Glassy thermal conductivity in Cs<sub>3</sub>Bi<sub>2</sub>I<sub>6</sub>Cl<sub>3</sub> single crystal.

Acharyya, Paribesh; Ghosh, Tanmoy; Pal, Koushik; Rana, Kewal Singh; Dutta, Moinak; Swain, Diptikanta; Etter, Martin; Soni, Ajay et al. · Nat Commun · 2022

basic_science · Level V

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Abstract

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, κ<sub>L</sub>, decreases, and its fundamental characteristics changes. The realization of ultralow and unusual glass-like κ<sub>L</sub> 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 κ<sub>L</sub> in a single crystal of layered halide perovskite, Cs<sub>3</sub>Bi<sub>2</sub>I<sub>6</sub>Cl<sub>3</sub>. Acoustic phonons with low cut-off frequency (20 cm<sup>-1</sup>) are responsible for the low sound velocity in Cs<sub>3</sub>Bi<sub>2</sub>I<sub>6</sub>Cl<sub>3</sub> 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 κ<sub>L</sub> is intriguing from lattice dynamical perspective as well as have potential applications.