Probing femtosecond lattice displacement upon photo-carrier generation in lead halide perovskite

Nat Commun. 2018 May 17;9(1):1971. doi: 10.1038/s41467-018-04367-6.

Abstract

Electronic properties and lattice vibrations are expected to be strongly correlated in metal-halide perovskites, due to the soft fluctuating nature of their crystal lattice. Thus, unveiling electron-phonon coupling dynamics upon ultrafast photoexcitation is necessary for understanding the optoelectronic behavior of the semiconductor. Here, we use impulsive vibrational spectroscopy to reveal vibrational modes of methylammonium lead-bromide perovskite under electronically resonant and non-resonant conditions. We identify two excited state coherent phonons at 89 and 106 cm-1, whose phases reveal a shift of the potential energy minimum upon ultrafast photocarrier generation. This indicates the transition to a new geometry, reached after approximately 90 fs, and fully equilibrated within the phonons lifetime of about 1 ps. Our results unambiguously prove that these modes drive the crystalline distortion occurring upon photo-excitation, demonstrating the presence of polaronic effects.