English

Synthesis of Superclean Graphene

• Xiaoting Liu ^{1, 2, 3,} ,
• Jincan Zhang ^{1, 2, 3,} ,
• Heng Chen ^{1, 3,} ,
• Zhongfan Liu ^{1, 3, ,}

• 1.

  Center for Nanochemistry, Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

• 2.

  Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China

• 3.

  Beijing Graphene Institute (BGI), Beijing 100095, China

Corresponding author: Zhongfan Liu, E-mail: zfliu@pku.edu.cn

• Received Date: 17 December 2020
  Accepted Date: 05 January 2021
  Revised Date: 04 January 2021
  Available Online: 15 January 2022
• Fund Project:

  the National Key Basic Research Program of China 

  the National Key Basic Research Program of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  Beijing National Laboratory for Molecular Sciences 

  Beijing Municipal Science and Technology Planning Project 

  Beijing Municipal Science and Technology Planning Project 

Abstract: Graphene has attracted enormous interest in both academic and industrial fields, owing to its unique, extraordinary properties and significant potential applications. Various methods have been developed to synthesize high-quality graphene, among which chemical vapor deposition (CVD) has emerged as the most encouraging for scalable graphene film production with promising quality, controllability, and uniformity. However, a gap still exists between ideal graphene, having remarkable properties, and the currently available CVD-derived graphene films. To close this gap, numerous studies in the past decade have been devoted to decreasing defect density, grain boundaries, and wrinkles, and increasing the controllability of layer thickness and doping of graphene. Significant recent advances in this regard were the discovery of the inevitable contamination of graphene surface during high-temperature CVD growth and the synthesis of superclean graphene, representing a new growth frontier in CVD graphene research. Surface contamination of graphene is a major hurdle in probing its intrinsic properties, and strongly hinders its applications, for instance, in electrical and photonic devices. In this review, we aim to provide comprehensive knowledge on the inevitable contamination of CVD graphene and current synthesis strategies for preparing superclean graphene films, and an outlook for the future mass production of high-quality superclean graphene films. First, we focus on surface contamination formation, e.g. amorphous carbon, during the high-temperature CVD growth process of graphene. After introducing evidence to confirm the origin of surface contamination, the formation mechanism of the amorphous carbon is thoroughly discussed. Meanwhile, the influence of the intrinsic cleanness of graphene on the peeling and transfer quality is also revealed. Second, we summarize the state-of-the-art superclean growth strategies and classify them into direct-growth approaches and post-growth treatment approaches. For the former, modification of the CVD gas-phase reactions, for example, using metal-vapor-assisted methods or cold-wall CVD, is effective in inhibiting the formation of amorphous carbon. For the latter, both chemical and physical cleaning methods are employed to eliminate amorphous carbon without damaging the graphene, e.g. selective etching of as-formed amorphous carbon using CO₂, and removal of amorphous carbon from the graphene surface using a lint roller based on interfacial force control. Third, we summarize the outstanding electrical, optical, and thermal properties of superclean graphene. Superclean graphene exhibits high carrier mobility, low contact resistance, high transparency, and high thermal conductivity, further highlighting the significance of superclean graphene growth. Finally, future opportunities and challenges for the industrial production of high-quality superclean graphene are discussed.

Key words:
• Chemical vapor deposition
•  /  Superclean graphene
•  /  Origin of surface contamination
•  /  Growth strategies
•  /  Extraordinary property

• 1. [1]

     Neto, A. C.; Guinea, F.; Peres, N. M.; Novoselov, K. S.; Geim, A. K. Rev. Mod. Phys. 2009, 81, 109. doi: 10.1103/RevModPhys.81.109

  2. [2]

     Du, X.; Skachko, I.; Barker, A.; Andrei, E. Y. Nat. Nanotechnol. 2008, 3, 491. doi: 10.1038/nnano.2008.199

  3. [3]

     Balandin, A. A.; Ghosh, S.; Bao, W.; Calizo, I.; Teweldebrhan, D.; Miao, F.; Lau, C. N. Nano Lett. 2008, 8, 902. doi: 10.1021/nl0731872

  4. [4]

