Strong Raman Optical Activity and Chiral Phonons in Chiral Hybrid Organic–Inorganic Perovskites

Abstract Hybrid organic–inorganic perovskites with chiral organic cations are very interesting for optoelectronic applications because of their intrinsically chiral light‐matter interactions. Chiral distortions in these materials lead to circular dichroism, circular birefringence, and circularly polarized luminescence in the band transitions of the inorganic sublattice. Raman‐active vibrational modes in these crystals are governed by crystal symmetry and therefore are also strongly impacted by the nature and magnitude of the chiral distortions. Here, low‐frequency Raman modes that are sensitive to circularly polarized excitation are reported in chiral hybrid organic–inorganic perovskites (CHOIPs) across a wide range of structures and compositions. The circularly polarized Raman spectra from enantiomers of CHOIP single crystals exhibit sharp modes below 150 cm −1 , corresponding to vibrations of the lead iodide octahedra. These modes exhibit strong differences in intensities (Raman optical activity, ROA) depending on the handedness of the excitation, with high degree of polarization for several modes. Calculations reveal the presence of several chiral phonon modes with opposite phonon angular momenta. The strong ROA and the chiral phonon modes are a direct consequence of chirality transfer from the chiral organic linker to the lead iodide octahedra in the CHOIP structure, resulting in a strong chiroptical response in the phonon modes.