions within a LiO4 polyhedron, namely, edge-shared and corner-shared with MO6 polyhedra, the prototype of which, LiGa(SeO3)2, has been theoretically reported before with the similar structural features to NASICON and later experimentally synthesized with the room temperature conductivity ∼0.11 mS cm-1. It is interesting to note that LiM(SeO3)2 with a higher Li phonon band center shows higher Li conductivity, which is in contradiction to the conventional understanding of the importance for soft lattice to superionic conductors. The anharmonic and harmonic phonon interactions as well as the couplings between the vibration of the edge-bonded or corner-bonded anion in Li polyanions and the Li ion diffusion have been studied in detail. With transition metal M changing from La, Y, In, Ga, Al, and Sc, anharmonic phonons increase with reduced activation energy for Li diffusion. The phonon modes dominated by the edge-bonded oxygen anions contribute more to the migration of the Li ion than those dominated by the corner-bonded oxygen anions because of the greater atomic interaction between the Li ion and the edge-bonded anions. Thus, rather than the overall lattice softness, attention shall be given to reduce the frequency of the critical phonons contributing to Li ion diffusion as well as to increase the anharmonicity, i.e., through asymmetric Li polyhedra, for the design of Li ion superionic conductors for all-solid-state batteries.

Electronic structure investigation and anisotropic phonon anharmonicity in ternary ZrGeTe4 single crystals

Ternary two-dimensional (2D) transition metal chalcogenides have gained immense attention because of their ability to overcome the intrinsic limitations of their binary counterparts. Layered 2D materials are important for future electronic and photonic devices owing to their low structural symmetry and in-plane anisotropy with tunable bandgap. Herein, the electronic structure and detailed vibrational properties of bulk ZrGeTe4 layered single crystals were investigated using angle-resolved photoemission spectroscopy (ARPES) and Raman scattering (RS). The ARPES results revealed an anisotropic Fermi surface of different momentum along kx and ky from the zone center and an anisotropic band structure with varying band curvatures along the high-symmetry directions. Furthermore, the RS of ZrGeTe4 was investigated under different polarizations and varying temperatures. The polarized RS exhibited twofold and fourfold symmetry orientations in different configurations, revealing the anisotropic phonon dispersions for bulk ZrGeTe4. The observed softening of Raman modes was corroborated with the anharmonic phonon dispersion, which was further supported by our third-order force constant calculations of thermal transport using density functional theory. Low lattice thermal conductivity with increasing temperature is linked with enhanced phonon–phonon scattering, which is evident from the decreased phonon lifetime and peak linewidth. In addition to these fundamental aspects, the anisotropic nature and unique layered structure of such materials reveal their bright future for next-generation nanoelectronic applications.

Effects of thickness, temperature and substrate on phonon anisotropy in layered Ta2NiSe5

Anisotropy in crystal structure has provided a new degree of freedom to tune the physical and photoelectric properties of low-symmetrical materials, enabling the anisotropic band structure and polarization-resolved applications. Thus, the identification and control on the anisotropy is of great importance for the development of polarization-integrated devices. In this work, we introduce a promising two-dimensional (2D) dimetal chalcogenide Ta2NiSe5 with strong in-plane anisotropic structure and explore the effects of thickness, temperature and substrate on its in-plane anisotropy via an angle-resolved polarized Raman spectra. It is shown that the Raman mode softens with increasing temperature, revealing the anharmonic phonon properties of the Ta2NiSe5 flakes. We found that the anisotropy of phonon vibration is strongly related with the thickness, temperature and used substrate, which is more obvious at thinner samples, higher temperature and opaque silicon substrate compared to sapphire and suspended conditions. This work first reveals the influence factor on the anisotropy of phonon mode, which will guide the fundamental research of anisotropic physics and experimental design for the angle-resolved electronics.

Structural distortion-induced low-temperature dielectric dispersion in lanthanide titanate pyrochlores

