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Tuning inelastic light scattering via symmetry control in the two-dimensional magnet CrI3

Nature Nanotechnology volume 15, pages 212–216 (2020)Cite this article

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Abstract

The coupling between spin and charge degrees of freedom in a crystal gives rise to magneto-optical effects with applications in the sensitive detection of local magnetic order, optical modulation and data storage. In two-dimensional magnets these effects manifest themselves in the large magneto-optical Kerr effect1,2, spontaneous helical light emission3,4 from ferromagnetic (FM) monolayers and electric-field induced Kerr rotation5,6,7 and giant second-order non-reciprocal optical effects8 in antiferromagnetic (AFM) bilayers. Here we demonstrate the tuning of inelastically scattered light through symmetry control in atomically thin chromium triiodide (CrI3). In monolayers, we found an extraordinarily large magneto-optical Raman effect from an A1g phonon mode due to the emergence of FM order. The linearly polarized, inelastically scattered light rotates by ~40°, more than two orders of magnitude larger than the rotation from the magneto-optical Kerr effect under the same experimental conditions. In CrI3 bilayers, the same phonon mode becomes Davydov-split into two modes of opposite parity, which exhibit divergent selection rules that depend on inversion symmetry and the underlying magnetic order. We demonstrate the magneto-electrical control over these selection rules by activating or suppressing Raman activity for the odd-parity phonon mode and the magneto-optical rotation of scattered light from the even-parity phonon mode. Our work underlines the unique opportunities provided by two-dimensional magnets to control the combined time-reversal and inversion symmetries to manipulate Raman optical selection rules and for exploring emergent magneto-optical effects and spin–phonon coupled physics.

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Fig. 1: Raman scattering and its dependence on magnetic order in monolayer CrI3.
Fig. 2: The effects of FM order on the polarization of inelastically scattered light in monolayer CrI3.
Fig. 3: Coupling of magnetic order and Raman optical selection rules in bilayer CrI3.
Fig. 4: Electrical switching of a Raman-silent phonon in bilayer CrI3.

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Data availability

The datasets generated during and/or analysed during this study are available from the corresponding author upon reasonable request.

References

  1. Huang, B. et al. Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit. Nature 546, 270–273 (2017).

    Article  CAS  Google Scholar 

  2. Wu, M., Li, Z., Cao, T. & Louie, S. G. Physical origin of giant excitonic and magneto-optical responses in two-dimensional ferromagnetic insulators. Nat. Commun. 10, 2371 (2019).

    Article  Google Scholar 

  3. Seyler, K. L. et al. Ligand-field helical luminescence in a 2D ferromagnetic insulator. Nat. Phys. 14, 277–281 (2018).

    Article  CAS  Google Scholar 

  4. Zhang, Z. et al. Direct photoluminescence probing of ferromagnetism in monolayer two-dimensional CrBr3. Nano Lett. 19, 3138–3142 (2019).

    Article  CAS  Google Scholar 

  5. Huang, B. et al. Electrical control of 2D magnetism in bilayer CrI3. Nat. Nanotechnol. 13, 544–548 (2018).

    Article  CAS  Google Scholar 

  6. Jiang, S., Shan, J. & Mak, K. F. Electric-field switching of two-dimensional van der Waals magnets. Nat. Mater. 17, 406–410 (2018).

    Article  CAS  Google Scholar 

  7. Sivadas, N., Okamoto, S. & Xiao, D. Gate-controllable magneto-optic Kerr effect in layered collinear antiferromagnets. Phys. Rev. Lett. 117, 267203 (2016).

    Article  Google Scholar 

  8. Sun, Z. et al. Giant and nonreciprocal second harmonic generation from layered antiferromagnetism in bilayer CrI3. Nature 572, 497–501 (2019).

    Article  CAS  Google Scholar 

  9. Xi, X. et al. Strongly enhanced charge-density-wave order in monolayer NbSe2. Nat. Nanotechnol. 10, 765–769 (2015).

    Article  CAS  Google Scholar 

  10. Méasson, M. A. et al. Amplitude ‘Higgs’ mode in the 2H-NbSe2 superconductor. Phys. Rev. B 89, 060503 (2014).

    Article  Google Scholar 

  11. Tenne, D. A. et al. Probing nanoscale ferroelectricity by ultraviolet Raman spectroscopy. Science 313, 1614–1617 (2006).

    Article  CAS  Google Scholar 

  12. Kung, H. H. et al. Chiral spin mode on the surface of a topological insulator. Phys. Rev. Lett. 119, 136802 (2017).

    Article  Google Scholar 

  13. Tian, Y., Gray, M. J., Ji, H., Cava, R. J. & Burch, K. S. Magneto-elastic coupling in a potential ferromagnetic 2D atomic crystal. 2D Mater. 3, 025035 (2016).