     Nair, R. R.; Blake, P.; Grigorenko, A. N.; Novoselov, K. S.; Booth, T. J.; Stauber, T.; Peres, N. M.; Geim, A. K. Science 2008, 320, 1308. doi: 10.1126/science.1156965

  5. [5]

     Lee, C.; Wei, X.; Kysar, J. W.; Hone, J. Science 2008, 321, 385. doi: 10.1126/science.1157996

  6. [6]

     Novoselov, K. S.; Fal'ko, V. I.; Colombo, L.; Gellert, P. R.; Schwab, M. G.; Kim, K. Nature 2012, 490, 192. doi: 10.1038/nature11458

  7. [7]

     Ferrari, A. C.; Bonaccorso, F.; Fal'ko, V.; Novoselov, K. S.; Roche, S.; Boggild, P.; Borini, S.; Koppens, F. H. L.; Palermo, V.; Pugno, N.; et al. Nanoscale 2015, 7, 4598. doi: 10.1039/c4nr01600a

  8. [8]

     Bonaccorso, F.; Colombo, L.; Yu, G.; Stoller, M.; Tozzini, V.; Ferrari, A. C.; Ruoff, R. S.; Pellegrini, V. Science 2015, 347, 1246501. doi: 10.1126/science.1246501

  9. [9]

     Neumaier, D.; Pindl, S.; Lemme, M. C. Nat. Mater. 2019, 18, 525. doi: 10.1038/s41563-019-0359-7

  10. [10]

      Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Science 2004, 306, 666. doi: 10.1126/science.1102896

  11. [11]

      Voiry, D.; Yang, J.; Kupferberg, J.; Fullon, R.; Lee, C.; Jeong, H. Y.; Shin, H. S.; Chhowalla, M. Science 2016, 353, 1413. doi: 10.1126/science.aah3398

  12. [12]

      Hernandez, Y.; Nicolosi, V.; Lotya, M.; Blighe, F. M.; Sun, Z.; De, S.; McGovern, I. T.; Holland, B.; Byrne, M.; Gun'ko, Y. K.; et al. Nat. Nanotechnol. 2008, 3, 563. doi: 10.1038/nnano.2008.215

  13. [13]

      Huang, H.; Chen, W.; Chen, S.; Wee, A. T. S. ACS Nano 2008, 2, 2513. doi: 10.1021/nn800711v

  14. [14]

      Berger, C.; Song, Z.; Li, X.; Wu, X.; Brown, N.; Naud, C.; Mayou, D.; Li, T.; Hass, J.; Marchenkov, A. N.; et al. Science 2006, 312, 1191. doi: 10.1126/science.1125925

  15. [15]

      Li, X.; Cai, W.; An, J.; Kim, S.; Nah, J.; Yang, D.; Piner, R.; Velamakanni, A.; Jung, I.; Tutuc, E.; et al. Science 2009, 324, 1312. doi: 10.1126/science.1171245

  16. [16]

      Kim, K. S.; Zhao, Y.; Jang, H.; Lee, S. Y.; Kim, J. M.; Kim, K. S.; Ahn, J. -H.; Kim, P.; Choi, J. -Y.; Hong, B. H. Nature 2009, 457, 706. doi: 10.1038/nature07719

  17. [17]

      Lin, L.; Peng, H.; Liu, Z. F. Nat. Mater. 2019, 18, 520. doi: 10.1038/s41563-019-0341-4

  18. [18]

      Kong, W.; Kum, H.; Bae, S. -H.; Shim, J.; Kim, H.; Kong, L.; Meng, Y.; Wang, K.; Kim, C.; Kim, J. Nat. Nanotechnol. 2019, 14, 927. doi: 10.1038/s41565-019-0555-2

  19. [19]

      Pulizzi, F.; Bubnova, O.; Milana, S.; Schilter, D.; Abergel, D.; Moscatelli, A. Nat. Nanotechnol. 2019, 14, 914. doi: 10.1038/s41565-019-0552-5

  20. [20]

      Kim, H.; Song, I.; Park, C.; Son, M.; Hong, M.; Kim, Y.; Kim, J. S.; Shin, H. -J.; Baik, J.; Choi, H. C. ACS Nano 2013, 7, 6575. doi: 10.1021/nn402847w

