Ligand-field helical luminescence in a 2D ferromagnetic insulator

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

doi:10.1038/s41567-017-0006-7

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

Journal Article · 04 December 2017 · Nature Physics

DOI: https://doi.org/10.1038/s41567-017-0006-7 · OSTI ID:1430601

Seyler, Kyle L. ^[1]; Zhong, Ding ^[1]; Klein, Dahlia R. ^[2]; Gao, Shiyuan ^[3]; Zhang, Xiaoou ^[4]; Huang, Bevin ^[1]; Navarro-Moratalla, Efren ^[2]; Yang, Li ^[3];

^[1];

^[5];

^[6]; Xiao, Di ^[4]; Jarillo-Herrero, Pablo ^[2];

^[7]

Univ. of Washington, Seattle, WA (United States). Dept. of Physics
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Physics
Washington Univ., St. Louis, MO (United States). Dept. of Physics
Carnegie Mellon Univ., Pittsburgh, PA (United States). Dept. of Physics
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
Univ. of Hong Kong (China). Dept. of Physics and Center of Theoretical and Computational Physics
Univ. of Washington, Seattle, WA (United States). Dept. of Physics, and Dept. of Materials Science and Engineering

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.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Excitonics (CE); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1430601

Journal Information:: Nature Physics, Vol. 14, Issue 3; ISSN 1745-2473

Publisher:: Nature Publishing Group (NPG)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 236 works

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References (30)

