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Chirality-specific growth of single-walled carbon nanotubes on solid alloy catalysts

Nature volume 510, pages 522–524 (2014)Cite this article

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Abstract

Carbon nanotubes have many material properties that make them attractive for applications1,2. In the context of nanoelectronics3, interest has focused on single-walled carbon nanotubes4 (SWNTs) because slight changes in tube diameter and wrapping angle, defined by the chirality indices (n, m), will shift their electrical conductivity from one characteristic of a metallic state to one characteristic of a semiconducting state, and will also change the bandgap. However, this structure–function relationship can be fully exploited only with structurally pure SWNTs. Solution-based separation methods5 yield tubes within a narrow structure range, but the ultimate goal of producing just one type of SWNT by controlling its structure during growth has proved to be a considerable challenge over the last two decades6,7,8,9. Such efforts aim to optimize the composition6,10,11,12,13,14,15,16,17 or shape18,19,20,21 of the catalyst particles that are used in the chemical vapour deposition synthesis process to decompose the carbon feedstock and influence SWNT nucleation and growth22,23,24,25. This approach resulted in the highest reported proportion, 55 per cent, of single-chirality SWNTs in an as-grown sample11. Here we show that SWNTs of a single chirality, (12, 6), can be produced directly with an abundance higher than 92 per cent when using tungsten-based bimetallic alloy nanocrystals as catalysts. These, unlike other catalysts used so far, have such high melting points that they maintain their crystalline structure during the chemical vapour deposition process. This feature seems crucial because experiment and simulation both suggest that the highly selective growth of (12, 6) SWNTs is the result of a good structural match between the carbon atom arrangement around the nanotube circumference and the arrangement of the catalytically active atoms in one of the planes of the nanocrystal catalyst. We anticipate that using high-melting-point alloy nanocrystals with optimized structures as catalysts paves the way for total chirality control in SWNT growth and will thus promote the development of SWNT applications.

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Figure 1
Figure 2: Characterizations of SWNTs grown at 1,030 °C.
Figure 3: Characterizations of catalyst structure.
Figure 4: Characterizations of SWNTs nucleated on catalyst nanoparticles.

References

  1. Shulaker, M. M. et al. Carbon nanotube computer. Nature 501, 526–530 (2013)

    Article  ADS  CAS  Google Scholar 

  2. De Volder, M. F. L., Tawfick, S. H., Baughman, R. H. & Hart, A. J. Carbon Nanotubes: present and future commercial applications. Science 339, 535–539 (2013)

    ADS  CAS  PubMed  Google Scholar 

  3. Avouris, P., Chen, Z. & Perebeinos, V. Carbon-based electronics. Nature Nanotechnol. 2, 605–615 (2007)

    Article  ADS  CAS  Google Scholar 

  4. Iijima, S. & Ichihashi, T. Single-shell carbon nanotubes of 1-nm diameter. Nature 363, 603–605 (1993)

    Article  ADS  CAS  Google Scholar 

  5. Hersam, M. C. Progress towards monodisperse single-walled carbon nanotubes. Nature Nanotechnol. 3, 387–394 (2008)

    Article  ADS  CAS  Google Scholar 

  6. Bachilo, S. M. et al. Narrow (n,m)-distribution of single-walled carbon nanotubes grown using a solid supported catalyst. J. Am. Chem. Soc. 125, 11186–11187 (2003)

    Article  CAS  Google Scholar 

  7. Ding, F., Harutyunyan, A. R. & Yakobson, B. I. Dislocation theory of chirality-controlled nanotube growth. Proc. Natl Acad. Sci. USA 106, 2506–2509 (2009)

    Article  ADS  CAS  Google Scholar 

  8. Liu, J. et al. Chirality-controlled synthesis of single-wall carbon nanotubes using vapour-phase epitaxy. Nature Commun. 3, 1199 (2012)

    Article  ADS  Google Scholar 

  9. Chen, Y. et al. Helicity-dependent single-walled carbon nanotube alignment on graphite for helical angle and handedness recognition. Nature Commun. 4, 2205 (2013)

