Variations of the lattice parameter can significantly change the properties of a material, and, in particular, its electronic behaviour. In the case of graphene, however, variations of the lattice constant with respect to graphite have been limited to less than 2.5% due to its well-established high in-plane stiffness. Here, through systematic electronic and lattice structure studies, we report regions where the lattice constant of graphene monolayers grown on copper by chemical vapour deposition increases up to ~7.5% of its relaxed value. Density functional theory calculations confirm that this expanded phase is energetically metastable and driven by the enhanced interaction between the substrate and the graphene adlayer. We also prove that this phase possesses distinctive chemical and electronic properties. The inherent phase complexity of graphene grown on copper foils revealed in this study may inspire the investigation of possible metastable phases in other seemingly simple heterostructure systems.

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The Synchrotron SOLEIL is supported by the Centre National de la Recherche Scientifique (CNRS) and the Commissariat à l’Energie Atomique et aux Energies Alternatives (CEA), France. This work is supported by a public grant overseen by the French National Research Agency (ANR) as part of the ‘Investissements d’Avenir” program (Labex NanoSaclay, reference: ANR-10-LABX-0035), as well as the the French Ministère des affaires étrangères et européennes (MAEE), the Centre National de la Recherche Scientifique (CNRS) through the ICT-ASIA programme grant 3226/DGM/ATT/RECH. Y.C is grateful for the HKU Start-up Fund for New Staff and the research computing facilities offered by ITS, HKU. We thank S. Lorcy (beamline ANTARES, SOLEIL), D. Alamarguy (Centralesupelec) for the technical support, A. Ouerghi (CNRS, France) and Q. Wu (EPFL, Lausanne) for helpful discussions. We are also indebted to F. Borondics and C. Sandt (beamline SMIS, SOLEIL) for Raman measurement support, Y. Niu (Cardiff University), and S. Stanescu and R. Belkhou (beamline HERMES, SOLEIL) for LEEM/LEED measurement support and discussion.

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  1. ANTARES Beamline, Synchrotron SOLEIL & Université Paris-Saclay, L’Orme des Merisiers, Gif sur Yvette CEDEX, France

    • Chaoyu Chen
    • , José Avila
    •  & Maria C. Asensio
  2. Group of Electrical Engineering-Paris, UMR CNRS 8507, CentraleSupélec, Univ. Paris-Sud, Université Paris-Saclay; Sorbonne Universités, UPMC Univ Paris 06, Gif-sur-Yvette CEDEX, France

    • Hakim Arezki
    •  & Mohamed Boutchich
  3. IBS Center for Integrated Nanostructure Physics (CINAP), Institute for Basic Science, Sungkyunkwan University, Suwon, Korea

    • Van Luan Nguyen
    • , Fei Yao
    •  & Young Hee Lee
  4. Department of Mechanical Engineering, The University of Hong Kong, Hong Kong SAR, China

    • Jiahong Shen
    •  & Yue Chen
  5. Department of Materials Science, Fudan University, Shanghai, China

    • Jiahong Shen
  6. Department of Physics, University of Bath, Bath, UK

    • Marcin Mucha-Kruczyński
  7. Centre for Nanoscience and Nanotechnology, University of Bath, Bath, UK

    • Marcin Mucha-Kruczyński
  8. Department of Energy Science, Sungkyunkwan University, Suwon, Korea

    • Young Hee Lee


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C.C., J.A. and M.B. performed the nanoARPES experiments. C.C. and J.A. managed the data analysis. C.C. drafted the manuscript with the input from M.B., M.M.-K., Y.C. and M.C.A. The growth and characterization process of the CVD graphene samples was developed by V.L.N., F.Y., Y.H.L. and H.A. J.S. and Y.C. performed DFT calculations with results shown in Fig. 5 and Supplementary Fig. 8. M.M.-K. contributed to the theoretical analysis presented in Supplementary Section 6 and its corresponding discussions in the main text. C.C. and M.C.A. discussed and decided the main strategies of the project. M.C.A. directed this research project. All authors discussed and revised the manuscript.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Mohamed Boutchich or Yue Chen or Maria C. Asensio.

Supplementary information

  1. Supplementary information

    Ten sections, ten figures, ten references.

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