Size-Dependent Lattice Symmetry Breaking Determines the Exciton Fine Structure of Perovskite Nanocrystals

Weinberg, Daniel; Park, Yoonjae; Limmer, David T.; Rabani, Eran

doi:10.1021/acs.nanolett.3c00861

Size-Dependent Lattice Symmetry Breaking Determines the Exciton Fine Structure of Perovskite Nanocrystals

Journal Article · Thu May 25 00:00:00 EDT 2023 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.3c00861· OSTI ID:2323438

^[1]; Park, Yoonjae ^[1]; ^[2]; ^[3]

University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)
University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Tel Aviv University, Tel Aviv (Israel)

The order of bright and dark excitonic states in lead-halide perovskite nanocrystals is debated. It has been proposed that the Rashba effect, driven by lattice-induced symmetry breaking, causes a bright excitonic ground state. Direct measurements of excitonic spectra, however, show the signatures of a dark ground state, bringing the role of the Rashba effect into question. We use an atomistic theory to model the exciton fine structure of perovskite nanocrystals, accounting for realistic lattice distortions. We calculate optical gaps and excitonic features that compare favorably with experimental works. The exciton fine structure splittings show a nonmonotonic size dependence due to a structural transition between cubic and orthorhombic phases. Additionally, the excitonic ground state is found to be dark with spin triplet character, exhibiting a small Rashba coupling. Here we additionally explore the effects of nanocrystal shape on the fine structure, clarifying observations on polydisperse nanocrystals.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2323438

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 11 Vol. 23; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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