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 reported15,16,17,18,19. 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
- Purchase on SpringerLink
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1038%2Fnature09718/MediaObjects/41586_2011_Article_BFnature09718_Fig1_HTML.jpg)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1038%2Fnature09718/MediaObjects/41586_2011_Article_BFnature09718_Fig2_HTML.jpg)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1038%2Fnature09718/MediaObjects/41586_2011_Article_BFnature09718_Fig3_HTML.jpg)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1038%2Fnature09718/MediaObjects/41586_2011_Article_BFnature09718_Fig4_HTML.jpg)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1038%2Fnature09718/MediaObjects/41586_2011_Article_BFnature09718_Fig5_HTML.jpg)
Similar content being viewed by others
References
Li, X. et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 1312–1314 (2009)
Reina, A. et al. Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition. Nano Lett. 9, 30–35 (2009)
Li, X. et al. Graphene films with large domain size by a two-step chemical vapor deposition process. Nano Lett. 10, 4328–4334 (2010)
Bae, S. et al. Roll-to-roll production of 30-inch graphene films for transparent electrodes. Nature Nanotechnol. 5, 574–578 (2010)
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)
Peres, N. M. R., Guinea, F. & Castro-Neto, A. H. Electronic properties of disordered two-dimensional carbon. Phys. Rev. B 73, 125411 (2006)
Yazyev, O. V. & Louie, S. G. Electronic transport in polycrystalline graphene. Nature Mater. 6, 806–809 (2010)
Mesaros, A., Papanikolaou, S., Flipse, C. F. J., Sadri, D. & Zaanen, J. Electronic states of graphene grain boundaries. Phys. Rev. B 82, 205119 (2010)
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)
Malola, S., Hakkinen, H. & Koskinen, P. Structural, chemical, and dynamical trends in graphene grain boundaries. Phys. Rev. B 81, 165447 (2010)
Liu, Y. & Yakobson, B. I. Cones, pringles, and grain boundary landscapes in graphene topology. Nano Lett. 10, 2178–2183 (2010)
Grantab, R., Shenoy, V. B. & Ruoff, R. S. Anomalous strength characteristics of tilt grain boundaries in graphene. Science 330, 946–948 (2010)
Yazyev, O. V. & Louie, S. G. Topological defects in graphene: dislocations and grain boundaries. Phys. Rev. B 81, 195420 (2010)
Hirsch, P., Howie, A., Nicholson, R., Pashley, D. W. & Whelan, M. J. Electron Microscopy of Thin Crystals (Krieger, 1965)
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)
Gao, L., Guest, J. R. & Guisinger, N. P. Epitaxial graphene on Cu(111). Nano Lett. 10, 3512–3516 (2010)
Cockayne, E. et al. Rotational grain boundaries in graphene. Preprint at 〈http://arxiv.org/abs/1008.3574〉 (2010)
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)
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)
Regan, W. et al. A direct transfer of layer-area graphene. Appl. Phys. Lett. 96, 113102 (2010)
Krivanek, O. L. et al. Atom-by-atom structural and chemical analysis by annular dark-field electron microscopy. Nature 464, 571–574 (2010)
Hashimoto, A., Suenaga, K., Gloter, A., Urita, K. & Iijima, S. Direct evidence for atomic defects in graphene layers. Nature 430, 870–873 (2004)
Meyer, J. C. et al. Direct imaging of lattice atoms and topological defects in graphene membranes. Nano Lett. 8, 3582–3586 (2008)
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)
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)
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)
Geim, A. K. & Novoselov, K. S. The rise of graphene. Nature Mater. 6, 183–191 (2007)
Bachtold, A. et al. Scanned probe microscopy of electronic transport in carbon nanotubes. Phys. Rev. Lett. 84, 6082–6085 (2000)
Van Der Zande, A. M. et al. Large-scale arrays of single-layer graphene resonators. Nano Lett. 10, 4869–4873 (2010)
Thiel, S. et al. Electron scattering at dislocations in LaAlO3/SrTiO3 interfaces. Phys. Rev. Lett. 102, 046809 (2009)
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)
Suenaga, K. et al. Imaging active topological defects in carbon nanotubes. Nature Nanotechnol. 2, 358–360 (2007)
Jiao, L. et al. Creation of nanostructures with poly(methyl methacrylate)-mediated nanotransfer printing. J. Am. Chem. Soc. 130, 12612–12613 (2008)
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
Authors and Affiliations
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
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)
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
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nature09718
This article is cited by
-
Topological high-harmonic spectroscopy
Communications Physics (2024)
-
Prediction of highly stable 2D carbon allotropes based on azulenoid kekulene
Nature Communications (2024)
-
The Role of Graphene Defects in Graphene-Coated Copper Oxidation Behavior
Transactions of the Indian Institute of Metals (2024)
-
Step engineering for nucleation and domain orientation control in WSe2 epitaxy on c-plane sapphire
Nature Nanotechnology (2023)
-
Topological phenomena at defects in acoustic, photonic and solid-state lattices
Nature Reviews Physics (2023)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.