Rare-earth titanate pyrochlores have attracted significant attention for their unique magnetic frustration; however, research on the origin of low-temperature dielectric dispersion and the relationship between dielectric properties and structure lags far behind. Here, by systematically investigating the dielectric properties of representative rare-earth titanates R2Ti2O7 (R = La, Nd, Sm, Er, Yb, and Lu), we demonstrate that R2Ti2O7 with a cubic pyrochlore structure exhibits low-temperature dielectric dispersion behavior, while the other compounds with a monoclinic perovskite-like layered structure possess no dispersion behavior but excellent temperature-stable dielectric property. The dielectric dispersion in cubic pyrochlores arises from the structural distortion. Furthermore, the existence of structural distortion is affirmed by the anomalous phonon softening of A1g Raman mode around the dielectric dispersion temperature, and the origin of the structural distortion is attributed to anharmonic phonon–phonon interactions induced by intrinsic vacant oxygen at Wyckoff 8a sites. In addition, with increasing ionic radius from R = Lu to Sm, the increased lattice parameter leads to varied bond length and bond angle of Ti-O(1)-Ti, which strengthens the local lattice distortion of TiO(1)6 octahedra and thus enhances diffusion degree of dielectric dispersion. On the other hand, the absence of intrinsic vacant oxygen site hardly gives rise to the local structural distortion and thus no dielectric dispersion in monoclinic R2Ti2O7. Our work not only clarifies the mechanism of dielectric dispersion but also gives a comprehensive perspective on the structure–property relationship of rare-earth titanates R2Ti2O7, and thus lays a solid foundation for further work on related materials.

Design of an Oxide Monolayer with High ZT by a Strong Anharmonicity Unit.

In this paper, a new strategy to obtain a transition-metal oxide (TMO) thermoelectric monolayer is demonstrated. We show that the TMO thermoelectric monolayer can be achieved by the replacement of a transition-metal atom with a cluster, which is composed of heavy transition atoms with abundant valence electrons. Specifically, the transition-metal atom in the XO2 (X = Ti, Zr, Hf) monolayer is replaced by the [Ag6]4+ cluster and a stable structure Ag6O2 is achieved. Due to the abundant valence electrons in the [Ag6]4+ cluster unit, n-type Ag6O2 has high electrical conductivity, which leads to a satisfactory power factor. More importantly, Ag6O2 has an extremely low phonon thermal conductivity of 0.16 W·m-1·K-1, which is one of the lowest values in thermoelectric materials. An in-depth study reveals that the extremely low value originates from the strong phonon anharmonicity and weak metal bond of the [Ag6]4+ cluster unit. Due to the satisfactory power factor and ultralow phonon thermal conductivity, Ag6O2 has high ZT at 300-700 K, and the maximum ZT is 3.77, corresponding to an energy conversion efficiency of 22.24%. Our results demonstrate that replacement of the transition-metal atom by an appropriate cluster is a good way to obtain a TMO thermoelectric monolayer.

Ultralow Thermal Conductivity in Vacancy-Ordered Halide Perovskite Cs3Bi2Br9 with Strong Anharmonicity and Wave-Like Tunneling of Low-Energy Phonons.

Halide perovskites are of great interest due to their exceptional optical and optoelectronic properties. However, thermal conductivity of many halide perovskites remains unexplored. In this study, an ultralow lattice thermal conductivity κL (0.24W m-1 K-1 at 300 K) is reported and its weak temperature dependence (≈T-0.27) in an all-inorganic vacancy-ordered halide perovskite, Cs3Bi2Br9. The intrinsically ultralow κL can be attributed to the soft low-lying phonon modes with strong anharmonicity, which have been revealed by combining experimental heat capacity and Raman spectroscopy measurements, and first-principles calculations. It is shown that the highly anharmonic phonons originate from the Bi 6s2 lone pair expression with antibonding states of Bi 6s and Br 4p orbitals driven by the dynamic BiBr6 octahedral distortion. Theoretical calculations reveal that these low-energy phonons are mostly contributed by large Br motions induced dynamic distortion of BiBr6 octahedra and large Cs rattling motions, verified by the synchrotron X-ray pair distribution function analysis. In addition, the weak temperature dependence of κL can be traced to the wave-like tunneling of phonons, induced by the low-lying phonon modes. This work reveals the strong anharmonicity and wave-like tunneling of low-energy phonons for designing efficient vacancy-ordered halide perovskites with intrinsically low κL.

Improving thermoelectric properties in double half-Heusler M8FexNi8−xSb8 (M = TiZrHfNb)-InSb compounds via synergistic multiscale defects and high-mobility carrier injection

In this study, the modulation doping strategy combined with atomic-scale engineering is applied to the Double half-Heusler (DHH) system. Thermoelectric properties of multi-principal-element alloy Ti2Zr2Hf2Nb2FexNi8−xSb8 are first improved through composition optimization and then modulation doping with nano-InSb. First-principles calculations indicate that strong phonon anharmonicity results in low intrinsic lattice thermal conductivity (κL). Synergistic high-mobility carrier injection and multiscale defects caused by lattice distortion, sluggish diffusion effect, and inhomogeneous doping decouple electron and phonon transport that extrinsically intensified phonon scattering and optimized carrier transport. Consequently, the ZTmax values of nano-InSb doped p-type (x = 5.6) and n-type (x = 2.4) samples are 0.6 and 0.36, respectively, which increased by 663 % and 350 %, compared with the InSb-free x = 5 sample. The corresponding κL near room temperature are as low as ∼2.7 and ∼2.3 W m−1 K−1, respectively. Furthermore, the p-type composition exhibits a relatively high power factor (∼2 mW m−1 K−2), and the n-type samples show negligible bipolar effects at high temperatures. This work provides a novel strategy for the optimization of thermoelectric properties in DHH compounds.