    Article  ADS  Google Scholar 

  10. An, L., Owens, J. M., McNeil, L. E. & Liu, J. Synthesis of nearly uniform single-walled carbon nanotubes using identical metal-containing molecular nanoclusters as catalysts. J. Am. Chem. Soc. 124, 13688–13689 (2002)

    Article  CAS  Google Scholar 

  11. Lolli, G. et al. Tailoring (n, m) structure of single-walled carbon nanotubes by modifying reaction conditions and the nature of the support of CoMo catalysts. J. Phys. Chem. B 110, 2108–2115 (2006)

    Article  CAS  Google Scholar 

  12. Zhou, W. et al. Copper catalyzing growth of single-walled carbon nanotubes on substrates. Nano Lett. 6, 2987–2990 (2006)

    Article  ADS  CAS  Google Scholar 

  13. Li, X. et al. Selective synthesis combined with chemical separation of single-walled carbon nanotubes for chirality selection. J. Am. Chem. Soc. 129, 15770–15771 (2007)

    Article  CAS  Google Scholar 

  14. Chiang, W. H. & Sankaran, R. M. Linking catalyst composition to chirality distributions of as-grown single-walled carbon nanotubes by tuning NixFe1−x nanoparticles. Nature Mater. 8, 882–886 (2009)

    Article  ADS  CAS  Google Scholar 

  15. Wang, H. et al. Chiral-selective CoSO4/SiO2 catalyst for (9,8) single-walled carbon nanotube growth. ACS Nano 7, 614–626 (2013)

    Article  CAS  Google Scholar 

  16. Liu, B., Ren, W., Li, S., Liu, C. & Cheng, H.-M. High temperature selective growth of single-walled carbon nanotubes with a narrow chirality distribution from a CoPt bimetallic catalyst. Chem. Commun. 48, 2409–2411 (2012)

    Article  CAS  Google Scholar 

  17. Peng, F. et al. Diameter-controlled growth of aligned single-walled carbon nanotubes on quartz using molecular nanoclusters as catalyst precursors. Chin. Sci. Bull. 58, 433–439 (2013)

    Article  CAS  Google Scholar 

  18. Reich, S., Li, L. & Robertson, J. Control the chirality of carbon nanotubes by epitaxial growth. Chem. Phys. Lett. 421, 469–472 (2006)

    Article  ADS  CAS  Google Scholar 

  19. Harutyunyan, A. R. et al. Preferential growth of single-walled carbon nanotubes with metallic conductivity. Science 326, 116–120 (2009)

    Article  ADS  CAS  Google Scholar 

  20. Koziol, K. K. K., Ducati, C. & Windle, A. H. Carbon nanotubes with catalyst controlled chiral angle. Chem. Mater. 22, 4904–4911 (2010)

    Article  CAS  Google Scholar 

  21. He, M. et al. Chiral-selective growth of single-walled carbon nanotubes on lattice-mismatched epitaxial cobalt nanoparticles. Sci. Rep. 3, 1460 (2013)

    Article  Google Scholar 

  22. Li, Y. et al. How catalysts affect the growth of single-walled carbon nanotubes on substrates. Adv. Mater. 22, 1508–1515 (2010)

    Article  CAS  Google Scholar 

  23. Shibuta, Y. & Maruyama, S. Molecular dynamics simulation of formation process of single-walled carbon nanotubes by CCVD method. Chem. Phys. Lett. 382, 381–386 (2003)

    Article  ADS  CAS  Google Scholar 

  24. Raty, J.-Y., Gygi, F. & Galli, G. Growth of carbon nanotubes on metal nanoparticles: a microscopic mechanism from ab initio molecular dynamics simulations. Phys. Rev. Lett. 95, 096103 (2005)

    Article  ADS  Google Scholar 

  25. Hofmann, S. et al. In situ observations of catalyst dynamics during surface-bound carbon nanotube nucleation. Nano Lett. 7, 602–608 (2007)

