Pushing thermal conductivity to its lower limit in crystals with simple structures.

Materials with low thermal conductivity usually have complex crystal structures. Herein we experimentally find that a simple crystal structure material AgTlI2 (I4/mcm) owns an extremely low thermal conductivity of 0.25 W/mK at room temperature. To understand this anomaly, we perform in-depth theoretical studies based on ab initio molecular dynamics simulations and anharmonic lattice dynamics. We find that the unique atomic arrangement and weak chemical bonding provide a permissive environment for strong oscillations of Ag atoms, leading to a considerable rattling behaviour and giant lattice anharmonicity. This feature is also verified by the experimental probability density function refinement of single-crystal diffraction. The particularly strong anharmonicity breaks down the conventional phonon gas model, giving rise to non-negligible wavelike phonon behaviours in AgTlI2 at 300 K. Intriguingly, unlike many strongly anharmonic materials where a small propagative thermal conductivity is often accompanied by a large diffusive thermal conductivity, we find an unusual coexistence of ultralow propagative and diffusive thermal conductivities in AgTlI2 based on the thermal transport unified theory. This study underscores the potential of simple crystal structures in achieving low thermal conductivity and encourages further experimental research to enrich the family of materials with ultralow thermal conductivity.

Mechanistic insight on water dissociation on pristine low-index TiO2 surfaces from machine learning molecular dynamics simulations.

Water adsorption and dissociation processes on pristine low-index TiO2 interfaces are important but poorly understood outside the well-studied anatase (101) and rutile (110). To understand these, we construct three sets of machine learning potentials that are simultaneously applicable to various TiO2 surfaces, based on three density-functional-theory approximations. Here we show the water dissociation free energies on seven pristine TiO2 surfaces, and predict that anatase (100), anatase (110), rutile (001), and rutile (011) favor water dissociation, anatase (101) and rutile (100) have mostly molecular adsorption, while the simulations of rutile (110) sensitively depend on the slab thickness and molecular adsorption is preferred with thick slabs. Moreover, using an automated algorithm, we reveal that these surfaces follow different types of atomistic mechanisms for proton transfer and water dissociation: one-step, two-step, or both. These mechanisms can be rationalized based on the arrangements of water molecules on the different surfaces. Our finding thus demonstrates that the different pristine TiO2 surfaces react with water in distinct ways, and cannot be represented using just the low-energy anatase (101) and rutile (110) surfaces.

Pressure effects on the anomalous thermal transport and anharmonic lattice dynamics of CsX (X = Cl, Br, and I).

The lattice thermal conductivity of CsX (X = Cl, Br, and I) and its pressure dependence are investigated using first-principles third-order anharmonic force constants. Contrary to the expectation that compounds with heavier atoms usually exhibit lower lattice thermal conductivity (kL), the kL of CsI is higher than those of CsCl and CsBr. This anomalous behavior is examined by analyzing the group velocity, phonon lifetime, three-phonon scattering phase space and Grüneisen parameters. The higher kL of CsI can be attributed to its longer phonon lifetimes due to weaker absorption processes in the range of 1 ∼ 2.1 THz. It is found that the lattice thermal conductivity of CsI is more sensitive to hydrostatic pressure, and the kL of CsI becomes lower than those of CsCl and CsBr at -2 GPa due to the shorter phonon lifetimes and the smaller group velocities. Moreover, the changes in the bulk modulus and Bader charge of CsX are also discussed to provide further insight into its anomalous thermal behavior.

GPUMD: A package for constructing accurate machine-learned potentials and performing highly efficient atomistic simulations.

We present our latest advancements of machine-learned potentials (MLPs) based on the neuroevolution potential (NEP) framework introduced in Fan et al. [Phys. Rev. B 104, 104309 (2021)] and their implementation in the open-source package gpumd. We increase the accuracy of NEP models both by improving the radial functions in the atomic-environment descriptor using a linear combination of Chebyshev basis functions and by extending the angular descriptor with some four-body and five-body contributions as in the atomic cluster expansion approach. We also detail our efficient implementation of the NEP approach in graphics processing units as well as our workflow for the construction of NEP models and demonstrate their application in large-scale atomistic simulations. By comparing to state-of-the-art MLPs, we show that the NEP approach not only achieves above-average accuracy but also is far more computationally efficient. These results demonstrate that the gpumd package is a promising tool for solving challenging problems requiring highly accurate, large-scale atomistic simulations. To enable the construction of MLPs using a minimal training set, we propose an active-learning scheme based on the latent space of a pre-trained NEP model. Finally, we introduce three separate Python packages, viz., gpyumd, calorine, and pynep, that enable the integration of gpumd into Python workflows.

