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Title: Ligand-field helical luminescence in a 2D ferromagnetic insulator

Abstract

Bulk chromium tri-iodide (CrI3) has long been known as a layered van der Waals ferromagnet. However, its monolayer form was only recently isolated and confirmed to be a truly two-dimensional (2D) ferromagnet, providing a new platform for investigating light–matter interactions and magneto-optical phenomena in the atomically thin limit. Here in this paper, we report spontaneous circularly polarized photoluminescence in monolayer CrI3 under linearly polarized excitation, with helicity determined by the monolayer magnetization direction. In contrast, the bilayer CrI3 photoluminescence exhibits vanishing circular polarization, supporting the recently uncovered anomalous antiferromagnetic interlayer coupling in CrI3 bilayers. Distinct from the Wannier–Mott excitons that dominate the optical response in well-known 2D van der Waals semiconductors, our absorption and layer-dependent photoluminescence measurements reveal the importance of ligand-field and charge-transfer transitions to the optoelectronic response of atomically thin CrI3. We attribute the photoluminescence to a parity-forbidden d–d transition characteristic of Cr3+ complexes, which displays broad linewidth due to strong vibronic coupling and thickness-independent peak energy due to its localized molecular orbital nature.

Authors:
 [1];  [1];  [2];  [3];  [4];  [1];  [2];  [3]; ORCiD logo [1]; ORCiD logo [5]; ORCiD logo [6];  [4];  [2]; ORCiD logo [7]
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Physics
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Physics
  3. Washington Univ., St. Louis, MO (United States). Dept. of Physics
  4. Carnegie Mellon Univ., Pittsburgh, PA (United States). Dept. of Physics
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  6. Univ. of Hong Kong (China). Dept. of Physics and Center of Theoretical and Computational Physics
  7. Univ. of Washington, Seattle, WA (United States). Dept. of Physics, and Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Excitonics (CE); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1430601
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Nature Physics
Additional Journal Information:
Journal Volume: 14; Journal Issue: 3; Journal ID: ISSN 1745-2473
Publisher:
Nature Publishing Group (NPG)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Seyler, Kyle L., Zhong, Ding, Klein, Dahlia R., Gao, Shiyuan, Zhang, Xiaoou, Huang, Bevin, Navarro-Moratalla, Efren, Yang, Li, Cobden, David H., McGuire, Michael A., Yao, Wang, Xiao, Di, Jarillo-Herrero, Pablo, and Xu, Xiaodong. Ligand-field helical luminescence in a 2D ferromagnetic insulator. United States: N. p., 2017. Web. https://doi.org/10.1038/s41567-017-0006-7.
Seyler, Kyle L., Zhong, Ding, Klein, Dahlia R., Gao, Shiyuan, Zhang, Xiaoou, Huang, Bevin, Navarro-Moratalla, Efren, Yang, Li, Cobden, David H., McGuire, Michael A., Yao, Wang, Xiao, Di, Jarillo-Herrero, Pablo, & Xu, Xiaodong. Ligand-field helical luminescence in a 2D ferromagnetic insulator. United States. https://doi.org/10.1038/s41567-017-0006-7
Seyler, Kyle L., Zhong, Ding, Klein, Dahlia R., Gao, Shiyuan, Zhang, Xiaoou, Huang, Bevin, Navarro-Moratalla, Efren, Yang, Li, Cobden, David H., McGuire, Michael A., Yao, Wang, Xiao, Di, Jarillo-Herrero, Pablo, and Xu, Xiaodong. Mon . "Ligand-field helical luminescence in a 2D ferromagnetic insulator". United States. https://doi.org/10.1038/s41567-017-0006-7. https://www.osti.gov/servlets/purl/1430601.
@article{osti_1430601,
title = {Ligand-field helical luminescence in a 2D ferromagnetic insulator},
author = {Seyler, Kyle L. and Zhong, Ding and Klein, Dahlia R. and Gao, Shiyuan and Zhang, Xiaoou and Huang, Bevin and Navarro-Moratalla, Efren and Yang, Li and Cobden, David H. and McGuire, Michael A. and Yao, Wang and Xiao, Di and Jarillo-Herrero, Pablo and Xu, Xiaodong},
abstractNote = {Bulk chromium tri-iodide (CrI3) has long been known as a layered van der Waals ferromagnet. However, its monolayer form was only recently isolated and confirmed to be a truly two-dimensional (2D) ferromagnet, providing a new platform for investigating light–matter interactions and magneto-optical phenomena in the atomically thin limit. Here in this paper, we report spontaneous circularly polarized photoluminescence in monolayer CrI3 under linearly polarized excitation, with helicity determined by the monolayer magnetization direction. In contrast, the bilayer CrI3 photoluminescence exhibits vanishing circular polarization, supporting the recently uncovered anomalous antiferromagnetic interlayer coupling in CrI3 bilayers. Distinct from the Wannier–Mott excitons that dominate the optical response in well-known 2D van der Waals semiconductors, our absorption and layer-dependent photoluminescence measurements reveal the importance of ligand-field and charge-transfer transitions to the optoelectronic response of atomically thin CrI3. We attribute the photoluminescence to a parity-forbidden d–d transition characteristic of Cr3+ complexes, which displays broad linewidth due to strong vibronic coupling and thickness-independent peak energy due to its localized molecular orbital nature.},
doi = {10.1038/s41567-017-0006-7},
journal = {Nature Physics},
number = 3,
volume = 14,
place = {United States},
year = {2017},
month = {12}
}

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