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High-quality bilayer graphene grown on softened copper foils by atmospheric pressure chemical vapor deposition

常压化学气相沉积法在软化铜箔上生长高质量双 层石墨烯

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Abstract

Bilayer graphene (BLG) shows great application prospect and potential in next-generation electronics because of its unique electrical and mechanical properties. However, the scalable synthesis of large-area high-quality BLG films is still a great challenge, despite the maturity of chemical vapor deposition (CVD) technique. In this study, we report a robust method to grow BLGs on flat, softened Cu foils by atmospheric pressure CVD. A moderate amount of residual oxygen accelerates the growth of BLG domains while suppressing the formation of multilayers. Raising the nucleation density at low hydrogen pressure efficiently increases the film continuity. Based on the optimized CVD process, the growth of graphene films on 4×4 cm2 Cu foils with an average BLG coverage of 76% is achieved. The morphology and structure characterizations demonstrate a high quality of the BLG. Dual gate field-effect transistors are investigated based on AB-stacked BLG, with a tunable bandgap and high carrier mobility of up to 6790 cm2 V−1 s−1 at room temperature.

摘要

双层石墨烯因其独特的物理性质在新型电子器件等领域具 有广阔的应用前景. 大面积高质量双层石墨烯的批量化制备是实 现其后续应用的关键. 目前, 基于铜表面自限制催化的化学气相沉 积法可有效实现单层石墨烯的生长, 但由于第二层石墨烯结构导 致更复杂的生长过程, 双层石墨烯的可控制备极具挑战性. 本文系 统研究了石墨烯的常压化学气相沉积制备过程, 提出了一种在软 化铜箔基底上生长高质量双层石墨烯的方法. 铜箔在随炉升温过 程中软化并贴合至背面的石英舟/管表面, 形成具有差异反应条件 的铜箔双面, 从而促使双层石墨烯在其正面生长. 反应系统中的残 余氧气有效加快了双层石墨烯的生长. 同时, 适量的残余氧气可抑 制三层及少数层石墨烯的形成, 提高双层石墨烯产物的均匀性. 基 于优化的生长条件, 在4×4 cm2铜箔上实现了双层覆盖率达76%的 高质量石墨烯薄膜的生长. 基于AB堆垛双层石墨烯的双栅场效应 晶体管, 室温载流子迁移率达6790 cm2 V−1 s−1. 本研究有助于推动 石墨烯等二维材料的层数可控合成技术的发展.

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References

  1. Zhang Y, Tang TT, Girit C, et al. Direct observation of a widely tunable bandgap in bilayer graphene. Nature, 2009, 459: 820–823

    CAS  Google Scholar 

  2. Cao Y, Fatemi V, Fang S, et al. Unconventional superconductivity in magic-angle graphene superlattices. Nature, 2018, 556: 43–50

    CAS  Google Scholar 

  3. Gao Y, Cao T, Cellini F, et al. Ultrahard carbon film from epitaxial two-layer graphene. Nat Nanotech, 2018, 13: 133–138

    CAS  Google Scholar 

  4. Li X, Cai W, An J, et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science, 2009, 324: 1312–1314

    CAS  Google Scholar 

  5. Bae S, Kim H, Lee Y, et al. Roll-to-roll production of 30-inch graphene films for transparent electrodes. Nat Nanotech, 2010, 5: 574–578

    CAS  Google Scholar 

  6. Li X, Cai W, Colombo L, et al. Evolution of graphene growth on Ni and Cu by carbon isotope labeling. Nano Lett, 2009, 9: 4268–4272

    CAS  Google Scholar 

  7. López GA, Mittemeijer EJ. The solubility of C in solid Cu. Scripta Mater, 2004, 51: 1–5

    Google Scholar 

  8. Wu J, Wang J, Pan D, et al. Synchronous growth of high-quality bilayer Bernal graphene: from hexagonal single-crystal domains to wafer-scale homogeneous films. Adv Funct Mater, 2017, 27: 1605927

    Google Scholar 

  9. Zhou H, Yu WJ, Liu L, et al. Chemical vapour deposition growth of large single crystals of monolayer and bilayer graphene. Nat Commun, 2013, 4: 2096

    Google Scholar 

  10. Liu L, Zhou H, Cheng R, et al. High-yield chemical vapor deposition growth of high-quality large-area AB-stacked bilayer graphene. ACS Nano, 2012, 6: 8241–8249

    CAS  Google Scholar 

  11. Qi Z, Shi H, Zhao M, et al. Chemical vapor deposition growth of bernal-stacked bilayer graphene by edge-selective etching with H2O. Chem Mater, 2018, 30: 7852–7859

    CAS  Google Scholar 

  12. Wu Y, Chou H, Ji H, et al. Growth mechanism and controlled synthesis of AB-stacked bilayer graphene on Cu-Ni alloy foils. ACS Nano, 2012, 6: 7731–7738

    CAS  Google Scholar 

  13. Liu W, Kraemer S, Sarkar D, et al. Controllable and rapid synthesis of high-quality and large-area Bernal stacked bilayer graphene using chemical vapor deposition. Chem Mater, 2013, 26: 907–915

