Grains and grain boundaries in single-layer graphene atomic patchwork quilts (original) (raw)

Nature volume 469, pages 389–392 (2011)Cite this article

Abstract

The properties of polycrystalline materials are often dominated by the size of their grains and by the atomic structure of their grain boundaries. These effects should be especially pronounced in two-dimensional materials, where even a line defect can divide and disrupt a crystal. These issues take on practical significance in graphene, which is a hexagonal, two-dimensional crystal of carbon atoms. Single-atom-thick graphene sheets can now be produced by chemical vapour deposition1,2,3 on scales of up to metres4, making their polycrystallinity almost unavoidable. Theoretically, graphene grain boundaries are predicted to have distinct electronic5,6,7,8, magnetic9, chemical10 and mechanical11,12,13 properties that strongly depend on their atomic arrangement. Yet because of the five-order-of-magnitude size difference between grains and the atoms at grain boundaries, few experiments have fully explored the graphene grain structure. Here we use a combination of old and new transmission electron microscopy techniques to bridge these length scales. Using atomic-resolution imaging, we determine the location and identity of every atom at a grain boundary and find that different grains stitch together predominantly through pentagon–heptagon pairs. Rather than individually imaging the several billion atoms in each grain, we use diffraction-filtered imaging14 to rapidly map the location, orientation and shape of several hundred grains and boundaries, where only a handful have been previously reported[15](/articles/nature09718#ref-CR15 "Zhao, L. et al. The atomic-scale growth of large-area monolayer graphene on single-crystal copper substrates. Preprint at 〈 http://arxiv.org/abs/1008.3542

            〉 (2010)"),[16](/articles/nature09718#ref-CR16 "Gao, L., Guest, J. R. & Guisinger, N. P. Epitaxial graphene on Cu(111). Nano Lett. 10, 3512–3516 (2010)"),[17](/articles/nature09718#ref-CR17 "Cockayne, E. et al. Rotational grain boundaries in graphene. Preprint at 〈
              http://arxiv.org/abs/1008.3574
              
            〉 (2010)"),[18](/articles/nature09718#ref-CR18 "Wofford, J. M., Nie, S., McCarty, K. F., Bartlet, N. C. & Dubon, O. D. Graphene islands on Cu foils: the interplay between shape, orientation, and defects. Nano Lett. 10, 4890–4896 (2010)"),[19](/articles/nature09718#ref-CR19 "Park, H. J., Meyer, J., Roth, S. & Skakalova, V. Growth and properties of few-layer graphene prepared by chemical vapor deposition. Carbon 48, 1088–1094 (2010)"). The resulting images reveal an unexpectedly small and intricate patchwork of grains connected by tilt boundaries. By correlating grain imaging with scanning probe and transport measurements, we show that these grain boundaries severely weaken the mechanical strength of graphene membranes but do not as drastically alter their electrical properties. These techniques open a new window for studies on the structure, properties and control of grains and grain boundaries in graphene and other two-dimensional materials.

This is a preview of subscription content, access via your institution

Access options

Subscribe to this journal

Receive 51 print issues and online access

$199.00 per year

only $3.90 per issue

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Additional access options:

