Large exchange-driven intrinsic circular dichroism of a chiral 2D hybrid perovskite

Li, Shunran; Xu, Xian; Kocoj, Conrad A.; Zhou, Chenyu; Li, Yanyan; Chen, Du; Bennett, Joseph A.; Liu, Sunhao; Quan, Lina; Sarker, Suchismita; Liu, Mingzhao; Qiu, Diana Y.; Guo, Peijun

doi:10.1038/s41467-024-46851-2

Title: Large exchange-driven intrinsic circular dichroism of a chiral 2D hybrid perovskite

Journal Article · 22 March 2024 · Nature Communications

DOI: https://doi.org/10.1038/s41467-024-46851-2 · OSTI ID:2327035

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^[2]; Li, Yanyan ^[1];

^[1]; Bennett, Joseph A. ^[1]; Liu, Sunhao ^[3];

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Yale Univ., New Haven, CT (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Cornell Univ., Ithaca, NY (United States). Cornell High Energy Synchrotron Source (CHESS)

In two-dimensional chiral metal-halide perovskites, chiral organic spacers endow structural and optical chirality to the metal-halide sublattice, enabling exquisite control of light, charge, and electron spin. The chiroptical properties of metal-halide perovskites have been measured by transmissive circular dichroism spectroscopy, which necessitates thin-film samples. Here, by developing a reflection-based approach, we characterize the intrinsic, circular polarization-dependent complex refractive index for a prototypical two-dimensional chiral lead-bromide perovskite and report large circular dichroism for single crystals. Comparison with ab initio theory reveals the large circular dichroism arises from the inorganic sublattice rather than the chiral ligand and is an excitonic phenomenon driven by electron-hole exchange interactions, which breaks the degeneracy of transitions between Rashba-Dresselhaus-split bands, resulting in a Cotton effect. Our study suggests that previous data for spin-coated films largely underestimate the optical chirality and provides quantitative insights into the intrinsic optical properties of chiral perovskites for chiroptical and spintronic applications.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE

Grant/Contract Number:: SC0012704; CHE-2305138; DMR-2313648; AC02-05CH11231; AC05-00OR22725

OSTI ID:: 2327035

Alternate ID(s):: OSTI ID: 2403451

Report Number(s):: BNL-225829-2024-JAAM

Journal Information:: Nature Communications, Vol. 15, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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