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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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.).
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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.
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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.
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Supplementary Information
Supplementary Figs. 1–11, Tables 1 and 2, Notes 1–7 and References.
Source data
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Source Data Fig. 3
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Source Data Fig. 4
Statistical source data.
Source Data Extended Data Fig. 1
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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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DOI: https://doi.org/10.1038/s41565-021-00953-w
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