Similar content being viewed by others

Molecular embroidering of graphene

Article Open access 22 January 2021

References

  1. Li, X. et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 1312–1314 (2009)
    Article ADS CAS Google Scholar
  2. Reina, A. et al. Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition. Nano Lett. 9, 30–35 (2009)
    Article ADS CAS Google Scholar
  3. Li, X. et al. Graphene films with large domain size by a two-step chemical vapor deposition process. Nano Lett. 10, 4328–4334 (2010)
    Article ADS CAS Google Scholar
  4. Bae, S. et al. Roll-to-roll production of 30-inch graphene films for transparent electrodes. Nature Nanotechnol. 5, 574–578 (2010)
    Article ADS CAS Google Scholar
  5. Cervenka, J. & Flipse, C. F. J. Structural and electronic properties of grain boundaries in graphite: planes of periodically distributed point defects. Phys. Rev. B 79, 195429 (2009)
    Article ADS Google Scholar
  6. Peres, N. M. R., Guinea, F. & Castro-Neto, A. H. Electronic properties of disordered two-dimensional carbon. Phys. Rev. B 73, 125411 (2006)
    Article ADS Google Scholar
  7. Yazyev, O. V. & Louie, S. G. Electronic transport in polycrystalline graphene. Nature Mater. 6, 806–809 (2010)
    Article ADS Google Scholar
  8. Mesaros, A., Papanikolaou, S., Flipse, C. F. J., Sadri, D. & Zaanen, J. Electronic states of graphene grain boundaries. Phys. Rev. B 82, 205119 (2010)
    Article ADS Google Scholar
  9. Cervenka, J., Katsnelson, M. I. & Flipse, C. F. J. Room-temperature ferromagnetism in graphite driven by two-dimensional networks of point defects. Nature Phys. 5, 840–844 (2009)
    Article ADS CAS Google Scholar
  10. Malola, S., Hakkinen, H. & Koskinen, P. Structural, chemical, and dynamical trends in graphene grain boundaries. Phys. Rev. B 81, 165447 (2010)
    Article ADS Google Scholar
  11. Liu, Y. & Yakobson, B. I. Cones, pringles, and grain boundary landscapes in graphene topology. Nano Lett. 10, 2178–2183 (2010)
    Article ADS CAS Google Scholar
  12. Grantab, R., Shenoy, V. B. & Ruoff, R. S. Anomalous strength characteristics of tilt grain boundaries in graphene. Science 330, 946–948 (2010)
    Article ADS CAS Google Scholar
  13. Yazyev, O. V. & Louie, S. G. Topological defects in graphene: dislocations and grain boundaries. Phys. Rev. B 81, 195420 (2010)
    Article ADS Google Scholar
  14. Hirsch, P., Howie, A., Nicholson, R., Pashley, D. W. & Whelan, M. J. Electron Microscopy of Thin Crystals (Krieger, 1965)
    Google Scholar
  15. Zhao, L. et al. The atomic-scale growth of large-area monolayer graphene on single-crystal copper substrates. Preprint at 〈http://arxiv.org/abs/1008.3542〉 (2010)
  16. Gao, L., Guest, J. R. & Guisinger, N. P. Epitaxial graphene on Cu(111). Nano Lett. 10, 3512–3516 (2010)
    Article ADS CAS Google Scholar
  17. Cockayne, E. et al. Rotational grain boundaries in graphene. Preprint at 〈http://arxiv.org/abs/1008.3574〉 (2010)
  18. Wofford, J. M., Nie, S., McCarty, K. F., Bartlet, N. C. & Dubon, O. D. Graphene islands on Cu foils: the interplay between shape, orientation, and defects. Nano Lett. 10, 4890–4896 (2010)
    Article ADS CAS Google Scholar
  19. Park, H. J., Meyer, J., Roth, S. & Skakalova, V. Growth and properties of few-layer graphene prepared by chemical vapor deposition. Carbon 48, 1088–1094 (2010)
    Article CAS Google Scholar
  20. Regan, W. et al. A direct transfer of layer-area graphene. Appl. Phys. Lett. 96, 113102 (2010)
    Article ADS Google Scholar
  21. Krivanek, O. L. et al. Atom-by-atom structural and chemical analysis by annular dark-field electron microscopy. Nature 464, 571–574 (2010)
    Article ADS CAS Google Scholar
  22. Hashimoto, A., Suenaga, K., Gloter, A., Urita, K. & Iijima, S. Direct evidence for atomic defects in graphene layers. Nature 430, 870–873 (2004)
    Article ADS CAS Google Scholar
  23. Meyer, J. C. et al. Direct imaging of lattice atoms and topological defects in graphene membranes. Nano Lett. 8, 3582–3586 (2008)
    Article ADS CAS Google Scholar
  24. de Villeneuve, V. W. A. et al. Hard sphere crystal nucleation and growth near large spherical impurities. J. Phys. Condens. Matter 17, S3371–S3378 (2005)
    Article CAS Google Scholar
  25. Park, S., Floresca, H. C., Suh, Y. & Kim, M. J. Electron microscopy analyses of natural and highly oriented pyrolytic graphites and the mechanically exfoliated graphenes produced from them. Carbon 48, 797–804 (2010)
    Article CAS Google Scholar
  26. Lee, C., Wei, X., Kysar, J. W. & Hone, J. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321, 385–388 (2008)
    Article ADS CAS Google Scholar
  27. Geim, A. K. & Novoselov, K. S. The rise of graphene. Nature Mater. 6, 183–191 (2007)
    Article ADS CAS Google Scholar
  28. Bachtold, A. et al. Scanned probe microscopy of electronic transport in carbon nanotubes. Phys. Rev. Lett. 84, 6082–6085 (2000)
    Article ADS CAS Google Scholar
  29. Van Der Zande, A. M. et al. Large-scale arrays of single-layer graphene resonators. Nano Lett. 10, 4869–4873 (2010)
    Article ADS CAS Google Scholar
  30. Thiel, S. et al. Electron scattering at dislocations in LaAlO3/SrTiO3 interfaces. Phys. Rev. Lett. 102, 046809 (2009)
    Article ADS CAS Google Scholar
  31. Meyer, J. C., Chuvilin, A. & Kaiser, U. in MC2009, Vol. 3: Materials Science (eds Grogger, W., Hofer, F. & Polt, P. ) 347–348 (Graz Univ. Technology, 2009)
    Google Scholar
  32. Suenaga, K. et al. Imaging active topological defects in carbon nanotubes. Nature Nanotechnol. 2, 358–360 (2007)
    Article ADS CAS Google Scholar
  33. Jiao, L. et al. Creation of nanostructures with poly(methyl methacrylate)-mediated nanotransfer printing. J. Am. Chem. Soc. 130, 12612–12613 (2008)
    Article CAS Google Scholar

