Controlled synthesis of single-chirality carbon nanotubes

Abstract

Over the past two decades, single-walled carbon nanotubes (SWCNTs) have received much attention because their extraordinary properties are promising for numerous applications1,2. Many of these properties depend sensitively on SWCNT structure, which is characterized by the chiral index (n,m) that denotes the length and orientation of the circumferential vector in the hexagonal carbon lattice. Electronic properties are particularly strongly affected, with subtle structural changes switching tubes from metallic to semiconducting with various bandgaps. Monodisperse ‘single-chirality’ (that is, with a single (n,m) index) SWCNTs are thus needed to fully exploit their technological potential1,2. Controlled synthesis through catalyst engineering3,4,5,6, end-cap engineering7 or cloning strategies8,9, and also tube sorting based on chromatography10,11, density-gradient centrifugation, electrophoresis and other techniques12, have delivered SWCNT samples with narrow distributions of tube diameter and a large fraction of a predetermined tube type. But an effective pathway to truly monodisperse SWCNTs remains elusive. The use of template molecules to unambiguously dictate the diameter and chirality of the resulting nanotube8,13,14,15,16 holds great promise in this regard, but has hitherto had only limited practical success7,17,18. Here we show that this bottom-up strategy can produce targeted nanotubes: we convert molecular precursors into ultrashort singly capped (6,6) ‘armchair’ nanotube seeds using surface-catalysed cyclodehydrogenation on a platinum (111) surface, and then elongate these during a subsequent growth phase to produce single-chirality and essentially defect-free SWCNTs with lengths up to a few hundred nanometres. We expect that our on-surface synthesis approach will provide a route to nanotube-based materials with highly optimized properties for applications such as light detectors, photovoltaics, field-effect transistors and sensors2.

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Figure 1: Two-step bottom-up synthesis of SWCNTs.
Figure 2: Formation of (6,6) SWCNT seeds S1.
Figure 3: Epitaxial elongation of singly capped SWCNT with (6,6) chiral index defined by the seed S1.
Figure 4: SWCNT orientation determination and single chirality assessment by Raman spectroscopy.

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Acknowledgements

This research was supported in part by the Swiss National Science Foundation and by the State Secretariat for Education, Research and Innovation via the COST Action MP0901 ‘NanoTP’. K.A. acknowledges financial support from Deutsche Forschungsgemeinschaft.

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Authors

Contributions

K.A., M.J. and R.F. initiated and conceived this work. K.A. designed the precursor molecules and the corresponding synthetic routes, K.A. and A.M. synthesised precursor molecules and performed HPLC, NMR and MS analyses. J.R.S.-V. carried out on-surface synthesis work. J.R.S.-V. and T.D. performed STM and Raman measurements, I.S. did the He ion microscopy analysis. O.G. performed the calculations. All authors participated in analysis and interpretation of the results. J.R.S.-V. drafted the manuscript, with contributions from P.R. and O.G. R.F. and K.A. edited the manuscript and coordinated the efforts of the research teams.

Corresponding authors

Correspondence to Konstantin Amsharov or Roman Fasel.

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The authors declare no competing financial interests.

Extended data figures and tables

Extended Data Figure 1 Conformations of precursor P1 adsorbed on Pt(111).

a, Sketch of the molecular conformations due to the axial chirality of the benzo[c]phenanthrene moieties. b, c, Simulations of the extended HOMO (LUMO shows a similar structure) with the outer biphenyls at a lower (b) or higher (c) elevation (left), and with the corresponding molecular structure superposed (right). dh, Conformational analysis of P1 (top) and STM images of observed conformations of the P1 molecules on Pt(111) (bottom). i, Statistical analysis of the different molecular conformations shows that at least 50% of the molecules adopt a configuration suitable for a correct dehydrogenation pathway (red square).

Extended Data Figure 2 Dehydrogenation pathways for ‘right’ and ‘wrong’ conformations of P1.

a–d, Molecular dehydrogenation pathways for a ‘right’ conformation (a), and for ‘wrong’ conformations with 1 (b), 2 (c) and 3 (d) biphenyl arms rotated. Cases b, c, and d do not lead to a completed singly capped SWCNT and do not act as seeds for nanotube growth on epitaxial elongation.

Extended Data Figure 3 Scanning helium ion microscopy images.

SHIM images of epitaxially elongated SWCNTs obtained by exposing seeds S1 to 1 × 10−7 mbar of ethanol for 1 h (270 L) at 770 K. Long carbon nanotubes can be observed to lie on the surface, and in some cases to shake under the ion beam (indicated by light green arrows, bottom). Top left, lower-magnification view of surface: numbered coloured boxes are shown at higher magnification to the right. The unnumbered grey-scale images show different surface locations at higher magnifications. The rightmost panel gives a higher magnification image of the long SWCNT seen in panel 1.

Extended Data Figure 4 Synthesis of SWCNT precursor P1.

Details are given in Methods: here we describe reaction steps a to j. a, PPh3, toluene, reflux, 95%; b, BrPh3PCH2PhBr, KOtBu, EtOH, reflux, 81%; c, I2, hv, propylene oxide, cyclohexane, 72%; d, Pd(PPh3)4, Cs2CO3, toluene/MeOH, 110°C, 79%; e, NBS, DBPO, CCl4, reflux, 70%; f, NaCN, DMSO, RT, 40%; g, H2SO4, H2O, HOAc, reflux, 98%; h, SOCl2, 65 °C; i, AlCl3, CH2Cl2, RT, 57%; j, propanoic acid, TsOH, o-DCB, 180 °C, 65%.

Extended Data Figure 5 LDI mass spectra of precursor P1 (C96H54).

a, b, LDI mass spectra of P1 before (a) and after (b) sublimation. Computed and experimentally observed isotope distribution patterns for C96H54 are given in the inset of b.

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Sanchez-Valencia, J., Dienel, T., Gröning, O. et al. Controlled synthesis of single-chirality carbon nanotubes. Nature 512, 61–64 (2014). https://doi.org/10.1038/nature13607

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