Atomistic Insights into the Origin of High‐Performance Thermoelectric Response in Hybrid Perovskites

Abstract Due to their tantalizing prospect of heat‐electricity interconversion, hybrid organic–inorganic perovskites have sparked considerable research interests recently. Nevertheless, understanding their complex interplay between the macroscopic properties, nonintuitive transport processes, and basic chemical structures still remains far from completion, although it plays a fundamental role in systematic materials development. On the basis of multiscale first‐principles calculations, this understanding is herein advanced by establishing a comprehensive picture consisting of atomic and charge dynamics. It is unveiled that the ultralow room‐temperature lattice thermal conductivity (≈0.20 W m −1 K −1 ) of hybrid perovskites is critical to their decent thermoelectric figure of merit (≈0.34), and such phonon‐glass behavior stems from not only the inherent softness but also the strong anharmonicity. It is identified that the 3D electrostatic interaction and hydrogen‐bonded networks between the PbI 3− cage and embedded cations result in the strongly coupled motions of inorganic framework and cation, giving rise to their high degree of anharmonicity. Furthermore, such coupled motions bring about low‐frequency optical vibrational modes, which leads to the dominant role of electron scattering with optical phonons in charge transport. It is expected that these new atomistic‐level insights offer a standing point where the performance of thermoelectric perovskites can be further enhanced.