English

Crack-Free Transfer of Graphene Wafers via Photoresist as Transfer Medium

• Junhao Liao ^{1, 2, 3, 4,} ,
• Yixuan Zhao ^{1, 3,} ,
• Zhaoning Hu ^{3, 5,} ,
• Saiyu Bu ^5, ,
• Qi Lu ^{3, 6,} ,
• Mingpeng Shang ^{1, 2, 3,} ,
• Kaicheng Jia ^3, ,
• Xiaohui Qiu ^{4, ,} ,
• Qin Xie ^{1, 2, 3, ,} ,
• Li Lin ^{1, 2, 3, 5, ,} ,
• Zhongfan Liu ^{1, 2, 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

• 4.

  National Center for Nanoscience and Technology, Beijing 100190, China

• 5.

  School of Materials Science and Engineering, Peking University, Beijing 100871, China

• 6.

  College of Science, China University of Petroleum, Beijing 102249, China

Corresponding author: Email: xhqiu@nanoctr.cn (X.Q.); Email: xieqin-cnc@pku.edu.cn (Q.X.); Email: linli-cnc@pku.edu.cn (L.L.); Email: zfliu@pku.edu.cn (Z.L.)

• Received Date: 26 June 2023
  Accepted Date: 24 July 2023
  Revised Date: 19 July 2023
  Available Online: 15 October 2023
• Fund Project:

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  Beijing Municipal Science & Technology Commission 

  Beijing Municipal Science & Technology Commission 

  Beijing Municipal Science & Technology Commission 

  Beijing Municipal Science & Technology Commission 

  National Basic Research Program of China 

  National Basic Research Program of China 

  National Basic Research Program of China 

  Beijing National Laboratory for Molecular Sciences 

Abstract: Graphene offers exceptional properties, such as ultra-high carrier mobility, near-ballistic transport characteristics, and ultra-high-frequency operational response, making it an ideal material for radio-frequency devices and high-speed optical communications. To realize its potential applications, high-quality graphene films must be integrated onto target substrates with reliability, uniformity, and scalability. Despite significant progress in the chemical vapor deposition of high-quality graphene on catalytic metal substrates, the transfer of such films onto application-targeted substrates remains necessary for large-scale technological use, but it faces challenges like contaminations and cracks. Graphene's flexibility and single-atom thickness make it vulnerable to damage and folding during the transfer process due to force disturbances and uneven force distribution. Traditional graphene transfer methods employ organic polymers as a medium and remove them using organic solvents after transferring graphene onto the desired substrates. However, this repetitive process generates organic waste and leaves unavoidable contamination due to the limited solubility of the polymer. Furthermore, selective interlacing of organic solvents during polymer removal can detach graphene from the substrate and cause cracks. In this study, we demonstrate a novel approach to address these issues. Instead of using organic polymers, we directly use the photoresist as the transfer medium to mechanically delaminate graphene from the metal growth substrate onto the targeted substrate. By doing so, we eliminate the need for repeated polymer coating on the graphene surface, enabling successful transfer without crack formation, wrinkles, or unintentional doping. The strong interaction between graphene and the photoresist, coupled with the weakened interaction between graphene and the growth substrate due to oxidation, ensures crack-free delamination. Moreover, the photoresist serves as a patterned mask plate for exposure, etching, and other subsequent device fabrication processes. As a result, the electrical properties of graphene are improved, achieving an average carrier mobility of 6200 cm²·V⁻¹·s⁻¹. This integrated approach not only enhances the device performance of two-dimensional materials but also paves the way for future applications of such materials in electronics and photonics. In conclusion, our method offers a promising solution for the successful transfer and device fabrication of graphene, enhancing its potential in the field of electronics and photonics.

