Observation of anomalous time-delayed electron-lattice coupling in organic blends and hybrid perovskites

Elucidating the role of atomic degrees of freedom in organic blends and hybrid perovskites is crucial to understanding the non-adiabatic dynamics within their energy landscape and to their implementation in photovoltaics technologies. Here, we report the direct visualization of the long-range lattice dynamics in rr-P3HT:PC71BM and CH3NH3PbI3 upon femtosecond optical excitation by combining ultrafast electron diffraction and time-dependent ab initio calculations. We find that both materials exhibit a common time-lagged lattice response induced by an impulsive high-intensity photoexcitation. This process, which is observed to occur on a time scale governed by carrier diffusion, is ascribed to the suppression of the incoherent coupling between the photoexcited species (excitons in the organic blends and free charges in the perovskite) and acoustic modes through a phonon-bottleneck effect. Only once excitons or free charges have significantly accumulated at the surface or interface, multiple decay channels open up and the phonon emission proceeds in a regenerative manner with a mechanism similar to a phonon 'avalanche'. The presence of this suppression mechanism creates a dynamic protection of the carriers from incoherent energy dissipation and could contribute to the high photovoltaic efficiencies observed in these materials.

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