Structural descriptor for enhanced spin-splitting in 2D hybrid perovskites

Creators: Jana, Manoj K.; Song, Ruyi; Xie, Yi; Zhao, Rundong; Sercel, Peter C.; Blum, Volker; Mitzi, David B.

Abstract

Two-dimensional (2D) hybrid metal halide perovskites have emerged as outstanding optoelectronic materials and are potential hosts of Rashba/Dresselhaus spin-splitting for spin-selective transport and spin-orbitronics. However, a quantitative microscopic understanding of what controls the spin-splitting magnitude is generally lacking. Through crystallographic and first-principles studies on a broad array of chiral and achiral 2D perovskites, we demonstrate that a specific bond angle disparity connected with asymmetric tilting distortions of the metal halide octahedra breaks local inversion symmetry and strongly correlates with computed spin-splitting. This distortion metric can serve as a crystallographic descriptor for rapid discovery of potential candidate materials with strong spin-splitting. Our work establishes that, rather than the global space group, local inorganic layer distortions induced via appropriate organic cations provide a key design objective to achieve strong spin-splitting in perovskites. New chiral perovskites reported here couple a sizeable spin-splitting with chiral degrees of freedom and offer a unique paradigm of potential interest for spintronics.

Additional Information

© The Author(s) 2021. This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. Received 17 June 2021; Accepted 26 July 2021; Published 17 August 2021. All authors acknowledge funding from the Center for Hybrid Organic-Inorganic Semiconductors for Energy (CHOISE), an Energy Frontier Research Center funded by the Office of Basic Energy Sciences, Office of Science within the U.S. Department of Energy (DOE) through contract number DE-AC36-08G028308. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work or allow others to do so, for U.S. Government purposes. R.Z. was supported by the National Science Foundation under Award Number DMR-1729297. An award of computer time was provided by the Innovative and Novel Computational Impact on Theory and Experiment (INCITE) program. This research used resources of the Argonne Leadership Computing Facility, which is a DOE Office of Science User Facility supported under Contract DE-AC02-06CH11357. This research also used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy (DOE) Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. Authors also thank Tianyang Li for useful discussions. Data availability: Additional data supporting the findings of this work are provided in Supplementary Information. The single-crystal X-ray structures of the new chiral MHPs, namely, [R-4-Cl-MBA]2PbBr4, [S-1-Me-HA]2PbI4, [S-4-NO2-MBA]2PbBr4∙H2O, [S-2-Me-BuA]2PbBr4, and [S-4-NH3-MBA]PbI4 have been deposited in The Cambridge Crystallographic Data Center (CCDC) database under deposition numbers 2095482-2095486. These data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/ and also from the Hybrid3 perovskite database via https://materials.hybrid3.duke.edu/materials/search using the search terms: "R-4-Cl-MBA2PbBr4", "S-1-Me-HA2PbI4", "S-4-NO2-MBA2PbBr4.H2O", "S-2-Me-BuA2PbBr4", and "S-4-NH3-MBAPbI4". Atomic coordinates for the experimental and relaxed structures of MHPs and Cs2PbBr4 models used for band structure calculations in this study have been provided in Supplementary Note 6. Relevant DFT band structure data is available in the NOMAD repository (https://doi.org/10.17172/NOMAD/2021.07.17-1). Other relevant data can be obtained from the corresponding authors upon reasonable request. Author Contributions: M.K.J. and R.S. contributed equally to the work. M.K.J., R.S., P.S., V.B., and D.B.M. conceived the idea and designed the work. M.K.J. led and coordinated the work. M.K.J., Y.X., and D.B.M. carried out the synthesis and crystallographic investigations of chiral MHPs. R.S., R.Z., and V.B. carried out first principles DFT calculations. P.S. carried out the analysis of spin-splitting using multiband k.p theory and the theory of invariants. All authors analyzed the results and jointly prepared the paper. Competing interests: V.B. is a member of the executive board of MS1P e.V., the non-profit which licenses the FHI-aims electronic structure code used in this work. V.B. does not receive any financial gains from this position. The remaining authors declare no competing interests. Peer review information: Nature Communications thanks Ron Naaman and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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