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Anharmonic phonon renormalization and thermoelectric properties of CsPbX 3 (X = Cl, Br, and I): first-principles calculations.

Ziang YaoWei CaoZiyu WangLing MiaoJing ShiRui Xiong
Published in: Physical chemistry chemical physics : PCCP (2023)
Halide perovskites with ultralow thermal conductivity have emerged as promising candidates for thermoelectric materials. We study the lattice dynamics and thermoelectric properties of cubic all-inorganic lead halide perovskites CsPbX 3 (X = Cl, Br, and I) through first-principles calculations. Combined with self-consistent phonon theory, we have successfully renormalized the phonon frequency using a quartic anharmonic term, allowing us to accurately reproduce the phonon dispersion of the high-temperature cubic phase of CsPbX 3 without any imaginary frequencies. Cubic CsPbX 3 exhibit ultralow lattice thermal conductivities (0.61-1.71 Wm -1 K -1 ) at room temperature. Because of the strong quartic anharmonic renormalization and hardening of the soft modes, the lattice thermal conductivities of cubic CsPbX 3 all exhibit weak temperature dependence. Notably, CsPbCl 3 exhibits remarkably high thermal conductivity and a long phonon lifetime. This can be attributed to the smallest atomic mean square displacement and the weakest tilting and distortions of PbCl 6 octahedra, resulting from the strongest Pb-Cl covalent bonding. Furthermore, the maximum ZT value of 0.63 at 900 K is obtained for the n-type CsPbBr 3 .
Keyphrases
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