Grains and grain boundaries in single-layer graphene atomic patchwork quilts


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.

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Figure 1: Atomic-resolution ADF-STEM images of graphene crystals.
Figure 2: Large-scale grain imaging using DF-TEM.
Figure 3: Statistical analysis of grain size and orientation.
Figure 4: Grain structure and mobilities for three growth conditions.
Figure 5: AFM indentation and AC-EFM studies of graphene grain boundaries.


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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.

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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.

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Correspondence to David A. Muller.

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The authors declare no competing financial interests.

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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).

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