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Reproducible graphene synthesis by oxygen-free chemical vapour deposition

Abstract

Chemical vapour deposition (CVD) synthesis of graphene on copper has been broadly adopted since the first demonstration of this process1. However, widespread use of CVD-grown graphene for basic science and applications has been hindered by challenges with reproducibility2 and quality3. Here we identify trace oxygen as a key factor determining the growth trajectory and quality for graphene grown by low-pressure CVD. Oxygen-free chemical vapour deposition (OF-CVD) synthesis is fast and highly reproducible, with kinetics that can be described by a compact model, whereas adding trace oxygen leads to suppressed nucleation and slower/incomplete growth. Oxygen affects graphene quality as assessed by surface contamination, emergence of the Raman D peak and decrease in electrical conductivity. Epitaxial graphene grown in oxygen-free conditions is contamination-free and shows no detectable D peak. After dry transfer and boron nitride encapsulation, it shows room-temperature electrical-transport behaviour close to that of exfoliated graphene. A graphite-gated device shows well-developed integer and fractional quantum Hall effects. By highlighting the importance of eliminating trace oxygen, this work provides guidance for future CVD system design and operation. The increased reproducibility and quality afforded by OF-CVD synthesis will broadly influence basic research and applications of graphene.

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Fig. 1: OF-CVD system design, influence of trace oxygen and high reproducibility.
Fig. 2: Kinetics of graphene grain growth.
Fig. 3: Effects of trace O2 on graphene growth under typical (hydrogen-rich) CVD conditions.
Fig. 4: High-quality OF-CVD graphene.

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Data availability

Experimental data relevant to figures in the main text and data of numerical calculations are available at https://doi.org/10.5281/zenodo.1095734242. All other raw data are available from the corresponding author on request.

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Acknowledgements

This work was primarily supported by the NSF MRSEC programme at Columbia through the Center for Precision-Assembled Quantum Materials (DMR-2011738). Magnetotransport studies were supported by the Department of Energy (DE-SC0016703). J.A. acknowledges support from NASA STRF (80NSSC19K1180). C.R.D. and J.H. acknowledge further support from the Gordon and Betty Moore Foundation’s EPiQS Initiative, grant GBMF10277. R.M. and P.L.L. acknowledge support by the Canada Research Chair and the Natural Sciences and Engineering Research Council of Canada (grants nos. RGPIN-2019-06545 and RGPAS-2019-00050). Synthesis of boron nitride (K.W. and T.T.) was supported by the Elemental Strategy Initiative conducted by the MEXT, Japan (grant no. JPMXP0112101001) and JSPS KAKENHI (grant nos. JP19H05790 and JP20H00354). Analysis of Raman spectra (C.E.W.-S.) was supported by the National Science Foundation through the Howard-Columbia Partnership for Research and Education in Superatomic and 2D Materials (PRES2M) (DMR-2122151). Development of techniques for graphene transfer was supported by Hyundai Motor Company and the National Institute of Standards and Technology (NIST) (60NANB21D178). Certain commercial equipment, instruments or materials are identified in this manuscript to specify the experimental procedure adequately. Such identification is not intended to imply recommendation or endorsement by the NIST, nor is it intended to imply that the materials or equipment are necessarily the best available for the purpose. We would like to thank the following students for their contributions to set the stage for this project: E. Yanev for system design/installation and substrate optimization, N. Guillomaitre for substrate optimization and graphene synthesis process automation, A. Santimetaneedol for substrate optimization and process automation and A. Vera for analysis on the impact of copper morphology on graphene growth kinetics.

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Authors

Contributions

J.A., X.Y., C.S.D. and J.H. conceived the experiments. J.H. supervised the project. J.A. and X.Y. performed the OF-CVD graphene growths. X.Y. prepared the electropolished Cu foils. J.A. and X.Y. prepared the Cu(111)/sapphire samples. T.A., J.A., X.Y., C.E.W.-S. and A.R.H.W. were responsible for Raman spectroscopy. X.Y. was responsible for AFM. M.H. was responsible for STM. A.J.B. was responsible for XPS. X.Y. and J.A. were responsible for EBSD. J.A. and X.Y. were responsible for wet graphene transfer. X.Y. prepared the suspended graphene samples. K.W. and T.T. supplied the h-BN. J.A. fabricated the OF-CVD graphene transport devices and J.A., J.P. and D.S. measured the devices. Z.W. and X.Y. fabricated and measured the exfoliated graphene transport devices. X.Y., K.B., R.M. and J.H. derived the growth kinetics model. J.A., X.Y. and C.C. were responsible for data analysis. C.S.D., X.Y., J.A. and P.L.L. designed and constructed the OF-CVD system. P.L.L. provided the comparative graphene sample from Infinite Potential Laboratories. C.S.D. and P.L.L. contributed theoretical discussion and guidance. J.H., J.A. and X.Y. drafted the manuscript and R.M., K.B., T.A. and A.R.H.W. revised it. All co-authors commented on the manuscript before its submission.

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Correspondence to Katayun Barmak, Richard Martel or James Hone.

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Competing interests

Two of the authors (P.L.L. and R.M.) are inventors on US Patent 11447391. One author (C.S.D.) is founder of a company (Sindri Materials) seeking to commercialize advances in graphene synthesis.

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Amontree, J., Yan, X., DiMarco, C.S. et al. Reproducible graphene synthesis by oxygen-free chemical vapour deposition. Nature 630, 636–642 (2024). https://doi.org/10.1038/s41586-024-07454-5

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