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Research Article

Invisible vapor catalysis in graphene growth by chemical vapor deposition

Xiucai Sun1,2, Xiaoting Liu1,3, Zhongti Sun4, Xintong Zhang2, Yuzhu Wu1,2, Yeshu Zhu1,3, Yuqing Song2, Kaicheng Jia2, Jincan Zhang2,5, Luzhao Sun2, Wan-Jian Yin2,6( ), Zhongfan Liu1,2( )
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
Beijing Graphene Institute (BGI), Beijing 100095, China
Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China
School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China
Department of Engineering, University of Cambridge, Cambridge CB3 0FA, UK
College of Energy, Soochow Institute for Energy and Materials InnovationS (SIEMIS), Jiangsu Provincial Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies, Soochow University, Suzhou 215006, China
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Graphical Abstract

Cu vapor dominated by substrate evaporation exhibits excellent catalytic activity than the Cu(111) surface owing to the quantum confinement effect and abundant catalytic surface. Cu clusters in vapor phase can significantly promote the adsorption and dehydrogenation of CH4 molecules and also accelerate the decomposition of larger hydrocarbon species (e.g., C4H10) aggregated from insufficiently dehydrogenated CH3 groups in the gas phase, thus providing sufficient supply of active C atoms for the rapid graphene growth and improving the surface cleanliness of synthesized graphene.

Abstract

Vapor catalysis was recently found to play a crucial role in superclean graphene growth via chemical vapor decomposition (CVD). However, knowledge of vapor-phase catalysis is scarce, and several fundamental issues, including vapor compositions and their impact on graphene growth, are ambiguous. Here, by combining density functional theory (DFT) calculations, an ideal gas model, and a designed experiment, we found that the vapor was mainly composed of Cui clusters with tens of atoms. The vapor pressure was estimated to be ~ 10−12–10−11 bar under normal low-pressure CVD system (LPCVD) conditions for graphene growth, and the exposed surface area of Cui clusters in the vapor was 22–269 times that of the Cu substrate surface, highlighting the importance of vapor catalysis. DFT calculations show Cu clusters, represented by Cu17, have strong capabilities for adsorption, dehydrogenation, and decomposition of hydrocarbons. They exhibit an adsorption lifetime and reaction flux six orders of magnitude higher than those on the Cu surface, thus providing a sufficient supply of active C atoms for rapid graphene growth and improving the surface cleanliness of the synthesized graphene. Further experimental validation showed that increasing the amount of Cu vapor improved the as-synthesized graphene growth rate and surface cleanliness. This study provides a comprehensive understanding of vapor catalysis and the fundamental basis of vapor control for superclean graphene rapid growth.

Keywords

chemical vapor depositionfirst-principles calculationgraphene growthvapor catalysis

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Nano Research
Volume 17 Issue 5,
May 2024
Pages 4259-4269
DOI: 10.1007/s12274-023-6260-3
Cite this article:
Sun X, Liu X, Sun Z, et al. Invisible vapor catalysis in graphene growth by chemical vapor deposition. Nano Research, 2024, 17(5): 4259-4269. https://doi.org/10.1007/s12274-023-6260-3
Topics:
Chemical vapor deposition

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Received: 22 August 2023
Revised: 10 October 2023
Accepted: 11 October 2023
Published: 01 December 2023
© Tsinghua University Press 2023
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