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Arrays of horizontal carbon nanotubes of controlled chirality grown using designed catalysts

Nature volume 543, pages 234–238 (2017)Cite this article

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Abstract

The semiconductor industry is increasingly of the view that Moore’s law—which predicts the biennial doubling of the number of transistors per microprocessor chip—is nearing its end1. Consequently, the pursuit of alternative semiconducting materials for nanoelectronic devices, including single-walled carbon nanotubes (SWNTs), continues2,3,4. Arrays of horizontal nanotubes are particularly appealing for technological applications because they optimize current output. However, the direct growth of horizontal SWNT arrays with controlled chirality, that would enable the arrays to be adapted for a wider range of applications and ensure the uniformity of the fabricated devices, has not yet been achieved. Here we show that horizontal SWNT arrays with predicted chirality can be grown from the surfaces of solid carbide catalysts by controlling the symmetries of the active catalyst surface. We obtained horizontally aligned metallic SWNT arrays with an average density of more than 20 tubes per micrometre in which 90 per cent of the tubes had chiral indices of (12, 6), and semiconducting SWNT arrays with an average density of more than 10 tubes per micrometre in which 80 per cent of the nanotubes had chiral indices of (8, 4). The nanotubes were grown using uniform size Mo2C and WC solid catalysts. Thermodynamically, the SWNT was selectively nucleated by matching its structural symmetry and diameter with those of the catalyst. We grew nanotubes with chiral indices of (2m, m) (where m is a positive integer), the yield of which could be increased by raising the concentration of carbon to maximize the kinetic growth rate in the chemical vapour deposition process. Compared to previously reported methods, such as cloning5,6, seeding7,8 and specific-structure-matching growth9,10,11, our strategy of controlling the thermodynamics and kinetics offers more degrees of freedom, enabling the chirality of as-grown SWNTs in an array to be tuned, and can also be used to predict the growth conditions required to achieve the desired chiralities.

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Figure 1: Two-step control of the chirality of SWNTs in ethanol chemical vapour deposition (CVD).
Figure 2: The effects of symmetry matching and kinetic growth on the distribution of the chirality of SWNTs.
Figure 3: Formation of uniform catalysts using a monodispersed process.
Figure 4: Successful growth of (12, 6) and (8, 4) SWNTs arrays using uniform catalysts, and their characterizations.

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Acknowledgements

We are grateful to K. Jiang (Tsinghua University, China), K. Liu (Peking University, China) and R. Horn (Deakin University, Australia) for discussions. This work was supported by the Ministry of Science and Technology of China (2016YFA0200101 and 2016YFA0200104) and the National Natural Science Foundation of China (grant 51432002, 21129001 and 21233001).

Author information

Author notes

  1. Shuchen Zhang and Lixing Kang: These authors contributed equally to this work.

Authors and Affiliations

  1. Center for Nanochemistry, Beijing Science and Engineering Center for Nanocarbons, Beijing National Laboratory for Molecular Sciences, Key Laboratory for the Physics and Chemistry of Nanodevices, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China

    Shuchen Zhang, Lixing Kang, Lianming Tong, Liangwei Yang, Zequn Wang, Shibin Deng & Jin Zhang

  2. Suzhou Institute of Nanotech and Nanobionics, Chinese Academy of Sciences, Suzhou, 215123, China

    Lixing Kang & Qingwen Li

  3. Center for Multidimensional Carbon Materials, Institute for Basic Science, Ulsan, 689-798, South Korea

    Xiao Wang & Feng Ding

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

    Xiao Wang & Feng Ding

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

    Kuo Qi & Xuedong Bai

  6. School of Materials Science and Engineering, Ulsan National Institute of Science and Technology, Ulsan, 689-798, South Korea

    Feng Ding

Authors
  1. Shuchen Zhang
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Contributions

J.Z., S.Z., L.K. and F.D. conceived and designed the experiments. S.Z., L.K., X.W., L.Y. and Z.W. performed the experiments. K.Q. and X.B. were responsible for technical assistance with the electron diffraction pattern of carbon nanotubes using HRTEM. J.Z., S.Z., L.K., L.T., F. D. and X.W. performed the data analysis. J.Z., S.Z. and L.T. wrote the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Jin Zhang.