Magnetization, Resonance, and Optical Properties of the Ferromagnet CrI ₃ Dillon, J. F.; Olson, C. E. Journal of Applied Physics, Vol. 36, Issue 3 https://doi.org/10.1063/1.1714194	journal	March 1965
Defects activated photoluminescence in two-dimensional semiconductors: interplay between bound, charged and free excitons Tongay, Sefaattin; Suh, Joonki; Ataca, Can Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02657	journal	September 2013
Discovery of intrinsic ferromagnetism in two-dimensional van der Waals crystals Gong, Cheng; Li, Lin; Li, Zhenglu Nature, Vol. 546, Issue 7657 https://doi.org/10.1038/nature22060	journal	April 2017
Effect of magnetic ordering on the optical properties of transition-metal halides: Ni Cl 2 , Ni Br 2 , Cr Cl 3 , and Cr Br 3 Nosenzo, L.; Samoggia, G.; Pollini, I. Physical Review B, Vol. 29, Issue 6 https://doi.org/10.1103/PhysRevB.29.3607	journal	March 1984
Insulating Ferromagnetic Spinels Baltzer, P. K.; Lehmann, H. W.; Robbins, M. Physical Review Letters, Vol. 15, Issue 11 https://doi.org/10.1103/PhysRevLett.15.493	journal	September 1965
Spin and pseudospins in layered transition metal dichalcogenides Xu, Xiaodong; Yao, Wang; Xiao, Di Nature Physics, Vol. 10, Issue 5 https://doi.org/10.1038/nphys2942	journal	April 2014
Photonics and optoelectronics of 2D semiconductor transition metal dichalcogenides Mak, Kin Fai; Shan, Jie Nature Photonics, Vol. 10, Issue 4 https://doi.org/10.1038/nphoton.2015.282	journal	March 2016
Coupling of Crystal Structure and Magnetism in the Layered, Ferromagnetic Insulator CrI ₃ McGuire, Michael A.; Dixit, Hemant; Cooper, Valentino R. Chemistry of Materials, Vol. 27, Issue 2 https://doi.org/10.1021/cm504242t	journal	January 2015
Dielectric Spectroscopy of Ferromagnetic Semiconductors Miles, P. A.; Westphal, W. B.; Von Hippel, A. Reviews of Modern Physics, Vol. 29, Issue 3 https://doi.org/10.1103/RevModPhys.29.279	journal	July 1957
Refraction and Dispersion of Synthetic Sapphire Malitson, Irving H. Journal of the Optical Society of America, Vol. 52, Issue 12 https://doi.org/10.1364/JOSA.52.001377	journal	January 1962
The optical electrical and magnetic properties of the europium chalcogenides and the rare earth pnictides Wachter, P. C R C Critical Reviews in Solid State Sciences, Vol. 3, Issue 2 https://doi.org/10.1080/10408437208244865	journal	July 1972
Ising-Type Magnetic Ordering in Atomically Thin FePS ₃ Lee, Jae-Ung; Lee, Sungmin; Ryoo, Ji Hoon Nano Letters, Vol. 16, Issue 12 https://doi.org/10.1021/acs.nanolett.6b03052	journal	November 2016
Differential reflection spectroscopy of very thin surface films McIntyre, J. D. E.; Aspnes, D. E. Surface Science, Vol. 24, Issue 2 https://doi.org/10.1016/0039-6028(71)90272-X	journal	February 1971
Spectroscopic studies of the two-dimensional magnetic insulators chromium trichloride and chromium tribromide—I Bermudez, Victor M.; McClure, Donald S. Journal of Physics and Chemistry of Solids, Vol. 40, Issue 2 https://doi.org/10.1016/0022-3697(79)90030-1	journal	January 1979
Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit Huang, Bevin; Clark, Genevieve; Navarro-Moratalla, Efrén Nature, Vol. 546, Issue 7657 https://doi.org/10.1038/nature22391	journal	June 2017
On the Magnetic Properties of a CrBr ₃ Single Crystal Tsubokawa, Ichiro Journal of the Physical Society of Japan, Vol. 15, Issue 9 https://doi.org/10.1143/JPSJ.15.1664	journal	September 1960
Intrinsic Optical Properties of CrCl3 Pollini, I.; Spinolo, G. physica status solidi (b), Vol. 41, Issue 2 https://doi.org/10.1002/pssb.19700410224	journal	January 1970
Valleytronics in 2D materials Schaibley, John R.; Yu, Hongyi; Clark, Genevieve Nature Reviews Materials, Vol. 1, Issue 11 https://doi.org/10.1038/natrevmats.2016.55	journal	August 2016
Diluted magnetic semiconductors Furdyna, J. K. Journal of Applied Physics, Vol. 64, Issue 4 https://doi.org/10.1063/1.341700	journal	August 1988
Optical properties of III-Mn-V ferromagnetic semiconductors Burch, K. S.; Awschalom, D. D.; Basov, D. N. Journal of Magnetism and Magnetic Materials, Vol. 320, Issue 23 https://doi.org/10.1016/j.jmmm.2008.08.060	journal	December 2008
(Ga,Mn)As: A new diluted magnetic semiconductor based on GaAs Ohno, H.; Shen, A.; Matsukura, F. Applied Physics Letters, Vol. 69, Issue 3 https://doi.org/10.1063/1.118061	journal	July 1996
Magneto-optical properties of ferromagnetic chromium trihalides Dillon, J. F.; Kamimura, H.; Remeika, J. P. Journal of Physics and Chemistry of Solids, Vol. 27, Issue 9 https://doi.org/10.1016/0022-3697(66)90148-X	journal	September 1966
Dilute ferromagnetic semiconductors: Physics and spintronic structures Dietl, Tomasz; Ohno, Hideo Reviews of Modern Physics, Vol. 86, Issue 1 https://doi.org/10.1103/RevModPhys.86.187	journal	March 2014
Charge-transfer transitions in chromium trihalides Shinagawa, K.; Sato, H.; Ross, H. J. Journal of Physics: Condensed Matter, Vol. 8, Issue 44 https://doi.org/10.1088/0953-8984/8/44/002	journal	October 1996
Magneto-optical properties of ferromagnetic chromium trihalides Dillon, J. F.; Kamimura, H.; Remeika, J. P. Solid State Communications, Vol. 4, Issue 4 https://doi.org/10.1016/0038-1098(66)90016-0	journal	April 1966
Insulating Ferromagnetic Spinels Baltzer, P. K.; Lehmann, H. W.; Robbins, M. Physical Review Letters, Vol. 15, Issue 13 https://doi.org/10.1103/physrevlett.15.572.3	journal	September 1965
Discovery of Intrinsic Ferromagnetism in Two-Dimensional van der Waals Crystals Gong, Cheng; Li, Lin; Li, Zhenglu CLEO: Applications and Technology, Conference on Lasers and Electro-Optics https://doi.org/10.1364/cleo_at.2017.jth5c.2	conference	January 2017
Spectroscopic studies of the two-dimensional magnetic insulators chromium trichloride and chromium tribromide—II Bermudez, Victor M.; McClure, Donald S. Journal of Physics and Chemistry of Solids, Vol. 40, Issue 2 https://doi.org/10.1016/0022-3697(79)90031-3	journal	January 1979
Optical Properties of III-Mn-V Ferromagnetic Semiconductors Burch, K. S.; Awschalom, D. D.; Basov, D. N. arXiv https://doi.org/10.48550/arxiv.0810.3669	text	January 2008
Layer-dependent Ferromagnetism in a van der Waals Crystal down to the Monolayer Limit Huang, Bevin; Clark, Genevieve; Navarro-Moratalla, Efren arXiv https://doi.org/10.48550/arxiv.1703.05892	text	January 2017

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