Abstract
Multilayer graphene and its stacking order provide both fundamentally intriguing properties and technological engineering applications. Several approaches to control the stacking order have been demonstrated, but a method of precisely controlling the number of layers with desired stacking sequences is still lacking. Here, we propose an approach for controlling the layer thickness and crystallographic stacking sequence of multilayer graphene films at the wafer scale via Cu–Si alloy formation using direct chemical vapour deposition. C atoms are introduced by tuning the ultra-low-limit CH4 concentration to form a SiC layer, reaching one to four graphene layers at the wafer scale after Si sublimation. The crystallographic structure of single-crystalline or uniformly oriented bilayer (AB), trilayer (ABA) and tetralayer (ABCA) graphene are determined via nano-angle-resolved photoemission spectroscopy, which agrees with theoretical calculations, Raman spectroscopy and transport measurements. The present study takes a step towards the layer-controlled growth of graphite and other two-dimensional materials.
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Data availability
The data that support the findings of this study are presented in the main text and the Supplementary Information, and are available from the corresponding author upon reasonable request. Source data are provided with this paper.
Change history
07 December 2020
A Correction to this paper has been published: https://doi.org/10.1038/s41565-020-00821-z.
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Acknowledgements
This work was supported by the Institute for Basic Science (IBS-R011-D1), Republic of Korea. S.-Y.J. thanks the Basic Science Research Program of the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (no. NRF-2017R1A2B3011822). The Antares’s group at the Synchrotron SOLEIL is supported by Université Paris Saclay, Centre National de la Recherche Scientique (CNRS) and Commissariat à l’Energie Atomique et aux Energies Alternatives (CEA), France. Y.-M.K. was supported in part by an NRF grant (NRF-2015M3D1A1070672) in Korea.
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V.L.N. performed most of the experiments, measurements and data analysis, and prepared the manuscript. D.L.D. performed the DFT calculations for graphene band structure, data analysis and manuscript preparation. S.H.L. conducted the graphene growth experiments. J.A. and M.C.A. designed, conducted and analysed the nano-ARPES measurements. S.-Y.J. prepared monocrystalline Cu films on sapphire. G.H. and Y.-M.K. conducted STEM analysis. Y.H.L. contributed to experimental planning, data analysis and manuscript preparation. All the authors discussed the results and commented on the manuscript.
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Peer review information Nature Nanotechnology thanks Jeremy Robinson and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Extended data
Extended Data Fig. 1 SIMS profiles of O and Si obtained after annealing the Cu film in an H2-rich environment at atmospheric pressure.
The O depth profile indicates that the oxygen exists only within 1–2 nm from the surface. In contrast, the Si depth profile indicates that the silicon exists up to 8 nm from the surface. Thus, it is evident that the thickness of Si is greater than that of O, implying that only the Si atoms were extracted from the quartz tube and deposited on the Cu surface to form a Cu-Si alloy. The presence of O atoms within 2 nm is unavoidable owing to the native oxide formation in the samples when exposed to ambient conditions. In Supplementary Fig. 1, the O content is in the range of 38.8–40.1 at.%, and the Si content increases from 15.1 to 38.6 at.% when the Cu film is annealed at atmospheric pressure (H2-rich environment, 1 atm) for 60 min. A similar O content (~40.5%) was revealed even when no Si was deposited. However, when the Cu substrate is annealed at a low pressure, a much higher O content (64.3 at.%) is observed owing to the deposition of SiO2 (Supplementary Fig. 3). These results also indicate that only the Si atoms are deposited on the Cu surface when annealed in an H2-rich environment at 1 atm, and the presence of O atoms is attributed to the native oxide formation occurring when the samples are exposed to ambient conditions. The O content will be much higher if SiO2 is deposited.
Extended Data Fig. 2 Schematic of graphene growth processes and the corresponding flow rates in each step for uniform multilayer growth.
Three mass flow controllers were employed to control the flow rates of H2, CH4, and Ar, respectively. The H2 and Ar gas bottles had a 6N purity. CH4 was introduced only to form SiC in step II. The temperature was increased to 1075 °C, and 200 sccm of Ar was injected into the chamber for the Si sublimation in step III. Pre-diluted CH4 (with Ar) gas of different concentrations was purchased. For growth in Fig. 2, the concentration of CH4 was 0.1%. The growth times of the island and full film were 5 and 10 min, respectively.
