p Dynamic Exciton Polaron in Two-Dimensional Lead Halide Perovskites and Implications for Optoelectronic Applications

CONSPECTUS: The past few years have witnessed an exciting revival of the research interest in two-dimensional (2D) lead halide perovskites. The renaissance is strongly motivated by the great success of their three-dimensional (3D) counterparts in optoelectronic applications. Different from 3D lead halide perovskites where free carriers are generated upon photoexcitation, 2D lead halide perovskites experience weaker dielectric screening and stronger quantum confinement effects. Therefore, strongly bound excitons with binding energy of up to a few hundreds of meV are considered to be the main excited-state species responsible for optoelectronic processes in 2D perovskites. In addition to strong excitonic effects, polaronic effects are also inherent in the soft and anharmonic lattice of lead halide perovskites, and polaronic structural relaxation is found to strongly renormalize carrier excited-state behaviors. For example, ferroelectric large polaron formation and liquid-like solvation of band edge carriers are proposed to account for the exceptional properties of 3D lead halide perovskites. As for 2D lead halide perovskites, polaronic characteristics have also been observed in exciton spectral characters, but how the interplay between excitonic effect and polaronic effect redefines the nature of exciton polarons and their excited-state behaviors still remains largely unexplored. In this Account, we discuss our recent experimental findings about the excited-state properties of exciton polarons in 2D lead halide perovskites. We begin our discussion by introducing a conventional view of strongly bound excitons in 2D lead halide perovskites with large exciton binding energy, which is typically estimated from steady-state absorption spectra. However, owing to the soft and anharmonic lattice, excitons in 2D lead halide perovskites exhibit significant polaronic characters and exist as exciton polarons. It is still unclear how polaronic effects would affect the exciton properties in 2D lead halide perovskites, especially in their excited-state dynamics. By probing exchange interaction, we found that both intra- and inter-exciton Coulomb interaction strengths are substantially weakened by the polaronic screening effect, which is manifested as (1) a counterintuitively longer exciton spin lifetime by almost an order of magnitude or a smaller intraexcitonic interaction strength with temperature increasing from 80 to 340 K and (2) an order of magnitude smaller interexcitonic interaction strength compared to another prototypical 2D semiconductor named transition-metal dichalcogenides (TMDCs) with a comparable steady-state exciton binding energy. We further discuss the interplay between the long- and short-range exciton-phonon interaction and conclude that the exciton-phonon interaction strength is in an intermediate regime and the exciton polaron is momentarily trapped in 2D perovskites, that is, a dynamic exciton polaron. Finally, we highlight prospective opportunities with ligand and cation engineering to regulate the exciton-phonon interaction and exciton polaron properties in 2D perovskites, which have strong implications toward future rational design for 2D perovskite-based efficient photovoltaics or light-emitting devices with high color purity.