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SCIENCE CHINA Materials, Volume 62 , Issue 8 : 1087-1095(2019) https://doi.org/10.1007/s40843-019-9406-7

Insight into the rapid growth of graphene single crystals on liquid metal via chemical vapor deposition

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  • ReceivedJan 29, 2019
  • AcceptedFeb 16, 2019
  • PublishedMar 15, 2019

Abstract

Previous reports about the growth of large graphene single crystals on polycrystalline metal substrates usually adopted the strategy of suppressing the nucleation by lowering the concentration of the feedstock, which greatly limited the rate of the nucleation and the sequent growth. The emerging liquid metal catalyst possesses the characteristic of quasi-atomically smooth surface with high diffusion rate. In principle, it should be a naturally ideal platform for the low-density nucleation and the fast growth of graphene. However, the rapid growth of large graphene single crystals on liquid metals has not received the due attention. In this paper, we firstly purposed the insight into the rapid growth of large graphene single crystals on liquid metals. We obtained the millimeter-size graphene single crystals on liquid Cu. The rich free-electrons in liquid Cu accelerate the nucleation, and the isotropic smooth surface greatly suppresses the nucleation. Moreover, the fast mass-transfer of carbon atoms due to the excellent fluidity of liquid Cu promotes the fast growth with a rate up to 79 µm s–1. We hope the research on the growth speed of graphene on liquid Cu can enrich the recognition of the growth behavior of two-dimensional (2D) materials on the liquid metal. We also believe that the liquid metal strategy for the rapid growth of graphene can be extended to various 2D materials and thus promote their future applications in the photonics and electronics.


Funded by

The research was supported by the National Natural Science Foundation of China(21673161)

the Sino-German Center for Research Promotion(1400)


Acknowledgment

The research was supported by the National Natural Science Foundation of China (21673161) and the Sino-German Center for Research Promotion (1400).


Interest statement

The authors declare no competing financial interest.


Contributions statement

Fu L and Zeng M developed the concept and conceived the experiments. Zheng S, Zeng M, Cao H, Zhang T, Gao X and Xiao Y carried out the experiments. Zheng S and Zeng M wrote the manuscript. Fu L revised the manuscript. All of the authors contributed to the data analysis and scientific discussion.


Author information

Shuting Zheng received her BSc from the Northwest University in 2016 and is now a master’s degree candidate under the supervision of Prof. Lei Fu at the College of Chemistry and Molecular Sciences at Wuhan University. Her current research interest is the controllable growth of 2D material


Mengqi Zeng received her BSc from Wuhan University in 2013. She obtained her PhD degree under the supervision of Prof. Lei Fu in 2018 from Wuhan University. In 2018, she joined Wuhan University as an Associate Professor. Her current research interest is the catalyst design for the controllable growth and self-assembly of 2D materials.


Lei Fu received his BSc degree in chemistry from Wuhan University in 2001. He obtained his PhD degree from the Institute of Chemistry, Chinese Academy of Sciences in 2006. After obtaining his PhD, he worked as a Director’s Postdoctoral Fellow at the Los Alamos National Laboratory, Los Alamos, NM (2006−2007). Thereafter, he became an Associate Professor at Peking University. In 2012, he joined Wuhan University as a Full Professor. His current interest of research focuses on the controlled growth and novel property exploration of 2D atomic layer thin crystals.


Supplement

Supplementary information

The supporting information is available in the online version of the paper. (The nucleation density of graphene on Cu at different temperatures, EBSD characterizations conducted on solidified liquid Cu and solid Cu, comparison of the growth rate of graphene single crystal between our work and the reported literatures, the growth rate of graphene single crystal grown on solid Cu, effect of diffusion rate on the growth rate of graphene single crystal on liquid Cu, the identification of the effect of the diffusion rate on the growth rate of graphene single crystal on liquid Cu, carbon isotope labeling experiments for elucidating the mechanism and kinetics of the growth of graphene on liquid Cu, the confirmation of the dissolution of carbon in liquid Cu, and the TEM characterizations of the as-obtained graphene single crystal grown on liquid Cu.)


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  • Figure 1

    The nucleation of graphene on liquid Cu. (a) Schematic of the graphene nucleation on liquid Cu under CH4 with extremely low concentration. The rich free electrons in liquid Cu can help grab the active carbon species for the graphene nucleation. (b) Plot of the nucleation density and nucleation time of graphene on Cu as a function of the temperature. (c) Arrhenius plot for the nucleation density of graphene on Cu.

  • Figure 2

    Time evolution of graphene single crystal grown on liquid Cu. (a–c) SEM images of graphene single crystals synthesized at t=2, 3 and 4 s. t=0 s is defined as the moment when CH4 is introduced to the CVD furnace. (d) Plot of graphene size as a function of growth time. (e) Comparison of the growth rate of graphene in the recent literatures. The growth was conducted in the atmosphere of Ar/H2/CH4 (800 sccm/5 sccm/5 sccm) at 1,120°C.

  • Figure 3

    Fast growth mechanism of graphene on liquid Cu. (a) Schematic illustration of the precursor supply for the graphene growth on liquid Cu, which can both come from the surface adsorption and the bulk segregation. (b) TOF‒SIMS characterizations to show the intensity profile of carbon along the surface of G/liquid Cu and G/solid Cu after graphene growth for 10 min, and liquid Cu after annealing for 10 min, respectively.

  • Figure 4

    Large graphene single crystals grown on liquid Cu and the related quality characterizations. (a) Photograph of graphene single crystals grown on liquid Cu. (b) OM image of a corner of graphene single crystal transferred onto 300 nm SiO2/Si substrate. (c) Intensity mapping of 2D band, corresponding to the region in (b), showing the uniformity of the graphene single crystal at macroscopic scale. (d) HRTEM image of graphene, revealing the perfect hexagonal honeycomb structure. (e) The typical transfer characteristic curve of the as-fabricated FET device based on the graphene single crystal grown on liquid Cu at room temperature. (f) A histogram plot of the mobility value distribution extracted from 30 devices.

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