Revisiting thermal transport in CuInTe2: Role of temperature-dependent anharmonicity and higher-order phonon–phonon interactions

The temperature-dependent phonon thermal transport in CuInTe2 is investigated by considering lattice thermal expansion, temperature-dependent anharmonicity, higher-order phonon–phonon interactions, and phonon renormalization with input from first-principles based density functional theory calculations. Incorporating these higher-order temperature-dependent effects reveals that the thermal conductivity varies with temperature as T−1.59 consistent with experimental measurements ranging from T−1.62 to T−1.78. Using the lowest-order theory or only temperature-dependent interatomic force constants or four-phonon scattering resulted in a wrong description of thermal transport physics.

Anharmonic and quantum effects in Pm3̄ AlM(M = Hf, Zr)H6 under high pressure: A first-principles study.

First-principles calculations were employed to investigate the impact of quantum ionic fluctuations and lattice anharmonicity on the crystal structure and superconductivity of Pm3̄ AlM(M = Hf, Zr)H6 at pressures of 0.3-21.2GPa (AlHfH6) and 4.7-39.5GPa (AlZrH6) within the stochastic self-consistent harmonic approximation. A correction is predicted for the crystal lattice parameters, phonon spectra, and superconducting critical temperatures, previously estimated without considering ionic fluctuations on the crystal structure and assuming the harmonic approximation for lattice dynamics. The findings suggest that quantum ionic fluctuations have a significant impact on the crystal lattice parameters, phonon spectra, and superconducting critical temperatures. Based on our anharmonic phonon spectra, the structures will be dynamically stable at 0.3GPa for AlHfH6 and 6.2GPa for AlZrH6, ∼6 and 7GPa lower than pressures given by the harmonic approximation, respectively. Due to the anharmonic correction of their frequencies, the electron-phonon coupling constants (λ) are suppressed by 28% at 11GPa for AlHfH6 and 22% at 30GPa for AlZrH6, respectively. The decrease in λ causes Tc to be overestimated by ∼12K at 11GPa for AlHfH6 and 30GPa for AlZrH6. Even if the anharmonic and quantum effects are not as strong as those of Pm3̄n-AlH3, our results also indicate that metal hydrides with hydrogen atoms in interstitial sites are subject to anharmonic effects. Our results will inevitably stimulate future high-pressure experiments on synthesis, structural, and conductivity measurements.

Comparison of lattice thermal conductivity using ab-initio DFT, machine learning interatomic potentials, and temperature dependent effective potential: a case study of hexagonal BN and BP bilayer

Discovering high thermal conductivity materials is essential for various practical applications, particularly in electronic cooling. The significance of two-dimensional (2D) materials lies in their unique properties that emerge due to their reduced dimensionality, making them highly promising for a wide range of applications. Hexagonal boron nitride (BN), both monolayer and bilayer forms, has garnered attention for its fascinating properties. In this work, we focus on bilayer boron phosphide (BP), which is isostructural to its BN analogue. The lattice thermal conductivity of both bilayer BN and BP have been calculated using ab-initio density functional theory, machine learning with the moment tensor potential method, and the temperature-dependent effective-potential method (TDEP). The TDEP approach gives more accurate results for both BN and BP materials. The lattice thermal conductivity of bilayer BP is lower than that of bilayer BN at room temperature, attributed to increased phonon anharmonicity. This study highlights the importance of understanding phonon scattering mechanisms in determining the thermal conductivity of 2D materials, contributing to the broader understanding and potential applications of these materials in future technologies.

Decoupling of Rattling Mode and Superconductivity in Filled-Skutterudite BaxIr4Sb12

Abstract The rattling mode, an anharmonic vibrational phonon, is widely recognized as a critical factor in the emergence of superconductivity in caged materials. Here, we present a counterexample in a filled-skutterudite superconductor Ba x Ir4Sb12 (x = 0.8, 0.9, 1.0), synthesized via a high-pressure route. Transport measurements down to liquid 3He temperatures reveal a transition temperature (T c) of 1.2 K and an upper critical field (H c2) of 1.3 T. Unlike other superconductors with caged structures, the Ba x Ir4 X 12 (X = P, As, Sb) family exhibits a monotonic decreasing T c with the enhancement of the rattling mode, as indicated by fitting the Bloch–Grüneisen formula. Theoretical analysis suggests that electron doping from Ba transforms the direct bandgap IrSb3 into a metal, with the Fermi surface dominated by the hybridization of Ir 5d and Sb 5p orbitals. Our findings of decoupled rattling modes and superconductivity distinguish the Ba x Ir4Sb12 family from other caged superconductors, warranting further exploration into the underlying mechanism.