Download references

Acknowledgements

The authors acknowledge discussions with M. Blees, J. Cha, S. Gerbode, J. Grazul, E. Kirkland, L. Fitting-Kourkoutis, O. Krivanek, S. Shi, S. Wang and H. Zhuang. This work was supported in part by the National Science Foundation through the Cornell Center for Materials Research and the Nanoscale Science and Engineering Initiative of the National Science Foundation under NSF Award EEC-0117770, 064654. Additional support was provided by the Army Research Office, CONACYT-Mexico, the Air Force Office of Scientific Research, DARPA-MTO and the MARCO Focused Research Center on Materials, Structures, and Devices. Sample fabrication was performed at the Cornell node of the National Nanofabrication Infrastructure Network, funded by the NSF. Additional facilities support was provided by the Cornell Center for Materials Research (NSF DMR-0520404 and IMR-0417392) and NYSTAR.

Author information

Author notes

  1. Pinshane Y. Huang, Carlos S. Ruiz-Vargas and Arend M. van der Zande: These authors contributed equally to this work.

Authors and Affiliations

  1. School of Applied and Engineering Physics, Cornell University, Ithaca, 14853, New York, USA
    Pinshane Y. Huang, Carlos S. Ruiz-Vargas, Jonathan S. Alden, Ye Zhu & David A. Muller
  2. Department of Physics, Cornell University, Ithaca, New York 14853, USA,
    Arend M. van der Zande, William S. Whitney & Paul L. McEuen
  3. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, 14853, New York, USA
    Mark P. Levendorf, Shivank Garg & Jiwoong Park
  4. Department of Physics, Oregon State University, Corvallis, 97331, Oregon, USA
    Joshua W. Kevek
  5. Department of Physics and Astronomy, Brigham Young University, Provo, 84602, Utah, USA
    Caleb J. Hustedt
  6. Kavli Institute at Cornell for Nanoscale Science, Ithaca, 14853, New York, USA
    Jiwoong Park, Paul L. McEuen & David A. Muller

Authors

  1. Pinshane Y. Huang
    You can also search for this author inPubMed Google Scholar
  2. Carlos S. Ruiz-Vargas
    You can also search for this author inPubMed Google Scholar
  3. Arend M. van der Zande
    You can also search for this author inPubMed Google Scholar
  4. William S. Whitney
    You can also search for this author inPubMed Google Scholar
  5. Mark P. Levendorf
    You can also search for this author inPubMed Google Scholar
  6. Joshua W. Kevek
    You can also search for this author inPubMed Google Scholar
  7. Shivank Garg
    You can also search for this author inPubMed Google Scholar
  8. Jonathan S. Alden
    You can also search for this author inPubMed Google Scholar
  9. Caleb J. Hustedt
    You can also search for this author inPubMed Google Scholar
  10. Ye Zhu
    You can also search for this author inPubMed Google Scholar
  11. Jiwoong Park
    You can also search for this author inPubMed Google Scholar
  12. Paul L. McEuen
    You can also search for this author inPubMed Google Scholar
  13. David A. Muller
    You can also search for this author inPubMed Google Scholar

Contributions

P.Y.H., C.S.R.-V. and A.M.v.d.Z. contributed equally to this work. Electron microscopy and data analysis were carried out by P.Y.H. and D.A.M., with Y.Z. contributing to initial DF-TEM. Graphene growth and sample fabrication were done by A.M.v.d.Z. and C.S.R.-V. under the supervision of P.L.M. and J.P., aided by M.P.L., S.G., W.S.W., J.W.K., J.S.A. and C.J.H. AC-EFM, mobility measurements and analysis were done by A.M.v.d.Z. and P.L.M., aided by C.S.R.-V. and J.W.K. AFM mechanical testing and analysis were done by C.S.R.-V. and J.P., aided by S.G. All authors discussed the results and implications at all stages. P.Y.H, A.M.v.d.Z., C.S.R.-V., P.L.M., J.P. and D.A.M. wrote the paper.

Corresponding author

Correspondence toDavid A. Muller.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

The file contains Supplementary Figures 1-12 with legends, Supplementary Methods and an additional reference. (PDF 4681 kb)

PowerPoint slides

Rights and permissions

About this article

Cite this article

Huang, P., Ruiz-Vargas, C., van der Zande, A. et al. Grains and grain boundaries in single-layer graphene atomic patchwork quilts.Nature 469, 389–392 (2011). https://doi.org/10.1038/nature09718

Download citation

This article is cited by

Editorial Summary

Graphene patchwork analysed

Single-atom-thick graphene sheets can now be produced at metre scales, bringing large-area applications in electronics and photovoltaics closer. But such large pieces can be expected to be polycrystalline, so it is important to determine the nature and size of the grains involved. Huang et al. use transmission electron microscopy to produce atomic-resolution images at grain boundaries, and map the location, orientation and shape of several hundred grains and boundaries using diffraction-filtered imaging. By correlating grain imaging with scanned probe and transport measurements, they show that the grain boundaries dramatically weaken the mechanical strength of graphene membranes, but do not as dramatically alter their electrical properties.

Associated content