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Research Article

Kinetics of hydrogen constrained graphene growth on Cu substrate

Xiucai Sun1,§( ), Shuang Lou1,2,§, Weizhi Wang1,3, Xuqin Liu1,2, Xiaoli Sun1, Yuqing Song1, Weimin Yang2, Zhongfan Liu1,4( )
Beijing Graphene Institute (BGI), Beijing 100095, China
College of Mechanical and Electrical Engineering, Beijing University of Chemical Technology, Beijing 100029, China
School of Instrument and Electronics, North University of China, Taiyuan 030051, China
Center for Nanochemistry, Beijing Science and Engineering Center for Nanocarbons, Beijing National Laboratory for Molecular Science, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

§ Xiucai Sun and Shuang Lou contributed equally to this work.

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Graphical Abstract

Graphene growth involves complicated hydrocarbon transitions rather than only carbon atomic activity. The dominant species of CH decomposed by CH4 leads to a localized sp3 hybridized carbon at the connecting site when attachment, and the excess H must be transferred and overcome the dehydrogenation process with high-energy barriers to achieve the sp2 reconstruction of the newly grown edge. Therefore, the growth of graphene is kinetically hydrogen-constrained and exhibits experimentally quantified growth rates.

Abstract

Chemical vapor deposition (CVD) has shown great promise for the large-scale production of high-quality graphene films for industrial applications. Atomic-scale theoretical studies can help experiments to deeply understand the graphene growth mechanism, and serve as theoretical guides for further experimental designs. Here, by using density functional theory calculations, ab-initio molecular dynamics simulations, and microkinetic analysis, we systematically investigated the kinetics of hydrogen constrained graphene growth on Cu substrate. The results reveal that the actual hydrogen-rich environment of CVD results in CH as the dominating carbon species and graphene H-terminated edges. CH participated island sp2 nucleation avoids chain cyclization process, thereby improving the nucleation and preventing the formation of non-hexameric ring defects. The graphene growth is not simply C-atomic activity, rather, involves three main processes: CH species attachment at the growth edge, leading to a localized sp3 hybridized carbon at the connecting site; excess H transfer from the sp3 carbon to the newly attached CH; and finally dehydrogenation to achieve the sp2 reconstruction of the newly grown edge. The threshold reaction barriers for the growth of graphene zigzag (ZZ) and armchair (AC) edges were calculated as 2.46 and 2.16 eV, respectively, thus the AC edge grows faster than the ZZ one. Our theory successfully explained why the circumference of a graphene island grown on Cu substrates is generally dominated by ZZ edges, which is a commonly observed phenomenon in experiments. In addition, the growth rate of graphene on Cu substrates is calculated and matches well with existing experimental observations.

Keywords

graphene growthchemical vapor depositiontheoretical calculationCu substratehydrogen constraint effect

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Nano Research
Volume 17 Issue 11,
November 2024
Pages 9284-9292
DOI: 10.1007/s12274-024-6945-2
Cite this article:
Sun X, Lou S, Wang W, et al. Kinetics of hydrogen constrained graphene growth on Cu substrate. Nano Research, 2024, 17(11): 9284-9292. https://doi.org/10.1007/s12274-024-6945-2
Topics:
Graphene

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Received: 11 June 2024
Revised: 02 August 2024
Accepted: 05 August 2024
Published: 03 September 2024
© Tsinghua University Press 2024
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