Direct Observation of Ultrafast Lattice Distortions during Exciton-Polaron Formation in Lead Halide Perovskite Nanocrystals.

ABSTRACT

The microscopic origin of slow hot-carrier cooling in lead halide perovskites remains debated and has direct implications for applications. Slow hot-carrier cooling of several picoseconds has been attributed to either polaron formation or a hot-phonon bottleneck effect at high excited carrier densities (>1018 cm-3). These effects cannot be unambiguously disentangled with optical experiments alone. However, they can be distinguished by direct observations of ultrafast lattice dynamics, as these effects are expected to create qualitatively distinct fingerprints. To this end, we employ femtosecond electron diffraction and directly measure the sub-picosecond lattice dynamics of weakly confined CsPbBr3 nanocrystals following above-gap photoexcitation. While we do not observe signatures of a hot-phonon bottleneck lasting several picoseconds, the data reveal a light-induced structural distortion appearing on a time scale varying between 380 and 1200 fs depending on the excitation fluence. We attribute these dynamics to the effect of exciton-polarons on the lattice and the slower dynamics at high fluences to slower sub-picosecond hot-carrier cooling, which slows down the establishment of the exciton-polaron population. Further analysis and simulations show that the distortion is consistent with motions of the [PbBr3]- octahedral ionic cage, and closest agreement with the data is obtained for Pb-Br bond lengthening. Our work demonstrates how direct studies of lattice dynamics on the sub-picosecond time scale can discriminate between competing scenarios proposed in the literature to explain the origin of slow hot-carrier cooling in lead halide perovskites.