In metal-halide perovskites (MHPs), the nature of organic cations affects both, the perovskite's structure and its optoelectronic properties. Using ultrafast pump-probe spectroscopy, we demonstrate that in state-of-the-art mixed-cation MHPs ultrafast photo-induced bandgap narrowing occurs, and linearly depends on the excited carrier density in the range from 1016 cm− 3 to above 1018 cm− 3. Furthermore, time-domain terahertz (td-THz) photoconductivity measurements reveal that the majority of

more »

... iers are localized and that the localization increases with the carrier density. Both observations, the bandgap narrowing and carrier localization, can be rationalized by ultrafast (sub-2ps) photo-induced enhancement of electron-phonon coupling, originating from dynamic disorder, as clearly evidenced by the presence of a Debye relaxation component in the terahertz photoconductivity spectra. The observation of photo-induced enhancement of electron-phonon coupling and dynamic disorder not only provides specific insight into the polaron-strain distribution of excited states in MHPs, but also adds to the development of a concise picture of the ultrafast physics of this important class of semiconductors.