Key words:
• Graphene transfer
•  /  Photoresist
•  /  Transfer medium
•  /  Carrier mobility

• 1. [1]

     Lange, K.; Muller-Seitz, G.; Sydow, J.; Windeler, A. Res. Policy 2013, 42 (3), 647. doi: 10.1016/j.respol.2012.12.001

  2. [2]

     Yeh, L. Y.; Liao, M. H.; Chen, C. H.; Wu, J.; Lee, J. Y. M.; Liu, C. W.; Lee, T. L.; Liang, M. S. IEEE Trans. Electron Devices 2009, 56 (11), 2848. doi: 10.1109/ted.2009.2030542

  3. [3]

     Welser, J.; Hoyt, J. L.; Gibbons, J. F. IEEE Electron. Device. Lett. 1994, 15 (3), 100. doi: 10.1109/55.285389

  4. [4]

     Radisavljevic, B.; Kis, A. Nat. Mater. 2013, 12 (9), 815. doi: 10.1038/nmat3687

  5. [5]

     Dennard, R. H.; Gaensslen, F. H.; Yu, H. N.; Rideout, V. L.; Bassous, E.; Leblanc, A. R. Proc. IEEE 1999, 87 (4), 668. doi: 10.1109/jproc.1999.752522

  6. [6]

     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 (5696), 666. doi: 10.1126/science.1102896

  7. [7]

     Kretinin, A. V.; Cao, Y.; Tu, J. S.; Yu, G. L.; Jalil, R.; Novoselov, K. S.; Haigh, S. J.; Gholinia, A.; Mishchenko, A.; Lozada, M.; et al. Nano Lett. 2014, 14 (6), 3270. doi: 10.1021/nl5006542

  8. [8]

     Castro Neto, A. H.; Guinea, F.; Peres, N. M. R.; Novoselov, K. S.; Geim, A. K. Rev. Mod. Phys. 2009, 81 (1), 109. doi: 10.1103/revmodphys.81.109

  9. [9]

     Cao, Y.; Fatemi, V.; Fang, S.; Watanabe, K.; Taniguchi, T.; Kaxiras, E.; Jarillo-Herrero, P. Nature 2018, 556 (7699), 43. doi: 10.1038/nature26160

  10. [10]

      Giambra, M. A.; Miseikus, V.; Pezzini, S.; Marconi, S.; Montanaro, A.; Fabbri, F.; Sorianello, V.; Ferrari, A. C.; Coletti, C.; Romagnoli, M. ACS Nano 2021, 15 (2), 3171. doi: 10.1021/acsnano.0c09758

  11. [11]

      Goossens, S.; Navickaite, G.; Monasterio, C.; Gupta, S.; Piqueras, J. J.; Perez, R.; Burwell, G.; Nikitskiy, I.; Lasanta, T.; Galan, T.; et al. Nat. Photonics 2017, 11 (6), 366. doi: 10.1038/nphoton.2017.75

  12. [12]

      Marconi, S.; Giambra, M. A.; Montanaro, A.; Miseikis, V.; Soresi, S.; Tirelli, S.; Galli, P.; Buchali, F.; Templ, W.; Coletti, C.; et al. Nat. Commun. 2021, 12 (1), 806. doi: 10.1038/s41467-021-21137-z

  13. [13]

      Liu, C. H.; Chang, Y. C.; Norris, T. B.; Zhong, Z. H. Nat. Nanotechnol. 2014, 9 (4), 273. doi: 10.1038/nnano.2014.31

  14. [14]

      Tian, H.; Yang, Y.; Xie, D.; Cui, Y. L.; Mi, W. T.; Zhang, Y. G.; Ren, T. L. Sci. Rep. 2014, 4, 3598. doi: 10.1038/srep03598

  15. [15]

      Wang, M.; Huang, M.; Luo, D.; Li, Y.; Choe, M.; Seong, W. K.; Kim, M.; Jin, S.; Wang, M.; Chatterjee, S.; et al. Nature 2021, 596 (7873), 519. doi: 10.1038/s41586-021-03753-3

  16. [16]

      Yuan, G. W.; Lin, D. J.; Wang, Y.; Huang, X. L.; Chen, W.; Xie, X. D.; Zong, J. Y.; Yuan, Q. Q.; Zheng, H.; Wang, D.; et al. Nature 2020, 577 (7789), 204. doi: 10.1038/s41586-019-1870-3

  17. [17]

