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The Role of Surface Oxygen in the Growth of Large Single-Crystal Graphene on Copper

Yufeng Hao, M. S. Bharathi, Lei Wang, Yuanyue Liu, Hua Chen, Shu Nie, Xiaohan Wang, Harry Chou, Cheng Tan, Babak Fallahazad, H. Ramanarayan, Carl W. Magnuson, Emanuel Tutuc, Boris I. Yakobson, Kevin F. McCarty, Yong-Wei Zhang, Philip Kim, James Hone, Luigi Colombo [email protected], and Rodney S. Ruoff [email protected]
Science • 8 Nov 2013 • Vol 342, Issue 6159 • pp. 720-723 • DOI: 10.1126/science.1243879
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Oxygen Control of Graphene Growth

The growth of graphene on copper surfaces through the decomposition of hydrocarbons such as methane can result in a wide variety of crystal domain sizes and morphologies. Hao et al. (p. 720, published online 24 October; see the cover) found that the presence of surface oxygen could limit the number of nucleation sites and allowed centimeter-scale domains to grow through a diffusion-limited mechanism. The electrical conductivity of the graphene was comparable to that of exfoliated graphene.

Abstract

The growth of high-quality single crystals of graphene by chemical vapor deposition on copper (Cu) has not always achieved control over domain size and morphology, and the results vary from lab to lab under presumably similar growth conditions. We discovered that oxygen (O) on the Cu surface substantially decreased the graphene nucleation density by passivating Cu surface active sites. Control of surface O enabled repeatable growth of centimeter-scale single-crystal graphene domains. Oxygen also accelerated graphene domain growth and shifted the growth kinetics from edge-attachment–limited to diffusion-limited. Correspondingly, the compact graphene domain shapes became dendritic. The electrical quality of the graphene films was equivalent to that of mechanically exfoliated graphene, in spite of being grown in the presence of O.
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Science
Volume 342 | Issue 6159
8 November 2013

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Copyright © 2013, American Association for the Advancement of Science.

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Received: 29 July 2013
Accepted: 1 October 2013
Published in print: 8 November 2013

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Acknowledgments

We thank V. B. Shenoy (University of Pennsylvania), Zhenyu Zhang [University of Science and Technology of China (USTC)], Zhenyu Li (USTC), N. C. Bartelt (Sandia Laboratories), P. Sutter (Brookhaven Laboratory), Gui-Chang Wang (Nankai University), Cheng Gong (University of Texas–Dallas), Zhen Yan (Texas A&M University), and C. R. Dean (City College of New York) for valuable discussions. We thank K. Watanabe and T. Taniguchi for providing h-BN substrates. This work acknowledges support from the W. M. Keck Foundation, the Office of Naval Research (ONR), and the South West Academy of Nanolectronics of the Nanoelectronics Research Initiative. Work at Columbia University was supported by the Center for Re-Defining Photovoltaic Efficiency through Molecular-Scale Control, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under award DE-SC0001085, National Science Foundation (NSF) grant DMR-1124894, and ONR grant N000141310662. Work at the Institute of High Performance Computing was supported by the Agency for Science, Technology And Research (A*STAR), Singapore. Work at Sandia was supported by the Office of Basic Energy Sciences, Division of Materials and Engineering Sciences, U.S. DOE, under contract no. DE-AC04-94AL85000. Work at Rice University was supported by the ONR and NSF’s Chemical, Bioengineering, Environmental, and Transport Systems Division. The first-principles computations were performed on Kraken at the National Institute for Computational Sciences (NSF grant OCI-1053575), Hopper at the National Energy Research Scientific Computing Center (DOE grant DE-AC02-05CH11231), and DaVinCI at Rice University (NSF grant OCI-0959097). H.C. acknowledges support from NSF grant DMR-1122603. A relevant patent application is in process.

Authors

Affiliations

Yufeng Hao
Department of Mechanical Engineering and the Materials Science and Engineering Program, The University of Texas at Austin, Austin, TX 78712, USA.
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M. S. Bharathi
Institute of High Performance Computing, A*STAR, 138632, Singapore.
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Lei Wang
Department of Mechanical Engineering, Columbia University, New York, NY 10027, USA.
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Yuanyue Liu
Department of Mechanical Engineering and Materials Science, and Department of Chemistry, Rice University, Houston, TX 77005, USA.
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Hua Chen
Department of Physics, The University of Texas at Austin, Austin, TX 78712, USA.
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Shu Nie
Sandia National Laboratories, Livermore, CA 94550, USA.
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Xiaohan Wang
Department of Mechanical Engineering and the Materials Science and Engineering Program, The University of Texas at Austin, Austin, TX 78712, USA.
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Harry Chou
Department of Mechanical Engineering and the Materials Science and Engineering Program, The University of Texas at Austin, Austin, TX 78712, USA.
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Cheng Tan
Department of Mechanical Engineering and the Materials Science and Engineering Program, The University of Texas at Austin, Austin, TX 78712, USA.
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Babak Fallahazad
Microelectronics Research Center, The University of Texas at Austin, Austin, TX 78758, USA.
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H. Ramanarayan
Institute of High Performance Computing, A*STAR, 138632, Singapore.
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Carl W. Magnuson
Department of Mechanical Engineering and the Materials Science and Engineering Program, The University of Texas at Austin, Austin, TX 78712, USA.
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Emanuel Tutuc
Microelectronics Research Center, The University of Texas at Austin, Austin, TX 78758, USA.
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Boris I. Yakobson
Department of Mechanical Engineering and Materials Science, and Department of Chemistry, Rice University, Houston, TX 77005, USA.
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Kevin F. McCarty
Sandia National Laboratories, Livermore, CA 94550, USA.
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Yong-Wei Zhang
Institute of High Performance Computing, A*STAR, 138632, Singapore.
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Philip Kim
Department of Physics, Columbia University, New York, NY 10027, USA.
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James Hone
Department of Mechanical Engineering, Columbia University, New York, NY 10027, USA.
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Luigi Colombo* [email protected]
Texas Instruments, Dallas, TX 75243, USA.
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Rodney S. Ruoff* [email protected]
Department of Mechanical Engineering and the Materials Science and Engineering Program, The University of Texas at Austin, Austin, TX 78712, USA.
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Notes

*Corresponding author. E-mail: [email protected] (R.S.R); [email protected] (L.C.)

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