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

XY Chen and JL Zhou and J Luo and JW Zhang and PF Qiu and X Shi, SMALL, 20 (2024).

DOI: 10.1002/smll.202405276

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 kappa(L) (0.24 W m(-1) K-1 at 300 K) is reported and its weak temperature dependence (approximate to T-0.27) in an all-inorganic vacancy-ordered halide perovskite, Cs3Bi2Br9. The intrinsically ultralow kappa(L) 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 6s(2) 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 kappa(L) 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 kappa(L).

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