  21. [21]

      Huang, P.; Ruiz-Vargas, C.; Zande, A.; Whitney, W.; Levendorf, M.; Kevek, J.; Garg, S.; Alden, J.; Hustedt, C.; Zhu, Y.; et al. Nature 2011, 469, 389. doi: 10.1038/nature09718

  22. [22]

      Yu, Q.; Jauregui, L.; Wu, W.; Colby, R.; Tian, J.; Su, Z.; Cao, H.; Liu, Z.; Pandey, D.; Wei, D.; et al. Nat. Mater. 2011, 10, 443. doi: 10.1038/nmat3010

  23. [23]

      Ni, G. -X.; Zheng, Y.; Bae, S.; Kim, H. R.; Pachoud, A.; Kim, Y. S.; Tan, C. -L.; Im, D.; Ahn, J. -H.; Hong, B. H.; et al. ACS Nano 2012, 6, 1158. doi: 10.1021/nn203775x

  24. [24]

      Deng, B.; Hou, Y.; Liu, Y.; Khodkov, T.; Goossens, S.; Tang, J.; Wang, Y.; Yan, R.; Du, Y.; Koppens, F. H.; et al. Nano Lett. 2020, 20, 6798. doi: 10.1021/acs.nanolett.0c02785

  25. [25]

      Lin, L.; Deng, B.; Sun, J. Y.; Peng, H. L.; Liu, Z. F. Chem. Rev. 2018, 118, 9281. doi: 10.1021/acs.chemrev.8b00325

  26. [26]

      Zhang, J.; Sun, L.; Jia, K.; Liu, X.; Cheng, T.; Peng, H.; Lin, L.; Liu, Z. F. ACS Nano 2020, 14, 10796. doi: 10.1021/acsnano.0c06141

  27. [27]

      Fang, W.; Hsu, A. L.; Song, Y.; Kong, J. Nanoscale 2015, 7, 20335. doi: 10.1039/c5nr04756k

  28. [28]

      Huang, M.; Bakharev, P. V.; Wang, Z. -J.; Biswal, M.; Yang, Z.; Jin, S.; Wang, B.; Park, H. J.; Li, Y.; Qu, D.; et al. Nat. Nanotechnol. 2020, 15, 289. doi: 10.1038/s41565-019-0622-8

  29. [29]

      Xue, Y.; Wu, B.; Jiang, L.; Guo, Y.; Huang, L.; Chen, J.; Tan, J.; Geng, D.; Luo, B.; Hu, W.; et al. J. Am. Chem. Soc. 2012, 134, 11060. doi: 10.1021/ja302483t

  30. [30]

      Lin, L.; Li, J.; Yuan, Q.; Li, Q.; Zhang, J.; Sun, L.; Rui, D.; Chen, Z.; Jia, K.; Wang, M.; et al. Sci. Adv. 2019, 5, eaaw8337. doi: 10.1126/sciadv.aaw8337

  31. [31]

      Vlassiouk, I. V.; Stehle, Y.; Pudasaini, P. R.; Unocic, R. R.; Rack, P. D.; Baddorf, A. P.; Ivanov, I. N.; Lavrik, N. V.; List, F.; Gupta, N.; et al. Nat. Mater. 2018, 17, 318. doi: 10.1038/s41563-018-0019-3

  32. [32]

      Xu, X.; Zhang, Z.; Dong, J.; Yi, D.; Niu, J.; Wu, M.; Lin, L.; Yin, R.; Li, M.; Zhou, J.; et al. Sci. Bull. 2017, 62, 1074. doi: 10.1016/j.scib.2017.07.005

  33. [33]

      Hao, Y.; Bharathi, M. S.; Wang, L.; Liu, Y.; Chen, H.; Nie, S.; Wang, X.; Chou, H.; Tan, C.; Fallahazad, B.; et al. Science 2013, 342, 720. doi: 10.1126/science.1243879

  34. [34]

      Zhou, H.; Yu, W. J.; Liu, L.; Cheng, R.; Chen, Y.; Huang, X.; Liu, Y.; Wang, Y.; Huang, Y.; Duan, X. Nat. Commun. 2013, 4, 2096. doi: 10.1038/ncomms3096