    Article  ADS  CAS  Google Scholar 

  26. Yao, S., Zhang, Z., Li, Y. & Wang, E. Two hexa-TM-containing (TM = Co2+ and Ni2+) {P2W12}-based trimeric tungstophosphates. Dalton Trans. 39, 3884–3889 (2010)

    Article  CAS  Google Scholar 

  27. Chu, H. et al. Decoration of gold nanoparticles on surface-grown single-walled carbon nanotubes for detection of every nanotube by surface-enhanced Raman spectroscopy. J. Am. Chem. Soc. 131, 14310–14316 (2009)

    Article  CAS  Google Scholar 

  28. Dresselhaus, M. S., Dresselhaus, G., Saito, R. & Jorio, A. Raman spectroscopy of carbon nanotubes. Phys. Rep. 409, 47–99 (2005)

    Article  ADS  Google Scholar 

  29. Naumov, A. V. et al. Quantifying the semiconducting fraction in single-walled carbon nanotube samples through comparative atomic force and photoluminescence microscopies. Nano Lett. 9, 3203–3208 (2009)

    Article  ADS  CAS  Google Scholar 

  30. Strano, M. S. Electronic structure control of single-walled carbon nanotube functionalization. Science 301, 1519–1522 (2003

    Article  ADS  CAS  Google Scholar 

Download references

Acknowledgements

We thank S. Iijima, S. Maruyama and J. Liu for advice on the manuscript; K. Lu, Y. Wang, E. Wang and S. Yao for discussions on catalyst preparation and properties; D. P. Nackashi, J. Ju, Y. Li and Protochips Inc. for in situ TEM measurements; H. Xu, H. Yang, K. Jiang and S. Wang for Raman measurements. This research was financially supported by MoST (project 2011CB933003), the NSFC of China (projects 21125103, 91333105, 21321001, 11179011 and 21273189) and a Hong Kong GRF research grant (G-YX4Q).

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Science, Key Laboratory for the Physics and Chemistry of Nanodevices, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China

    Feng Yang, Xiao Wang, Daqi Zhang, Juan Yang, Da Luo, Fei Peng, Ruoming Li, Yilun Li, Meihui Li & Yan Li

  2. Institute of Textiles and Clothing, Hong Kong Polytechnic University, Kowloon, Hong Kong, China,

    Ziwei Xu & Feng Ding

  3. Institute of Physics, Chinese Academy of Sciences, 100190, Beijing, China

    Jiake Wei, Zhi Xu & Xuedong Bai

  4. Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201204, China

    Jian-Qiang Wang

  5. Electron Microscopy Laboratory, Peking University, Beijing, 100871, China

    Xuemei Li

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  1. Feng Yang
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Contributions

Yan Li and F.Y. had the idea for and designed the experiments, analysed the results and wrote the manuscript. F.Y., D.Z., J.Y., D.L., J.W., J.-Q.W., Zhi Xu, X.L., F.P., Yilun Li, R.L., M.L. and X.B. performed the experiments and analysed the results. X.W., Ziwei Xu and F.D. contributed to theoretical calculations.

Corresponding author

Correspondence to Yan Li.

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Competing interests

Yan Li and F.Y. declare a financial interest: patents related to this research have been filed by Peking University. The University’s policy is to share financial rewards from the exploitation of patents with the inventors.

Extended data figures and tables

Extended Data Figure 1 Raman spectra of SWNTs grown at different temperatures and with different excitation wavelengths.

a, 950 °C; b, 980 °C; c, 1,000 °C; d, 1,030 °C.

Extended Data Figure 2 Surface enhanced Raman measurements of SWNTs grown at different temperatures.

SEM images (a, 950 °C; b, 1,030 °C) of SWNTs after decoration of Au nanoparticles (insets are amplified images; scale bars, 400 nm), and corresponding surface enhanced Raman spectra (c, d) measured using a laser beam size of 10 μm.

Extended Data Figure 3 AFM image (a) and the height profile (b) of the SWNTs grown at 1,030 °C.