Topological phonons and thermal conductivity of two-dimensional Dirac semimetal PtN4C2

PtN4C2 is a recently predicted two-dimensional (2D) Dirac semimetal exhibiting significant topological quantum spin and valley Hall effects. Herein, we explore its topological phonon states and thermal transport properties from first-principles calculations. In terms of symmetry arguments, we predict the existence of multiple topologically protected phononic Dirac points in the frequency range of 0–20 THz, which are evidenced by the relevant irreducible representations and calculated nontrivial edge states on the (100) surface. In addition, anharmonic phonon renormalization is found to play a significant role in determining the phonon spectrum, especially for the out-of-plane flexural acoustic (ZA) branch. Moreover, we explicitly consider three-phonon scattering, four-phonon scattering, and phonon renormalization to predict the lattice thermal conductivity κl of PtN4C2, by solving the Boltzmann transport equation. With the incorporation of four-phonon scattering, we predict that the intrinsic κl is 68 W/mK at room temperature, which is reduced by about 45% as compared to the value obtained by only including three-phonon scattering. This reduction is found to arise mainly from the ZA phonons, whose contribution to κl is significantly suppressed by four-phonon scattering, due to the restriction of the mirror symmetry-induced selection rules on three-phonon processes. We also unveil that the presence of Dirac points steepens the surrounding phonon dispersion and thus greatly increases the phonon group velocities, thereby making a considerable contribution to κl. This work establishes a thorough understanding of intrinsic topological phonons and thermal transport in PtN4C2 and highlights the importance of phonon renormalization and higher-order anharmonicity in determining the phonon transport properties of 2D materials.

Anharmonic Phonon Vibrations of Ag and Cu for Poor Lattice Thermal Conductivity in Superionic AgCrSe2 and CuCrSe2

Anharmonic Phonon Vibrations of Ag and Cu for Poor Lattice Thermal Conductivity in Superionic AgCrSe₂ and CuCrSe₂

Electronic Transport and Interaction of Lattice Dynamics in Topological Nodalline Semimetal HfAs2 Single Crystals

AbstractTopological semimetals represent a novel class of quantum materials displaying non‐trivial topological states that host Dirac/Weyl fermions. The intersection of Dirac/Weyl points gives rise to essential properties in a wide range of innovative transport phenomena, including extreme magnetoresistance, high mobilities, weak antilocalization, electron hydrodynamics, and various electro‐optical phenomena. In this study, the electronic, transport, phonon scattering, and interrelationships are explored in single crystals of the topological semimetal HfAs2. It reveals a weak antilocalization effect at low temperatures with high carrier density, which is attributed to perfectly compensated topological bulk and surface states. The angle‐resolved photoemission spectroscopy (ARPES) results show anisotropic Fermi surfaces and surface states indicative of the topological semimetal, further confirmed by first‐principle density functional theory (DFT) calculations. Moreover, the lattice dynamics in HfAs2 are investigated both with the Raman scattering and density functional theory. The phonon dispersion, density of states, lattice thermal conductivity, and the phonon lifetimes are computed to support the experimental findings. The softening of phonons, the broadening of Raman modes, and the reduction of phonon lifetimes with temperature suggest the enhancement of phonon anharmonicity in this new topological material, which is crucial for boosting the thermoelectric performance of topological semimetals.

Evidence of Higher Order Phonon Anharmonicity in Gray Arsenic Crystal.

Phonons play a key role in the heat transport process of quantum materials. The understanding of thermal behaviors of phonons will be beneficial for designing modern electronic devices. In this study, we utilize specific heat, Raman spectroscopy, and first-principles calculations combined with the phonon Boltzmann transport equation to explore the thermal transport of gray arsenic. Our specific heat data indicate the presence of the phonon anharmonicity at high temperature. This is further supported by temperature-dependent Raman data showing evident phonon softening and line width broadening. More interestingly, from the analysis of temperature-dependent Raman modes, we found that the four-phonon scattering process is indispensable for interpreting the line width broadening at high temperatures. Moreover, we evaluate the importance of the four-phonon scattering process in the heat transport of gray arsenic using the moment tensor potential method. Our work sheds light on the importance of a higher order phonon scattering process in heat transport of the materials with moderate thermal conductivity.