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Complete structural characterization of single carbon nanotubes by Rayleigh scattering circular dichroism

Nature Nanotechnology volume 16, pages 1073–1078 (2021)Cite this article

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Abstract

Non-invasive, high-throughput spectroscopic techniques can identify chiral indices (n,m) of carbon nanotubes down to the single-tube level1,2,3,4,5,6. Yet, for complete characterization and to unlock full functionality, the handedness, the structural property associated with mirror symmetry breaking, also needs to be identified accurately and efficiently7,8,9,10,11,12,13,14. So far, optical methods fail in the handedness characterization of single nanotubes because of the extremely weak chiroptical signals (roughly 10−7) compared with the excitation light15,16. Here we demonstrate the complete structure identification of single nanotubes in terms of both chiral indices and handedness by Rayleigh scattering circular dichroism. Our method is based on the background-free feature of Rayleigh scattering collected at an oblique angle, which enhances the nanotube’s chiroptical signal by three to four orders of magnitude compared with conventional absorption circular dichroism. We measured a total of 30 single-walled carbon nanotubes including both semiconducting and metallic nanotubes and found that their absolute chiroptical signals show a distinct structure dependence, which can be qualitatively understood through tight-binding calculations. Our strategy enables the exploration of handedness-related functionality of single nanotubes and provides a facile platform for chiral discrimination and chiral device exploration at the level of individual nanomaterials.

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Fig. 1: Chiroptical signal measurement for single nanotubes.
Fig. 2: Rayleigh circular dichroism measurement for a suspended nanotube.
Fig. 3: Typical Ray-CD results for three representative nanotubes and the summary of handedness results for 30 nanotubes.
Fig. 4: Structure-dependent Ray-CD peak intensity.

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Data availability

The data supporting the findings of this study are available within the paper, Extended Data Figs. 1 and 2 and the Supplementary Information. Extra data are available from the corresponding author upon request. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China under grant numbers 52021006 (J. Zhang), 52025023 (K.L.) and 51991342 (K.L.); the Key R&D Programme of Guangdong Province with grant numbers 2020B010189001 (K.L.), 2019B010931001 (K.L.) and 2018B030327001 (K.L.); the National Key R&D Programme of China under grant numbers 2016YFA0300903 (K.L.), 2017YFA0303800 (K.L.) and 2016YFA0300804 (P.G.); the Strategic Priority Research Programme of Chinese Academy of Sciences with grant number XDB33000000 (K.L.); Beijing Natural Science Foundation under grant number JQ19004 (K.L.); Beijing Graphene Innovation Programme under grant number Z181100004818003 (K.L.); the Pearl River Talent Recruitment Programme of Guangdong Province with grant number 2019ZT08C321 (K.L.); National Equipment Programme of China under grant number ZDYZ2015-1 (X.B.); National Postdoctoral Programme for Innovative Talents under award number BX20190016 (C.L.) and China Postdoctoral Science Foundation under award numbers 2019M660280 (C.L.) and 2019M660281 (R.Q.).

Author information

Author notes

  1. These authors contributed equally: Fengrui Yao, Wentao Yu, Can Liu.

Authors and Affiliations

  1. State Key Laboratory for Mesoscopic Physics, Frontiers Science Center for Nano-optoelectronics, School of Physics, Peking University, Beijing, China

    Fengrui Yao, Wentao Yu, Can Liu, Yingze Su, Yilong You, He Ma, Chunchun Wu, Chaojie Ma & Kaihui Liu

  2. International Center for Quantum Materials, Collaborative Innovation Center of Quantum Matter, Peking University, Beijing, China

    Ruixi Qiao, Peng Gao & Kaihui Liu

  3. Shanxi Key Laboratory of Optical Information Technology, School of Physical Science and Technology, Northwestern Polytechnical University, Xi’an, China

    Fajun Xiao & Jianlin Zhao

  4. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Xuedong Bai

  5. Songshan Lake Materials Laboratory, Institute of Physics, Chinese Academy of Sciences, Dongguan, China

    Xuedong Bai & Kaihui Liu

  6. Department of Electronics and Nanoengineering, QTF Center of Excellence, Aalto University, Espoo, Finland

    Zhipei Sun

  7. Department of Mechanical Engineering, The University of Tokyo, Tokyo, Japan

    Shigeo Maruyama

  8. Department of Physics, University of California at Berkeley, Berkeley, CA, USA

    Feng Wang

  9. Center for Nanochemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Jin Zhang

  10. Interdisciplinary Institute of Light-Element Quantum Materials and Research Center for Light-Element Advanced Materials, Peking University, Beijing, China

    Kaihui Liu

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  1. Fengrui Yao
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Contributions

K.L. conceived and supervised the project. F.Y., Y.S. and H.M. designed and built the optical setup. F.Y., W.Y. and C.L. conducted the optical experiments. C.L. performed sample growth and the scanning tunnelling microscope experiments. Y.S., Y.Y., F.Y., W.Y. and H.M. contributed the theoretical calculations. R.Q., P.G. and X.B. conducted the transmission electron microscopy experiments. C.W., C.M., J. Zhao, Z.S., S.M., F.W. and J. Zhang suggested optical experiments. All of the authors discussed the results and wrote the paper.

Corresponding author

Correspondence to Kaihui Liu.

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Peer review information Nature Nanotechnology thanks the anonymous reviewers for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Synthesis of SWNTs.

a, Schematic of SWNTs growth across open slit by kite-flying growth mechanism. b, SEM image of the as-grown SWNTs.

Extended Data Fig. 2 Structure-dependent Ray-CD peak intensity.

a,b, Calculated mapping of Ray-CD peak intensity as a function of the diameter and chiral angle of S33 transition for semiconducting type I (a) and type II (b) nanotubes. c,d, Calculated (green triangles) versus experimental (orange circles) peak intensities of Ray-CD for S33 transitions as a function of diameter for type I (c) and type II (d) family. The chiral angle of selected nanotubes is around 19 ° (black lines in calculated mappings). e,f, Calculated (green triangles) versus experimental (orange circles) peak intensities of Ray-CD for S33 transitions as a function of the chiral angle for type I (e) and type II (f) family. The diameters of the selected nanotubes are around 2.0 nm (white lines in calculated mappings). Error bars are derived from absolute Ray-CD values of armchair samples.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–11, Tables 1 and 2, Notes 1–7 and References.

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Source Data Fig. 2

Statistical source data.

Source Data Fig. 3

Statistical source data.

Source Data Fig. 4

Statistical source data.

Source Data Extended Data Fig. 1

Statistical source data.

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Yao, F., Yu, W., Liu, C. et al. Complete structural characterization of single carbon nanotubes by Rayleigh scattering circular dichroism. Nat. Nanotechnol. 16, 1073–1078 (2021). https://doi.org/10.1038/s41565-021-00953-w

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