Extended Data Figure 4 The 68 RBMs in Fig. 2a located in a Kataura plot, and the corresponding chirality assignment.

Extended Data Figure 5 Assignment of (n, m) by electron diffraction for SWNTs grown at 1,030 °C.

a, Scheme showing an isolated SWNT growing across the slit on a SiO2/Si substrate. b, Raman spectrum of the isolated suspended SWNT with ωRBM = 197 cm−1 taken with a 633-nm laser. c, d, SEM image showing the suspended SWNT grown across the slit for Raman and TEM characterizations. e–g, Electron diffraction patterns of (12, 6) SWNTs grown at 1,030 °C.

Extended Data Figure 6 Characterizing the (n, m) distribution of SWNTs grown at 1,030 °C by the combined AFM–Raman method.

a–c, SEM (a), AFM images (b) and Raman spectra (c) of individual SWNTs from the (12, 6)-enriched sample. d, Statistical data for SWNTs from AFM and Raman measurements.

Extended Data Figure 7 UV–Vis–NIR absorption spectrum of SWNTs grown at 1,030 °C by background subtraction.

a, UV–Vis–NIR absorption spectra of SDS suspended SWNTs grown with W–Co catalysts at 1,030 °C, the catalyst–SDS (1 wt%) dispersion and SDS (1 wt%) solution alone. Inset, absorption spectrum of the catalyst–SDS dispersion in the 500–700 nm wavelength range. b, Background-subtracted absorption spectrum of the SWNTs using the multiplied absorption spectrum of catalyst–SDS dispersion as baseline.

Extended Data Figure 8 XRD patterns of W–Co catalyst supported on SiO2 after ethanol CVD at 1,030 °C.

Standard cards from the JCPDS database are included for comparison: W6Co7 (JCPDS 2-1091), WC (JCPDS 2-1055), SiC (JCPDS 22-1316).

Extended Data Figure 9 Density functional theory simulation of SWNTs with similar diameters on catalyst nanoparticles.

a, Vertical view of the catalyst structure of the (0 0 12) plane of W6Co7 nanoparticle. The enlarged image is also the vertical view. b, c, Side view (b) and top view (c) of interfaces between SWNTs of different chiralities and the (0 0 12) plane of W6Co7. d, Side view of interfaces between SWNTs of different chirality and the (0 0 1) plane of face-centred-cubic Co nanoparticles.

Extended Data Figure 10 The Raman spectra of SWNTs grown by different processes.

a, b, e, f, Schemes showing the different growth processes. c, d, g, h, The Raman spectra of the corresponding SWNT samples: SWNTs grown at 1,000 °C with the catalysts prepared at 1,030 °C (c) and 1,000 °C (d); SWNTs grown at 950 °C with the catalysts prepared at 1,030 °C (g) and 950 °C (h). Regions in which (12, 6) tubes are located are indicated with green shading (excitation wavelength, 633 nm).

Supplementary information

Supplementary Information

This file contains Supplementary Methods, Supplementary Figures 1-10, Supplementary Tables 1-4, Supplementary Equations 1-2 and Supplementary References. The Supplementary experimental methods include the preparation of catalysts and growth of SWNTs, characterizations of SWNTs grown with W-Co catalysts and the W-Co catalyst nanoparticles as well as the DFT simulation methods; Supplementary data shows the selective growth of more chiralities and with more W-based alloys. (PDF 1875 kb)

Video 1: Real-time continuous Raman mapping of SWNTs

A real-time continuous Raman mapping of SWNTs grown at 1030oC with W6Co7 catalysts taken at excitation of 633 nm, laser beam spot of 3μm and integration time of 4 s within the detected range of 15μm × 30μm. (MOV 19305 kb)

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Yang, F., Wang, X., Zhang, D. et al. Chirality-specific growth of single-walled carbon nanotubes on solid alloy catalysts. Nature 510, 522–524 (2014). https://doi.org/10.1038/nature13434

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