  35. [35]

      姜蓓, 孙靖宇, 刘忠范. 物理化学学报, 2021, 37, 2007068. doi: 10.3866/PKU.WHXB202007068Jiang, B.; Sun, J.; Liu, Z. F. Acta Phys. -Chim. Sin. 2021, 37, 2007068. doi: 10.3866/PKU.WHXB202007068

  36. [36]

      Deng, B.; Pang, Z.; Chen, S.; Li, X.; Meng, C.; Li, J.; Liu, M.; Wu, J.; Qi, Y.; Dang, W.; et al. ACS Nano 2017, 11, 12337. doi: 10.1021/acsnano.7b06196

  37. [37]

      Li, B. -W.; Luo, D.; Zhu, L.; Zhang, X.; Jin, S.; Huang, M.; Ding, F.; Ruoff, R. S. Adv. Mater. 2018, 30, 1706504. doi: 10.1002/adma.201706504

  38. [38]

      Yuan, G.; Lin, D.; Wang, Y.; Huang, X.; Chen, W.; Xie, X.; Zong, J.; Yuan, Q. -Q.; Zheng, H.; Wang, D.; et al. Nature 2020, 577, 204. doi: 10.1038/s41586-019-1870-3

  39. [39]

      Jia, Y.; Gong, X.; Peng, P.; Wang, Z.; Tian, Z.; Ren, L.; Fu, Y.; Zhang, H. Nano-Micro Lett. 2016, 8, 336. doi: 10.1007/s40820-016-0093-5

  40. [40]

      Zhang, Z.; Du, J.; Zhang, D.; Sun, H.; Yin, L.; Ma, L.; Chen, J.; Ma, D.; Cheng, H. -M.; Ren, W. Nat. Commun. 2017, 8, 14560. doi: 10.1038/ncomms14560

  41. [41]

      Pettes, M. T.; Jo, I.; Yao, Z.; Shi, L. Nano Lett. 2011, 11, 1195. doi: 10.1021/nl104156y

  42. [42]

      Matković, A.; Ralević, U.; Chhikara, M.; Jakovljević, M. M.; Jovanović, D.; Bratina, G.; Gajić, R. J. Appl. Phys. 2013, 114, 093505. doi: 10.1063/1.4819967

  43. [43]

      Li, Z.; Wang, Y.; Kozbial, A.; Shenoy, G.; Zhou, F.; McGinley, R.; Ireland, P.; Morganstein, B.; Kunkel, A.; Surwade, S. P.; et al. Nat. Mater. 2013, 12, 925. doi: 10.1038/nmat3709

  44. [44]

      Kim, Y.; Cruz, S. S.; Lee, K.; Alawode, B. O.; Choi, C.; Song, Y.; Johnson, J. M.; Heidelberger, C.; Kong, W.; Choi, S.; et al. Nature 2017, 544, 340. doi: 10.1038/nature22053

  45. [45]

      Zheng, L.; Chen, Y.; Li, N.; Zhang, J.; Liu, N.; Liu, J.; Dang, W.; Deng, B.; Li, Y.; Gao, X.; et al. Nat. Commun. 2020, 11, 541. doi: 10.1038/s41467-020-14359-0

  46. [46]

      Han, Y.; Fan, X.; Wang, H.; Zhao, F.; Tully, C. G.; Kong, J.; Yao, N.; Yan, N. Proc. Natl. Acad. Sci. U. S. A. 2020, 117, 1009. doi: 10.1073/pnas.1919114117

  47. [47]

      Hong, H.; Zhang, J.; Zhang, J.; Qiao, R.; Yao, F.; Cheng, Y.; Wu, C.; Lin, L.; Jia, K.; Zhao, Y.; et al. J. Am. Chem. Soc. 2018, 140, 14952. doi: 10.1021/jacs.8b09353

  48. [48]

      Lin, Y. -C.; Lu, C. -C.; Yeh, C. -H.; Jin, C.; Suenaga, K.; Chiu, P. -W. Nano Lett. 2012, 12, 414. doi: 10.1021/nl203733r

  49. [49]

