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Single-atom vibrational spectroscopy with chemical-bonding sensitivity

Nature Materials volume 22, pages 612–618 (2023)Cite this article

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Abstract

Correlation of lattice vibrational properties with local atomic configurations in materials is essential for elucidating functionalities that involve phonon transport in solids. Recent developments in vibrational spectroscopy in a scanning transmission electron microscope have enabled direct measurements of local phonon modes at defects and interfaces by combining high spatial and energy resolution. However, pushing the ultimate limit of vibrational spectroscopy in a scanning transmission electron microscope to reveal the impact of chemical bonding on local phonon modes requires extreme sensitivity of the experiment at the chemical-bond level. Here we demonstrate that, with improved instrument stability and sensitivity, the specific vibrational signals of the same substitutional impurity and the neighbouring carbon atoms in monolayer graphene with different chemical-bonding configurations are clearly resolved, complementary with density functional theory calculations. The present work opens the door to the direct observation of local phonon modes with chemical-bonding sensitivity, and provides more insights into the defect-induced physics in graphene.

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Fig. 1: Vibrational spectroscopy of substitutional Si impurities in graphene with different bonding configurations.
Fig. 2: Atom-by-atom analysis of the vibrational EELS spectra in silicon-doped graphene.
Fig. 3: The origin of specific phonon modes observed in Si–C3 and Si–C4.
Fig. 4: Atom-by-atom vibrational spectroscopy analysis of the N–C3 defect in graphene.

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Source data are provided with this paper. Additional data of this study are available from the corresponding authors on reasonable request.

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Acknowledgements

The work at the University of Chinese Academy of Sciences (UCAS) and Institute of Physics (IoP) received financial support from the National Key R&D Program of China with grant no. 2018YFA0305800 (G.S. and W.Z.); the Beijing Outstanding Young Scientist Program with grant no. BJJWZYJH01201914430039 (W.Z.); and the National Natural Science Foundation of China under grant nos 51872285 (W.Z.), 51622211 (W.Z.) and 61888102 (S.D.). Theoretical work at Vanderbilt was supported by the US Department of Energy, Office of Science, Basic Energy Science, Materials Science and Engineering Directorate grant no. DE-FG02-09ER46554 (S.T.P. and D.-L.B.) and the McMinn Endowment (S.T.P.). The research was also supported in part by the Strategic Priority Research Program of the Chinese Academy of Sciences with grant no. XDB28000000 (G.S.); the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences with grant no. QYZDB-SSW-JSC019 (W.Z.); and the K. C. Wong Education Foundation of the Chinese Academy of Sciences (D.-L.B.). We thank T. Lovejoy for helping with setting up the electron optics.

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Author notes

  1. These authors contributed equally: Mingquan Xu, De-Liang Bao, Aowen Li.

Authors and Affiliations

  1. School of Physical Sciences and CAS Key Laboratory of Vacuum Physics, University of Chinese Academy of Sciences, Beijing, P. R. China

    Mingquan Xu, Aowen Li, Meng Gao, Dongqian Meng, Ang Li, Shixuan Du, Gang Su, Stephen J. Pennycook, Sokrates T. Pantelides & Wu Zhou

  2. Department of Physics and Astronomy, Vanderbilt University, Nashville, TN, USA

    De-Liang Bao & Sokrates T. Pantelides

  3. Institute of Physics, Chinese Academy of Sciences, Beijing, P. R. China

    Shixuan Du

  4. Kavli Institute for Theoretical Sciences, University of Chinese Academy of Sciences, Beijing, P. R. China

    Gang Su

  5. Department of Electrical and Computer Engineering, Vanderbilt University, Nashville, TN, USA

    Sokrates T. Pantelides

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Contributions

W.Z. designed the project. M.X. and Aowen Li performed the electron microscopy experiments under the supervision of W.Z.; D.-L.B. and S.T.P. performed the theoretical study. D.M. prepared the graphene sample. M.X., D.-L.B., Aowen Li, S.T.P. and W.Z. wrote the paper with additional input from M.G., S.D., G.S. and S.J.P. Ang Li contributed to the data processing. All authors discussed the results and the paper.

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Correspondence to Sokrates T. Pantelides or Wu Zhou.

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Nature Materials thanks Xingxu Yan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Xu, M., Bao, DL., Li, A. et al. Single-atom vibrational spectroscopy with chemical-bonding sensitivity. Nat. Mater. 22, 612–618 (2023). https://doi.org/10.1038/s41563-023-01500-9

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