Abstract

Organic–inorganic hybrid perovskites manifest unique photophysical properties in terms of their long carrier lifetime, low recombination rate, and high defect tolerance, enabling them to be promising candidates in optoelectronic devices. However, such advanced properties are unexpected in perovskite materials with moderate charge mobility. Recent investigations have revealed that these appealing properties were endowed due to the formation of large polarons in the perovskite crystals, resulting from the coupling of photogenerated carriers and a polarized crystal lattice, which largely affected the carrier-transport dynamics and structural stability of perovskite solar cells (PSCs). In this review, first the crystal structure of the perovskite lattice and the formation mechanism of polarons are elucidated. Then, the modulation of polaron states in PSCs, including large polaron stabilization, polaron-facilitated charge transport, hot-carrier solar cells, and polaron-related stability issues such as polaron-induced metastable defects, polaronic strain, and photostriction are systematically investigated. Finally, the prospect of further understanding and manipulating polaron-related phenomena, working toward highly efficient and stable PSCs, is suggested.

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