      Leong, W. S.; Wang, H.; Yeo, J.; Martin-Martinez, F. J.; Zubair, A.; Shen, P. -C.; Mao, Y.; Palacios, T.; Buehler, M. J.; Hong, J. -Y.; et al. Nat. Commun. 2019, 10, 867. doi: 10.1038/s41467-019-08813-x

  50. [50]

      Lin, Y. -C.; Jin, C.; Lee, J. -C.; Jen, S. -F.; Suenaga, K.; Chiu, P. -W. ACS Nano 2011, 5, 2362. doi: 10.1021/nn200105j

  51. [51]

      Wang, X.; Dolocan, A.; Chou, H.; Tao, L.; Dick, A.; Akinwande, D.; Wilison, C. G. Chem. Mat. 2017, 29, 2033. doi: 10.1021/acs.chemmater.6b03875

  52. [52]

      Li, W.; Liang, Y.; Yu, D.; Peng, L.; Pernstich, K. P.; Shen, T.; Walker, A. R. H.; Cheng, G.; Hacker, C. A.; Richter, C. A.; et al. Appl. Phys. Lett. 2013, 102, 183110. doi: 10.1063/1.4804643

  53. [53]

      Moser, J.; Barreiro, A.; Bachtold, A. Appl. Phys. Lett. 2007, 91, 163513. doi: 10.1063/1.2789673

  54. [54]

      成会明. 物理化学学报, 2020, 36, 1909042. doi: 10.3866/PKU.WHXB201909042Cheng, H. Acta Phys. -Chim. Sin. 2020, 36, 1909042. doi: 10.3866/PKU.WHXB201909042

  55. [55]

      Schuenemann, C.; Schaeffel, F.; Bachmatiuk, A.; Queitsch, U.; Sparing, M.; Rellinghaus, B.; Lafdi, K.; Schultz, L.; Buechner, B.; Ruemmeli, M. H. ACS Nano 2011, 5, 8928. doi: 10.1021/nn2031066

  56. [56]

      Lin, L.; Zhang, J.; Su, H.; Li, J.; Sun, L.; Wang, Z.; Xu, F.; Liu, C.; Lopatin, S.; Zhu, Y.; et al. Nat. Commun. 2019, 10, 1912. doi: 10.1038/s41467-019-09565-4

  57. [57]

      Zhang, J.; Lin, L.; Sun, L.; Huang, Y.; Koh, A. L.; Dang, W.; Yin, J.; Wang, M.; Tan, C.; Li, T.; et al. Adv. Mater. 2017, 29, 1700639. doi: 10.1002/adma.201700639

  58. [58]

      Zhang, J.; Jia, K.; Lin, L.; Zhao, W.; Quang, H. T.; Sun, L.; Li, T.; Li, Z.; Liu, X.; Zheng, L.; et al. Angew. Chem. Int. Ed. 2019, 58, 14446. doi: 10.1002/anie.201905672

  59. [59]

      Su, W.; Kumar, N.; Dai, N.; Roy, D. Chem. Commun. 2016, 52, 8227. doi: 10.1039/C6CC01990K

  60. [60]

      Li, X.; Cai, W.; Colombo, L.; Ruoff, R. S. Nano Lett. 2009, 9, 4268. doi: 10.1021/nl902515k

  61. [61]

      Zhang, X.; Li, H.; Ding, F. Adv. Mater. 2014, 26, 5488. doi: 10.1002/adma.201305922

  62. [62]

      Gao, J.; Yuan, Q.; Hu, H.; Zhao, J.; Ding, F. J. Phys. Chem. C 2011, 115, 17695. doi: 10.1021/jp2051454

  63. [63]

      Zhong, L.; Li, J.; Li, Y.; Lu, H.; Du, H.; Gan, L.; Xu, C.; Chiang, S. W.; Kang, F. J. Phys. Chem. C 2016, 120, 23239. doi: 10.1021/acs.jpcc.6b06750

  64. [64]

      Zhang, W.; Wu, P.; Li, Z.; Yang, J. J. Phys. Chem. C 2011, 115, 17782. doi: 10.1021/jp2006827

  65. [65]

