Understanding the interplay between various design strategies (for instance, bonding heterogeneity and lone pair induced anharmonicity) to achieve ultralow lattice thermal conductivity (κl) is indispensable for discovering novel functional materials for thermal energy applications. In the present study, we investigate layered PbXF (X = Cl, Br, I), which offers bonding heterogeneity through the layered crystal structure, anharmonicity through the Pb2+ 6s2 lone pair, and phonon softening through the mass difference between F and Pb/X. The weak interlayer van der Waals bonding and the strong intralayer ionic bonding with partial covalent bonding result in a significant bonding heterogeneity and a poor phonon transport in the out-of-plane direction. Large average Grüneisen parameters (≥2.5) demonstrate strong anharmonicity. The computed phonon dispersions show flat bands, which suggest short phonon lifetimes, especially for PbIF. Enhanced Born effective charges are due to cross-band-gap hybridization. PbIF shows lattice instability at a small volume expansion of 0.1%. The κl values obtained by the two channel transport model are 20–50% higher than those obtained by solving the Boltzmann transport equation. Overall, ultralow κl values are found at 300 K, especially for PbIF. We propose that the interplay of bonding heterogeneity, lone pair induced anharmonicity, and constituent elements with high mass difference aids the design of low κl materials for thermal energy applications.
Bibliographical noteKAUST Repository Item: Exported on 2022-09-14
Acknowledgements: N.Y. thanks the Stony Brook Research Computing and Cyberinfrastructure as well as the Institute for Advanced Computational Science at Stony Brook University for access to the high-performance SeaWulf computing system, which was made possible by a National Science Foundation Grant (1531492). The research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST). S.C.R.R. thanks Rajiv Gandhi University of Knowledge Technologies (RGUKT) Basar for providing computational facilities.
ASJC Scopus subject areas
- Materials Science(all)