Extended Data Fig. 3 Optimisation of temperature at step II for a uniform multilayer growth.
a, When step II was performed at 700 °C, no graphene was observed. At this temperature, CH4 could not be decomposed, and thus, SiC was not formed in this step. Therefore, graphene was not formed although the conditions were suitable for growth in step III. b, In contrast, when steps II and III were performed at 900 and 1075 °C, respectively, multilayer islands with considerable uniform thickness were obtained. c, However, when the temperature was set at 1075 °C in step II, the Si sublimation could occur partially at such a high temperature, resulting in a non-uniform Cu-Si alloy and consequently a non-uniform multilayer graphene in step III. Therefore, 900 °C is considered to be an optimal temperature for step II.
Extended Data Fig. 4 Optimisation of temperature at step III.
As shown in panels a and b, the growth rate of multilayer graphene domains is directly proportional to the temperature. However, when the temperature is increased to more than 1075 °C, the Cu-Si alloy melts. Therefore, 1075 °C is considered to be an optimal temperature for step III.
Extended Data Fig. 5 Optical contrast of multilayer graphene.
a–d, Optical images of monolayer, bilayer, trilayer, and tetralayer graphene islands on SiO2/Si. The inset in each image depicts the optical contrast profile across the dashed line. e, Contrast difference of different graphene layers. The optical contrast difference increases linearly from panels (a)–(d), with the number of graphene layers.
Extended Data Fig. 6 Uniformity of multilayer graphene.
a–d, Optical images of full films of monolayer, bilayer, trilayer, and tetralayered graphene on SiO2/Si, and the inset images depict the corresponding confocal Raman mapping images of two-dimensional FWHM. The uniform colour contrast of these mapping images suggests a uniform stacking order across the entire graphene film.
Extended Data Fig. 7 Uniformly oriented graphene domains.
SEM image of the tetralayer graphene islands on a TEM grid and the corresponding SEAD patterns of the highlighted points. The parallel yellow dotted-lines indicate the orientation of tetralayer islands aligned in one preferred orientation.
Extended Data Fig. 8 LEED measurements of tetra-layer graphene on a mono-crystalline Cu(111) film.
a, Image of tetralayer graphene on a Cu substrate; the enlarged optical image depicts the wrinkles in the graphene film. b–d, Three representative LEED patterns of the highlighted points in panel (a). All the LEED patterns exhibit an identical lattice orientation of the graphene film across the entire wafer. The misalignment between graphene and copper is below 0.4°, and the mismatch of the lattice constant between graphene and Cu(111) surface is approximately 4.6%.
Extended Data Fig. 9 EADM analysis of graphene on the Cu(111) surface.
The alignment of the graphene supercell on the surface of Cu(111) is illustrated in both small and large scales. EADM is obtained from the following expression: (Id – I′d′)/I′d′, where d and d′ are the two respective atomic distances of the epilayer and substrate. I and I′ are determined by the relationship between two structures, and I/I′ is determined to be the smallest integral ratio required to match the extended lattice. Considering 5 × dCu-Cu interatomic spacing (12.7810 nm) of Cu and 9 × dC-C interatomic spacing (12.7827 nm) of graphene, the EADM of the graphene/Cu interface is determined to be only 0.013%.
Extended Data Fig. 10 Confocal Raman mapping of the graphene domains grown on a pure Cu substrate with 0.1% CH4.
a, Optical image of the graphene domains. The interlayer rotation angle between 1L and 2L (red and black dashed-lines) is 30°, whereas the angle between 2L, 3L, and 4L (red dashed-lines) is 0°. b, Corresponding confocal Raman mapping of 2D FWHM. (c) Raman spectra corresponding to the points marked in panel (b). d–f, Identical measurements on another domain. The interlayer crystal orientation of the three layers is 0°, forming the Bernal-stacking order. These observations indicate that the stacking order in this growth mode was random.
Supplementary information
Supplementary Information
Supplementary Figs. 1–15, experimental methods, Tables 1–3 and refs. 1–11.
Source data
Source Data Fig. 1
Graph for Fig. 1c–e.
Source Data Fig. 3
Graph for Fig. 3f.
Source Data Fig. 4
Graph for Fig. 4e–k.
Source Data Extended Data Fig. 1
Graph for Extended Data Fig. 1.
Source Data Extended Data Fig. 5
Graph for Extended Data Fig. 5a–d.
Source Data Extended Data Fig. 10
Graph for Extended Data Fig. 10c,f.
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Nguyen, V.L., Duong, D.L., Lee, S.H. et al. Layer-controlled single-crystalline graphene film with stacking order via Cu–Si alloy formation. Nat. Nanotechnol. 15, 861–867 (2020). https://doi.org/10.1038/s41565-020-0743-0
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DOI: https://doi.org/10.1038/s41565-020-0743-0
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