      Li, Z.; Zhang, W.; Fan, X.; Wu, P.; Zeng, C.; Li, Z.; Zhai, X.; Yang, J.; Hou, J. J. Phys. Chem. C 2012, 116, 10557. doi: 10.1021/jp210814j

  66. [66]

      Kim, H.; Mattevi, C.; Calvo, M. R.; Oberg, J. C.; Artiglia, L.; Agnoli, S.; Hirjibehedin, C. F.; Chhowalla, M.; Saiz, E. ACS Nano 2012, 6, 3614. doi: 10.1021/nn3008965

  67. [67]

      Muñoz, R.; Gómez-Aleixandre, C. Chem. Vapor Depos. 2013, 19, 297. doi: 10.1002/cvde.201300051

  68. [68]

      Qing, F.; Jia, R.; Li, B. -W.; Liu, C.; Li, C.; Peng, B.; Deng, L.; Zhang, W.; Li, Y.; Ruoff, R. S.; et al. 2D Mater. 2017, 4, 025089. doi: 10.1088/2053-1583/aa6da5

  69. [69]

      Hu, C.; Li, H.; Zhang, S.; Li, W. J. Mater. Sci. 2016, 51, 3897. doi: 10.1007/s10853-015-9709-2

  70. [70]

      Qiu, Z.; Li, P.; Li, Z.; Yang, J. Acc. Chem. Res. 2018, 51, 728. doi: 10.1021/acs.accounts.7b00592

  71. [71]

      Shivayogimath, A.; Mackenzie, D.; Luo, B.; Hansen, O.; Bøggild, P.; Booth, T. J. Sci. Rep. 2017, 7, 6183. doi: 10.1038/s41598-017-06276-y

  72. [72]

      Lewis, A. M.; Derby, B.; Kinloch, I. A. ACS Nano 2013, 7, 3104. doi: 10.1021/nn305223y

  73. [73]

      Wang, X.; Yuan, Q.; Li, J.; Ding, F. Nanoscale 2017, 9, 11584. doi: 10.1039/c7nr02743e

  74. [74]

      Seah, C. -M.; Chai, S. -P.; Mohamed, A. R. Carbon 2014, 70, 1. doi: 10.1016/j.carbon.2013.12.073

  75. [75]

      Sun, J.; Gao, T.; Song, X.; Zhao, Y.; Lin, Y.; Wang, H.; Ma, D.; Chen, Y.; Xiang, W.; Wing, J.; et al. J. Am. Chem. Soc. 2014, 136, 6574. doi: 10.1021/ja5022602

  76. [76]

      Zheng, S.; Zhong, G.; Wu, X.; D'Arsie, L.; Robertson, J. RSC Adv. 2017, 7, 33185. doi: 10.1039/c7ra04162d

  77. [77]

      Teng, P. -Y.; Lu, C. -C.; Akiyama-Hasegawa, K.; Lin, Y. -C.; Yeh, C. -H.; Suenaga, K.; Chiu, P. -W. Nano Lett. 2012, 12, 1379. doi: 10.1021/nl204024k

  78. [78]

      Jia, K.; Zhang, J.; Lin, L.; Li, Z.; Gao, J.; Sun, L.; Xue, R.; Li, J.; Kang, N.; Luo, Z.; et al. J. Am. Chem. Soc. 2019, 58, 14446. doi: 10.1002/anie.201905672

  79. [79]

      Jia, K.; Ci, H.; Zhang, J.; Sun, Z.; Ma, Z.; Zhu, Y.; Liu, S.; Liu, J.; Sun, L.; Liu, X.; et al. Angew. Chem. Int. Ed. 2020, 59, 17214. doi: 10.1002/anie.202005406

  80. [80]

      Sun, L.; Lin, L.; Wang, Z.; Rui, D.; Yu, Z.; Zhang, J.; Li, Y.; Liu, X.; Jia, K.; Wang, K.; et al. Adv. Mater. 2019, 31, 1902978. doi: 10.1002/adma.201902978

  81. [81]

      Cai, W.; Moore, A. L.; Zhu, Y.; Li, X.; Chen, S.; Shi, L.; Ruoff, R. S. Nano Lett. 2010, 10, 1645. doi: 10.1021/nl9041966

•