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

TL;DR

This study demonstrates that chiral hybrid organic-inorganic perovskites exhibit strong circularly polarized Raman signals and chiral phonon modes, revealing the transfer of chirality from organic linkers to inorganic frameworks, with implications for chiroptical applications.

Contribution

It provides the first detailed observation of chiral phonon modes and circularly polarized Raman activity in chiral hybrid perovskites, linking molecular chirality to phonon behavior.

Findings

Sharp low-frequency Raman modes below 150 cm-1 show strong polarization dependence.

Chiral phonon modes exhibit opposite angular momenta, confirmed by calculations.

Chirality transfer results in significant chiroptical responses in phonon modes.

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, we report low-frequency Raman modes that are sensitive to circularly polarized excitation 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.