Vibrational Coupling between Organic and Inorganic Sublattices of Hybrid Perovskites

The interplay of electronic and nuclear degrees of freedom in semiconductor hybrid organic–inorganic perovskites determines many of their fundamental photophysical properties. For instance, charge carriers are dressed with phonons, that is, form polarons, and combination modes composed of strongly mixed localized vibrations and delocalized phonons can provide pathways for electronic energy relaxation and dissipation. Mixing of the different types of nuclear motion in vibrational combination modes requires their strong coupling. The direct measurement of coupling between the high‐frequency N−H stretch modes of the organic methylammonium and formamidinium ions and low‐frequency Pb−I phonon modes of the inorganic sub‐lattice in hybrid organic–inorganic perovskites is presented. The results reveal direct and substantial coupling between the non‐covalently interacting organic and inorganic sub‐lattices. Good vibrations: Interaction between different degrees of freedom provides pathways for charge‐carrier scattering and relaxation in perovskite semiconductors. Two‐dimensional terahertz‐infrared‐visible spectroscopy reveals direct coupling between phonon and high‐frequency molecular vibrations of inorganic and organic sub‐lattices, respectively. This coupling accounts for the faster hot‐carrier cooling in hybrid perovskites.