Leveraging bipolar effect to enhance transverse thermoelectricity in semimetal Mg2Pb for cryogenic heat pumping.

Toward high-performance thermoelectric energy conversion, the electrons and holes must work jointly like two wheels of a cart: if not longitudinally, then transversely. The bipolar effect - the main performance restriction in the traditional longitudinal thermoelectricity, can be manipulated to be a performance enhancer in the transverse thermoelectricity. Here, we demonstrate this idea in semimetal Mg2Pb. At 30 K, a giant transverse thermoelectric power factor as high as 400 µWcm-1K-2 is achieved, a 3 orders-of-magnitude enhancement than the longitudinal configuration. The resultant specific heat pumping power is ~ 1 Wg-1, higher than those of existing techniques at 10~100 K. A large number of semimetals and narrow-gap semiconductors making poor longitudinal thermoelectrics due to severe bipolar effect are thus revived to fill the conspicuous gap of thermoelectric materials for solid-state applications.

Anharmonic lattice dynamics and thermal transport of monolayer InSe under equibiaxial tensile strains.

Two-dimensional (2D) InSe, which exhibits high electron mobility and a wide band gap has emerged as a promising material for photoelectric and thermoelectric applications. The inadequate understanding of the lattice thermal conductivity (κ), however, hampers the advancement of 2D InSe. Herein, by taking into account anharmonicity up to the fourth order and introducing the equibiaxial tensile strain (ϵ), we have performed an in-depth study on the lattice dynamics of 2D InSe. Interestingly, the κ exhibits a non-monotonic behaviour as a function of equibiaxial tensile strain, which can be attributed to the changes in acoustic phonon lifetimes. At the Γ point, a blue-shift of the lowest optical mode and a red-shift of the uppermost optical mode are reported for the first time. More strikingly, the blue-shift can be largely suppressed by equibiaxial tensile strain. Further study indicates that the unique transition of the potential energy surface is responsible for the disappearance of the blue-shift. Our work may enlighten the future research on phonon engineering and management of the lattice thermal conductivity of 2D InSe.

Thermoelectric Enhancements in PbTe Alloys Due to Dislocation-Induced Strains and Converged Bands.

In-grain dislocation-induced lattice strain fluctuations are recently revealed as an effective avenue for minimizing the lattice thermal conductivity. This effect could be integratable with electronic enhancements such as by band convergence, for a great advancement in thermoelectric performance. This motivates the current work to focus on the thermoelectric enhancements of p-type PbTe alloys, where monotelluride-alloying and Na-doping are used for a simultaneous manipulation on both dislocation and band structures. As confirmed by synchrotron X-ray diffractions and Raman measurements, the resultant dense in-grain dislocations induce lattice strain fluctuations for broadening the phonon dispersion, leading to an exceptionally low lattice thermal conductivity of ≈0. 4 W m-K-1. Band structure calculations reveal the convergence of valence bands due to monotelluride-alloying. Eventually, the integration of both electronic and thermal improvements lead to a realization of an extraordinary figure of merit zT of ≈2.5 in Na0.03Eu0.03Cd0.03Pb0.91Te alloy at 850 K.

Manipulation of Band Degeneracy and Lattice Strain for Extraordinary PbTe Thermoelectrics.

Maximizing band degeneracy and minimizing phonon relaxation time are proven to be successful for advancing thermoelectrics. Alloying with monotellurides has been known to be an effective approach for converging the valence bands of PbTe for electronic improvements, while the lattice thermal conductivity of the materials remains available room for being further reduced. It is recently revealed that the broadening of phonon dispersion measures the strength of phonon scattering, and lattice dislocations are particularly effective sources for such broadening through lattice strain fluctuations. In this work, a fine control of MnTe and EuTe alloying enables a significant increase in density of electron states near the valence band edge of PbTe due to involvement of multiple transporting bands, while the creation of dense in-grain dislocations leads to an effective broadening in phonon dispersion for reduced phonon lifetime due to the large strain fluctuations of dislocations as confirmed by synchrotron X-ray diffraction. The synergy of both electronic and thermal improvements successfully leads the average thermoelectric figure of merit to be higher than that ever reported for p-type PbTe at working temperatures.