    Google Scholar 

  14. Yang C, Wu T, Wang H, et al. Copper-vapor-assisted rapid synthesis of large AB-stacked bilayer graphene domains on Cu-Ni alloy. Small, 2016, 12: 2009–2013

    CAS  Google Scholar 

  15. Yoo MS, Lee HC, Lee S, et al. Chemical vapor deposition of Bernal-stacked graphene on a Cu surface by breaking the carbon solubility symmetry in Cu foils. Adv Mater, 2017, 29: 1700753

    Google Scholar 

  16. Hao Y, Wang L, Liu Y, et al. Oxygen-activated growth and bandgap tunability of large single-crystal bilayer graphene. Nat Nanotech, 2016, 11: 426–431

    CAS  Google Scholar 

  17. Yan K, Peng H, Zhou Y, et al. Formation of bilayer Bernal graphene: layer-by-layer epitaxy via chemical vapor deposition. Nano Lett, 2011, 11: 1106–1110

    CAS  Google Scholar 

  18. Celebi K, Cole MT, Choi JW, et al. Evolutionary kinetics of graphene formation on copper. Nano Lett, 2013, 13: 967–974

    CAS  Google Scholar 

  19. Fang W, Hsu AL, Song Y, et al. Asymmetric growth of bilayer graphene on copper enclosures using low-pressure chemical vapor deposition. ACS Nano, 2014, 8: 6491–6499

    CAS  Google Scholar 

  20. Li Q, Chou H, Zhong JH, et al. Growth of adlayer graphene on Cu studied by carbon isotope labeling. Nano Lett, 2013, 13: 486–490

    CAS  Google Scholar 

  21. Chan CC, Chung WL, Woon WY. Nucleation and growth kinetics of multi-layered graphene on copper substrate. Carbon, 2018, 135: 118–124

    CAS  Google Scholar 

  22. Shen C, Yan X, Qing F, et al. Criteria for the growth of large-area adlayer-free monolayer graphene films by chemical vapor deposition. J Materiomics, 2019, 5: 463–470

    Google Scholar 

  23. Abidi IH, Liu Y, Pan J, et al. Regulating top-surface multilayer/single-crystal graphene growth by “gettering” carbon diffusion at backside of the copper foil. Adv Funct Mater, 2017, 27: 1700121

    Google Scholar 

  24. Han Z, Kimouche A, Kalita D, et al. Homogeneous optical and electronic properties of graphene due to the suppression of multilayer patches during CVD on copper foils. Adv Funct Mater, 2014, 24: 964–970

    CAS  Google Scholar 

  25. Yan Z, Liu Y, Ju L, et al. Large hexagonal bi- and trilayer graphene single crystals with varied interlayer rotations. Angew Chem Int Ed, 2014, 53: 1565–1569

    CAS  Google Scholar 

  26. Chen Q, Zhong Y, Huang M, et al. Direct growth of high crystallinity graphene from water-soluble polymer powders. 2D Mater, 2018, 5: 035001

    Google Scholar 

  27. Chen Q, Yi X, Huang M, et al. Sustained and controlled release of volatile precursors for chemical vapor deposition of graphene at atmospheric pressure. Chem Eur J, 2020, 26: 7463–7469

    CAS  Google Scholar 

  28. Liang T, Luan C, Chen H, et al. Exploring oxygen in graphene chemical vapor deposition synthesis. Nanoscale, 2017, 9: 3719–3735

    CAS  Google Scholar 

  29. Srinivasan BM, Hao Y, Hariharaputran R, et al. Oxygen-promoted chemical vapor deposition of graphene on copper: a combined modeling and experimental study. ACS Nano, 2018, 12: 9372–9380

    CAS  Google Scholar 

  30. Hao Y, Bharathi MS, Wang L, et al. The role of surface oxygen in the growth of large single-crystal graphene on copper. Science, 2013, 342: 720–723

    CAS  Google Scholar 

  31. Xu X, Zhang Z, Qiu L, et al. Ultrafast growth of single-crystal graphene assisted by a continuous oxygen supply. Nat Nanotech, 2016, 11: 930–935

    CAS  Google Scholar 

  32. Chen J, Cui M, Wu G, et al. Fast growth of large single-crystalline graphene assisted by sequential double oxygen passivation. Carbon, 2017, 116: 133–138

    CAS  Google Scholar 

  33. Ferrari AC, Basko DM. Raman spectroscopy as a versatile tool for studying the properties of graphene. Nat Nanotech, 2013, 8: 235–246

    CAS  Google Scholar 

  34. Ferrari AC, Meyer JC, Scardaci V, et al. Raman spectrum of graphene and graphene layers. Phys Rev Lett, 2006, 97: 187401

    CAS  Google Scholar 

  35. Wu R, Pan J, Ou X, et al. Concurrent fast growth of sub-centimeter single-crystal graphene with controlled nucleation density in a confined channel. Nanoscale, 2017, 9: 9631–9640

