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Dynamic topological domain walls driven by lithium intercalation in graphene

Nature Nanotechnology volume 18, pages 1154–1161 (2023)Cite this article

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Abstract

Stacking engineering in van der Waals (vdW) materials is a powerful method to control topological electronic phases for quantum device applications. Atomic intercalation into the vdW material can modulate the stacking structure at the atomic scale without a highly technical protocol. Here we report that lithium intercalation in a topologically structured graphene/buffer system on SiC(0001) drives dynamic topological domain wall (TDW) motions associated with stacking order change by using an in situ aberration-corrected low-energy electron microscope in combination with theoretical modelling. We observe sequential and selective lithium intercalation that starts at topological crossing points (AA stacking) and then selectively extends to AB stacking domains. Lithium intercalation locally changes the domain stacking order to AA and in turn alters the neighbouring TDW stacking orders, and continuous intercalation drives the evolution of the whole topological structure network. Our work reveals moving TDWs protected by the topology of stacking and lays the foundation for controlling the stacking structure via atomic intercalation. These findings open up new avenues to realize intercalation-driven vdW electronic devices.

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Fig. 1: Stacking domains in pristine graphene epitaxially grown on SiC(0001).
Fig. 2: Dynamic observation of lithium intercalation and deintercalation.
Fig. 3: Domain-selective lithium intercalation into the graphene/buffer interlayer.
Fig. 4: Dynamic evolution of topological defects following lithium intercalation for pinned TCPs and mobile TDWs.
Fig. 5: Atomistic understanding of stacking structure transition and TDWs evolution.

Data availability

Datasets used to construct plots and support other findings in this article are available at ScienceDB. Research data with the identifier https://doi.org/10.57760/sciencedb.07810 (ref. 45).

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Acknowledgements

We acknowledge R. M. Tromp and J. Jobst for the extensive discussion on the intercalation pathway in epitaxial graphene. We also thank H. Fukidome and N. Endoh for providing graphene samples at an early stage of this study. W.X.T. was supported by the NSFC as the National Key Instrumental Development Scheme (grant no. 0211002322010), the 985 Key National University Funding at Chongqing University (grant nos. 0211001104414 and 0211001104423) and Fundamental Research Funds for the Central Universities (grant no. 0903005203521). Y.E., R.A. and S.H. acknowledge support from the Japan Society for the Promotion of Science (JSPS) KAKENHI: a Grant-in-Aid for JSPS Fellows (grant no. 19J12818 to Y.E.); a Grant-in-Aid for Scientific Research (B) (grant no. 20H02616 to R.A.); and a Grant-in-Aid for Scientific Research (A) (grant no. 16H02108 to S.H.). J.Z.L. acknowledges support from the Australian Research Council Discovery Project (grant no. DP210103888). K.S.N. is grateful to the Ministry of Education, Singapore (Research Centre of Excellence award to the Institute for Functional Intelligent Materials, I-FIM, project no. EDUNC-33-18-279-V12), and to the Royal Society (UK, grant no. RSRP\R\190000) for support. The DFT calculations were undertaken with the assistance of resources and services from the National Computational Infrastructure (NCI), which is supported by the Australian Government. The molecular dynamics simulations were supported by resources provided by the Pawsey Supercomputing Research Centre with funding from the Australian Government and the Government of Western Australia.

Author information

Author notes

  1. These authors contributed equally: Yukihiro Endo, Xue Yan.

Authors and Affiliations

  1. Department of Physics, The University of Tokyo, Tokyo, Japan

    Yukihiro Endo, Ryota Akiyama, Rei Hobara & Shuji Hasegawa

  2. Department of Mechanical Engineering, The University of Melbourne, Parkville, Victoria, Australia

    Xue Yan, Christian Brandl & Jefferson Zhe Liu

  3. College of Materials Science and Engineering, Chongqing University, Chongqing, China

    Meng Li & Wen-Xin Tang

  4. ShanghaiTech University, Shanghai, China

    Weishi Wan

  5. Institute for Functional Intelligent Materials, National University of Singapore, Singapore, Singapore

    K. S. Novoselov

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  1. Yukihiro Endo
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Contributions

The experiment was designed by Y.E., R.A., S.H., J.Z.L. and W.X.T. Y.E. and M.L. performed the measurements and analysed the data. X.Y., C.B. and J.Z.L. developed theoretical models and performed calculations. M.L., W.W. and W.X.T. built the LEEM system. All of the authors contributed to the interpretation of the TDW’s evolution through discussion. Y.E., X.Y., M.L., R.A. and J.Z.L. wrote the paper with the input of C.B., R.H., S.H., K.S.N. and W.X.T.

Corresponding authors

Correspondence to Meng Li, Ryota Akiyama, Jefferson Zhe Liu or Wen-Xin Tang.

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Nature Nanotechnology thanks Jingshu Hui and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Stackings of graphene/SiC in simulation model.

(a) A slab model to simulate our sample, including SiC(0001) substrate, buffer layer, and one graphene top layer. The C3 and C4 atom are shown in the magnified picture, which represent buffer layer carbon atoms having 3 and 4 covalent bonds, respectively. (b)-(e) The different stacking order of a graphene layer on top of the buffer layer. (b) AA stacking; (c) AB stacking; (d) BA stacking; and (e) SP stacking. The blue, yellow, black, and red spheres represent Si atom, C atom in SiC bulk, C atom in buffer layer, and C atom in top graphene. Only the top bilayer SiC is shown. (f) The relative energy per C atom of AA, AB, BA, and SP stacking in the unit-cell of the 6√3 × 6√3R30° superstructure.

Supplementary information

Supplementary Information

Supplementary Information, Tables 1–6, Figs. 1–11, and captions for Extended Data Fig. 1 and Videos 1 and 2.

Supplementary Video 1

BF-LEEM movie of lithium intercalation process at room temperature with the incident electron energy of 3.3 eV (the snapshots were taken every 2 s).

Supplementary Video 2

BF-LEEM movie of lithium deintercalation process by heating at 100 °C with the incident electron energy of 3.3 eV (the snapshots were taken every 1.15 s).

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Endo, Y., Yan, X., Li, M. et al. Dynamic topological domain walls driven by lithium intercalation in graphene. Nat. Nanotechnol. 18, 1154–1161 (2023). https://doi.org/10.1038/s41565-023-01463-7

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