Volume 63, Issue 51 e202412131
Research Article

Growth Kinetics of Graphene on Cu(111) Foils from Methane, Ethyne, Ethylene, and Ethane

Meihui Wang

Meihui Wang

Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), 44919 Ulsan, Republic of Korea

State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 430074 Wuhan, China

These authors contributed equally to this work.

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Yong Chul Kim

Yong Chul Kim

Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), 44919 Ulsan, Republic of Korea

These authors contributed equally to this work.

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Yongqiang Meng

Yongqiang Meng

Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), 44919 Ulsan, Republic of Korea

Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), 44919 Ulsan, Republic of Korea

These authors contributed equally to this work.

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Shahana Chatterjee

Shahana Chatterjee

Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), 44919 Ulsan, Republic of Korea

Make Materials, M5B Toronto, Canada

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Pavel Bakharev

Pavel Bakharev

Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), 44919 Ulsan, Republic of Korea

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Da Luo

Da Luo

Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), 44919 Ulsan, Republic of Korea

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Yan Gong

Yan Gong

Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), 44919 Ulsan, Republic of Korea

Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), 44919 Ulsan, Republic of Korea

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Thomas Abadie

Thomas Abadie

Department of Chemical Engineering, Imperial College London, SW7 2AZ London, United Kingdom

School of Chemical Engineering, University of Birmingham, B15 2TT Birmingham, United Kingdom

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Min Hyeok Kim

Min Hyeok Kim

Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), 44919 Ulsan, Republic of Korea

Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), 44919 Ulsan, Republic of Korea

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Jakub Sitek

Jakub Sitek

Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), 44919 Ulsan, Republic of Korea

Faculty of Physics, Warsaw University of Technology, Koszykowa 75, 00-662 Warsaw, Poland

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Won Kyung Seong

Won Kyung Seong

Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), 44919 Ulsan, Republic of Korea

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Geunsik Lee

Geunsik Lee

Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), 44919 Ulsan, Republic of Korea

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Rodney S. Ruoff

Corresponding Author

Rodney S. Ruoff

Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), 44919 Ulsan, Republic of Korea

Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), 44919 Ulsan, Republic of Korea

Department of Materials Science and Engineering, Ulsan National Institute of Science and Technology (UNIST), 44919 Ulsan, Republic of Korea

School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), 44919 Ulsan, Republic of Korea

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First published: 28 October 2024
Citations: 1

Graphical Abstract

We obtained the activation enthalpies of graphene island growth on Cu(111) foils using H2 and: CH4, and C2H2, C2H4, and C2H6, respectively. The rate determining step (RDS) for CH4 is its gas phase decomposition to H and CH3. The RDS for C2H2, C2H4, and C2H6 is dehydrogenation on the Cu(111) surface yielding adsorbed C2H1, C2H3, and C2H5, respectively.

Abstract

Chemical vapor deposition of carbon precursors on Cu-based substrates at temperatures exceeding 1000 °C is currently a typical route for the scalable synthesis of large-area high-quality single-layer graphene (SLG) films. Using molecules with higher activities than CH4 may afford lower growth temperatures that might yield fold- and wrinkle-free graphene. The kinetics of growth of graphene using hydrocarbons other than CH4 are of interest to the scientific and industrial communities. We measured the growth rates of graphene islands on Cu(111) foils by using C2H2, C2H4, C2H6 and CH4, respectively (each mixed with H2). From such kinetics data we obtain the activation enthalpy (ΔH) of graphene growth as shown in parentheses (C2H2 (0.93±0.09 eV); C2H4 (2.05±0.19 eV); C2H6 (2.50±0.11 eV); CH4 (4.59±0.26 eV)); C2Hy (y=2, 4, 6) show similar growth behavior but CH4 is different. Computational fluid dynamics and density functional theory simulations suggest that C2Hy differs from CH4 due to different values of adsorption energy and the lifetime of relevant carbon precursors on the Cu(111) surface. Combining experimental and simulation results, we find that the rate determining step (RDS) is the dissociation of the first C−H bond of CH4 molecules in the gas phase, while the RDS using C2Hy is the first dehydrogenation of adsorbed C2Hy that happens with assistance of H atoms adsorbed on the Cu(111) surface. By using C2H2 as the carbon precursor, high-quality single-crystal adlayer-free SLG films are achieved on Cu(111) foils at 900 °C.

Conflict of Interests

The authors declare no conflict of interest.

Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.

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