    CAS  Google Scholar 

  36. Pang J, Bachmatiuk A, Fu L, et al. Oxidation as a means to remove surface contaminants on Cu foil prior to graphene growth by chemical vapor deposition. J Phys Chem C, 2015, 119: 13363–13368

    Google Scholar 

  37. Magnuson CW, Kong X, Ji H, et al. Copper oxide as a “self-cleaning” substrate for graphene growth. J Mater Res, 2014, 29: 403–409

    CAS  Google Scholar 

  38. Chen X, Zhao P, Xiang R, et al. Chemical vapor deposition growth of 5 mm hexagonal single-crystal graphene from ethanol. Carbon, 2015, 94: 810–815

    CAS  Google Scholar 

  39. Wang ZJ, Dong J, Cui Y, et al. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging. Nat Commun, 2016, 7: 13256

    CAS  Google Scholar 

  40. Wang H, Wang G, Bao P, et al. Controllable synthesis of submillimeter single-crystal monolayer graphene domains on copper foils by suppressing nucleation. J Am Chem Soc, 2012, 134: 3627–3630

    CAS  Google Scholar 

  41. Yan Z, Lin J, Peng Z, et al. Toward the synthesis of wafer-scale single-crystal graphene on copper foils. ACS Nano, 2012, 6: 9110–9117

    CAS  Google Scholar 

  42. Hernandez Y, Nicolosi V, Lotya M, et al. High-yield production of graphene by liquid-phase exfoliation of graphite. Nat Nanotech, 2008, 3: 563–568

    CAS  Google Scholar 

  43. Yi D, Jeon S, Hong SW. Selectively patterned regrowth of bilayer graphene for self-integrated electronics by sequential chemical vapor deposition. ACS Appl Mater Interfaces, 2018, 10: 40014–40023

    CAS  Google Scholar 

  44. Zou K, Zhu J. Transport in gapped bilayer graphene: the role of potential fluctuations. Phys Rev B, 2010, 82: 081407

    Google Scholar 

Download references

Acknowledgements

This work was supported by China Postdoctoral Science Foundation (2018M642831), and Shenzhen Science and Technology Project JCYJ20180507183904841).

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Authors and Affiliations

  1. MOE Key Lab of Fundamental Physical Quantities Measurement & Hubei Key Lab of Gravitation and Quantum Physics, School of Physics, Huazhong University of Science and Technology, Wuhan, 430074, China

    Qiao Chen  (陈巧), Qiyang Song  (宋启扬), Xin Yi  (易新), Qiao Chen  (陈乔), Wenjia Wu  (吴文嘉), Chuanwen Zhao  (赵传文) & Shun Wang  (王顺)

  2. State Key Lab of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing, 100084, China

    Qiao Chen  (陈巧), Meirong Huang  (黄美榕) & Hongwei Zhu  (朱宏伟)

  3. Shenzhen Huazhong University of Science and Technology Research Institute, Shenzhen, 518057, China

    Shun Wang  (王顺)

Authors
  1. Qiao Chen  (陈巧)
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  2. Qiyang Song  (宋启扬)
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  3. Xin Yi  (易新)
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  4. Qiao Chen  (陈乔)
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  5. Wenjia Wu  (吴文嘉)
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  6. Meirong Huang  (黄美榕)
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  7. Chuanwen Zhao  (赵传文)
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  8. Shun Wang  (王顺)
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  9. Hongwei Zhu  (朱宏伟)
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Contributions

Chen Q, Wang S, and Zhu H proposed the concept and conceived the experiments. Chen Q, Song Q, Yi X, Chen Q, Wu W, Huang M, and Zhao C carried out the experiments. Chen Q drafted the manuscript and all authors discussed and revised it.

Corresponding authors

Correspondence to Shun Wang  (王顺) or Hongwei Zhu  (朱宏伟).

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Conflict of interest

The authors declare no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper.

Qiao Chen received her BSc degree from Zhengzhou University in 2013. She obtained her PhD degree under the supervision of Prof. Hongwei Zhu in 2018 from Tsinghua University. She then worked as a postdoctoral fellow at Huazhong University of Science and Technology. Her current research interest is the design and preparation of low dimensional carbon structures by CVD.

Shun Wang received his PhD degree from the University of Minnesota in 2010. He then worked as a postdoctoral researcher at the University of Minnesota and as an associate professor at Shanghai Jiao Tong University. Currently he is a professor at Huazhong University of Science and Technology. His research interests are the electrical and optoelectronic properties of low dimensional materials.

Hongwei Zhu is a professor of the School of Materials Science and Engineering, Tsinghua University. He received his BSc degree in mechanical engineering (1998) and PhD degree in materials processing engineering (2003) from Tsinghua University. After postdoc experience in Japan and USA, he began his independent career as a faculty member at Tsinghua University (2008-present). His current research interests involve the structural design and engineering of nanomaterials for energy and environmental applications.

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Chen, Q., Song, Q., Yi, X. et al. High-quality bilayer graphene grown on softened copper foils by atmospheric pressure chemical vapor deposition. Sci. China Mater. 63, 1973–1982 (2020). https://doi.org/10.1007/s40843-020-1394-3

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