    Article  Google Scholar 

  14. Kim, K. et al. Antiferromagnetic ordering in van der Waals 2D magnetic material MnPS3 probed by Raman spectroscopy. 2D Mater. 6, 041001 (2019).

    Article  CAS  Google Scholar 

  15. Klein, D. R. et al. Enhancement of interlayer exchange in an ultrathin two-dimensional magnet. Nat. Phys. 15, 1255–1260 (2019).

    Article  CAS  Google Scholar 

  16. Lee, J. U. et al. Ising-type magnetic ordering in atomically thin FePS3. Nano Lett. 16, 7433–7438 (2016).

    Article  CAS  Google Scholar 

  17. Kim, K. et al. Suppression of magnetic ordering in XXZ-type antiferromagnetic monolayer NiPS3. Nat. Commun. 10, 345 (2019).

    Article  Google Scholar 

  18. Wang, X. et al. Raman spectroscopy of atomically thin two-dimensional magnetic iron phosphorus trisulfide (FePS3) crystals. 2D Mater. 3, 031009 (2016).

    Article  Google Scholar 

  19. Webster, L., Liang, L. & Yan, J. A. Distinct spin–lattice and spin–phonon interactions in monolayer magnetic CrI3. Phys. Chem. Chem. Phys. 20, 23546–23555 (2018).

    Article  CAS  Google Scholar 

  20. Jin, W. et al. Raman fingerprint of two terahertz spin wave branches in a two-dimensional honeycomb Ising ferromagnet. Nat. Commun. 9, 5122 (2018).

    Article  Google Scholar 

  21. Larson, D. T. & Kaxiras, E. Raman spectrum of CrI3: an ab initio study. Phys. Rev. B 98, 085406 (2018).

    Article  CAS  Google Scholar 

  22. Long, D. A. Raman Spectroscopy (McGraw-Hill, 1977).

  23. Verble, J. L. & Wieting, T. J. Lattice mode degeneracy in MoS2 and other layer compounds. Phys. Rev. Lett. 25, 362–365 (1970).

    Article  CAS  Google Scholar 

  24. Song, Q. J. et al. Physical origin of Davydov splitting and resonant Raman spectroscopy of Davydov components in multilayer MoTe2. Phys. Rev. B 93, 115409 (2016).

    Article  Google Scholar 

  25. Castellanos-Gomez, A., Buscema, M. & Molenaar, R. Deterministic transfer of two-dimensional materials by all-dry viscoelastic stamping. 2D Mater. 1, 011002 (2014).

    Article  Google Scholar 

  26. Shubnikov, A. V. & Belov, N. V. Colored Symmetry (Permagon Press, 1964).

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Acknowledgements

This work was mainly supported by the Department of Energy, Basic Energy Sciences, Materials Sciences and Engineering Division (DE-SC0012509). Understanding of magnetoelectric switching of Raman optical selection rules is partially supported by AFOSR MURI 2D MAGIC (FA9550-19-1-0390). Work at ORNL (M.A.M.) was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. K.W. and T.T. acknowledge support from the Elemental Strategy Initiative conducted by the MEXT, Japan and JSPS KAKENHI Grant nos JP15K21722. B.H. acknowledges partial support from NW IMPACT. X.X. acknowledges the support from the State of Washington funded and from the Boeing Distinguished Professorship in Physics.

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Author notes

  1. These authors contributed equally: Bevin Huang, John Cenker.

Authors and Affiliations

  1. Department of Physics, University of Washington, Seattle, WA, USA

    Bevin Huang, John Cenker, Essance L. Ray, Tiancheng Song & Xiaodong Xu

  2. Department of Physics, Carnegie Mellon University, Pittsburgh, PA, USA

    Xiaoou Zhang & Di Xiao

  3. National Institute for Materials Science, Tsukuba, Japan

    Takashi Taniguchi & Kenji Watanabe

  4. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Michael A. McGuire

  5. Department of Materials Science and Engineering, University of Washington, Seattle, WA, USA

    Xiaodong Xu

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  1. Bevin Huang
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Contributions

X.X., B.H. and J.C. conceived the experiment. B.H. and J.C. fabricated and characterized the samples, assisted by E.L.R. and T.S. B.H. and J.C. performed the Raman and magnetic circular dichroism measurements. B.H., J.C., X.X., X.Z. and D.X. analysed and interpreted the results. T.T. and K.W. synthesized the hBN crystals. M.A.M. synthesized and characterized the bulk CrI3 crystals. B.H., J.C., X.X. and D.X. wrote the paper with input from all the authors. All the authors discussed the results.

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Correspondence to Xiaodong Xu.

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Supplementary Figs. 1–8.

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Huang, B., Cenker, J., Zhang, X. et al. Tuning inelastic light scattering via symmetry control in the two-dimensional magnet CrI3. Nat. Nanotechnol. 15, 212–216 (2020). https://doi.org/10.1038/s41565-019-0598-4

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