Direct Observation of Circularly Polarized Nonlinear Optical Activities in Chiral Hybrid Lead Halides

Liu, Sunhao; Wang, Xiaoming; Dou, Yixuan; Wang, Qian; Kim, Jiyoon; Slebodnick, Carla; Yan, Yanfa; Quan, Lina

doi:10.1021/jacs.4c00619

Title: Direct Observation of Circularly Polarized Nonlinear Optical Activities in Chiral Hybrid Lead Halides

Journal Article · 03 April 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.4c00619 · OSTI ID:2471147

Liu, Sunhao ^[1];

^[2];

^[1]; Wang, Qian ^[1]; Kim, Jiyoon ^[1];

^[1];

^[2];

^[1]

Virginia Tech, Blacksburg, VA (United States)
The University of Toledo, OH (United States)

Circularly polarized light emission is a crucial application in imaging, sensing, and photonics. However, utilizing low-energy photons to excite materials, as opposed to high-energy light excitation, can facilitate deep-tissue imaging and sensing applications. The challenge lies in finding materials capable of directly generating circularly polarized nonlinear optical effects. In this study, we introduce a chiral hybrid lead halide (CHLH) material system, R/S-DPEDPb₃Br₈·H₂O (DPED = 1,2-diphenylethylenediammonium), which can directly produce circularly polarized second harmonic generation (CP-SHG) through linearly polarized infrared light excitation, exhibiting a polarization efficiency as high as 37% at room temperature. To understand the spin relaxation mechanisms behind the high polarization efficiency, we utilized two models, so-called D’yakonov–Perel’ (DP) and Bir–Aronov–Pikus (BAP) mechanisms. The unique zigzag inorganic frameworks within the hybrid structure are believed to reduce the dielectric confinement and exciton binding energy, thus enhancing spin polarization, especially in regions with a high excitation pump fluence based on the DP mechanism. In the case of low excitation pump fluence, the BAP mechanism dominates, as evidenced by the observed decrease in the polarization ratio from CP-SHG measurement. Using density functional theory analysis, we elucidate how the distinctive 8-coordination environment of lead bromide building blocks effectively suppresses spin–orbit coupling at the conduction band minimum. This suppression significantly diminishes spin-splitting, thereby slowing the spin relaxation rate.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2471147

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 17 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Direct Observation of Circularly Polarized Nonlinear Optical Activities in Chiral Hybrid Lead Halides

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