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The authors declare no competing financial interests.

Additional information

Reviewer Information Nature thanks A. Harutyunyan and the other anonymous reviewer(s) for their contribution to the peer review of this work.

Extended data figures and tables

Extended Data Figure 1 Models and theoretical calculations on the symmetry matching between catalysts and carbon nanotubes.

a–c, The high-symmetry relative position of SWNT on WC (100) surface: square (a), diamond (b) and rectangle (c). The relative positions are indicated by red dashed lines. The tungsten and carbon atoms are coloured blue and grey, respectively. The top layer consists of tungsten atoms, and is highlighted in green. d–f, The lowest formation energies of SWNTs with different chiralities on WC (100) surface: zigzag-SWNTs (d), armchair-SWNTs (e) and SWNTs with similar diameters (f).

Source data

Extended Data Figure 2 The effect of growth time on the length of tubes.

a, b, The tubes that were grown for 15 min (a) are much longer than those grown for 5 min (b). Consequently, we were able to demonstrate kinetically controlled growth following a short period of general growth, as shown in Fig. 2g.

Extended Data Figure 3 The effects of initial reducing temperature and C/H ratio on the species of tubes.

a, The percentages of (12, 6) (black) and (8, 4) (red) SWNTs in (2m, m) carbon nanotubes grown when using catalysts reduced at different initial temperatures. b, The percentage of as-grown (12, 6) nanotubes as a function of C/H ratio during growth at 850 °C when the catalysts were reduced from 450 °C. The error bars show the standard deviations, which are 3%.

Source data

Extended Data Figure 4 SEM and AFM images of the tubes at different scales.

a–d, SEM images (a, b) and AFM images (c, d) showing the high density of (12, 6) SWNTs in an array grown on the sapphire surface. The average density was about 20 tubes per micrometre, with local densities of more than 40 tubes per micrometre in certain regions (d and the inset in b).

Extended Data Figure 5 Raman characterizations for (12, 6) and (8, 4) tubes.

a–h, Raman spectra of (12, 6) SWNTs using excitation wavelengths of 488 nm (a), 514 nm (b), 633 nm (c) and 785 nm (d), and those of (8, 4) SWNTs using excitation wavelengths of 488 nm (e), 514 nm (f), 633 nm (g) and 785 nm (h).

Extended Data Figure 6 Electron diffraction patterns of (12, 6) tubes on a copper grid.

a, b, Images of the (12, 6) SWNT array transferred to a copper grid with markers. c–e, Electron diffraction patterns of the as-grown (12, 6) SWNTs at different places on the different tubes.

Extended Data Figure 7 Spectral characterization of (12, 6) tubes.

a, b, Ultraviolet–visible–near-infrared absorption spectrum of (12, 6) SWNTs (a) and their Raman spectrum showing the high quality as indicated by the D peak, G peak and 2D peak (b).

Source data

Extended Data Figure 8 SEM images and the distribution of the diameter of the (8, 4) tubes.

a, High density of (8, 4) SWNTs in an array grown on the sapphire surface. b, For the (8, 4) array, the average diameter is 0.87 nm, with a standard deviation of 0.17 nm.

Source data

Extended Data Figure 9 Optical absorption spectrum of the (8, 4) nanotube-enriched arrays on the substrate.

There are some (12, 6) tubes in the (8, 4) tubes array. The asterisk represents the (8, 4) tube and the triangles represent the (12, 6) tubes.

Source data

Extended Data Figure 10 Electrical properties of as-grown carbon nanotube arrays.

a, Typical transfer characteristic curves of field-effect transistor devices fabricated on (12, 6)- and (8, 4)-enriched SWNT arrays. b, Corresponding statistical results of Ion/Ioff ratios for the two different samples. Ids, drain–source current; Ion, maximum Ids; Ioff, minimum Ids.

Source data

Supplementary information

Supplementary Information

This file contains Supplementary Methods, Supplementary Figures 1-24, Supplementary Tables 1-7 and Supplementary References. (PDF 3412 kb)

Supplementary Data

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Zhang, S., Kang, L., Wang, X. et al. Arrays of horizontal carbon nanotubes of controlled chirality grown using designed catalysts. Nature 543, 234–238 (2017). https://doi.org/10.1038/nature21051

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