      Chen, T. A.; Chuu, C. P.; Tseng, C. C.; Wen, C. K.; Wong, H. S. P.; Pan, S. Y.; Li, R. T.; Chao, T. A.; Chueh, W. C.; Zhang, Y. F.; et al. Nature 2020, 579 (7798), 219. doi: 10.1038/s41586-020-2009-2

  18. [18]

      Li, Y. L. Z.; Sun, L. Z.; Chang, Z. H.; Liu, H. Y.; Wang, Y. C.; Liang, Y.; Chen, B. H.; Ding, Q. J.; Zhao, Z. Y.; Wang, R. Y.; et al. Adv. Mater. 2020, 32 (29), 2002034. doi: 10.1002/adma.202002034

  19. [19]

      Zhang, J. C.; Lin, L.; Jia, K. C.; Sun, L. Z.; Peng, H. L.; Liu, Z. F. Adv. Mater. 2020, 32 (1), 1903266. doi: 10.1002/adma.201903266

  20. [20]

      Liu, L.; Li, T. T.; Ma, L.; Li, W. S.; Gao, S.; Sun, W. J.; Dong, R. K.; Zou, X. L.; Fan, D. X.; Shao, L. W.; et al. Nature 2022, 605 (7908), 69. doi: 10.1038/s41586-022-04523-5

  21. [21]

      Liu, X. T.; Zhang, J. C.; Wang, W. D.; Zhao, W.; Chen, H.; Liu, B. Y.; Zhang, M. Q.; Liang, F. S.; Zhang, L. J.; Zhang, R.; et al. Nano Res. 2022, 15 (4), 3775. doi: 10.1007/s12274-021-3922-x

  22. [22]

      Ci, H. N.; Chen, J. T.; Ma, H.; Sun, X. L.; Jiang, X. Y.; Liu, K. C.; Shan, J. Y.; Lian, X. Y.; Jiang, B.; Liu, R. J.; et al. Adv. Mater. 2022, 34 (51), 2206389. doi: 10.1002/adma.202206389

  23. [23]

      Akinwande, D.; Huyghebaert, C.; Wang, C. H.; Serna, M. I.; Goossens, S.; Li, L. J.; Wong, H. S. P.; Koppens, F. H. L. Nature 2019, 573 (7775), 507. doi: 10.1038/s41586-019-1573-9

  24. [24]

      Gao, L. B.; Ni, G. X.; Liu, Y. P.; Liu, B.; Neto, A. H. C.; Loh, K. P. Nature 2014, 505 (7482), 190. doi: 10.1038/nature12763

  25. [25]

      Kim, J.; Park, H.; Hannon, J. B.; Bedell, S. W.; Fogel, K.; Sadana, D. K.; Dimitrakopoulos, C. Science 2013, 342 (6160), 833. doi: 10.1126/science.1242988

  26. [26]

      Qing, F. Z.; Zhang, Y. F.; Niu, Y. T.; Stehle, R.; Chen, Y. F.; Li, X. S. Nanoscale 2020, 12 (20), 10890. doi: 10.1039/d0nr01198c

  27. [27]

      Leong, W. S.; Wang, H. Z.; Yeo, J. J.; Martin-Martinez, F. J.; Zubair, A.; Shen, P. C.; Mao, Y. W.; Palacios, T.; Buehler, M. J.; Hong, J. Y.; et al. Nat. Commun. 2019, 10 (1), 867. doi: 10.1038/s41467-019-08813-x

  28. [28]

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

  29. [29]

      Zhao, Y. X.; Song, Y. Q.; Hu, Z. N.; Wang, W. D.; Chang, Z. H.; Zhang, Y.; Lu, Q.; Wu, H. T.; Liao, J. H.; Zou, W. T.; et al. Nat. Commun. 2022, 13 (1), 4409. doi: 10.1038/s41467-022-31887-z

  30. [30]

      Hu, Z. N.; Li, F. F.; Wu, H. T.; Liao, J. H.; Wang, Q.; Chen, G.; Shi, Z. F.; Zhu, Y. Q.; Bu, S. Y.; Zhao, Y. X.; et al. Adv. Mater. 2023, 35 (29), 2300621. doi: 10.1002/adma.202300621

  31. [31]

      De Fazio, D.; Purdie, D. G.; Ott, A. K.; Braeuninger-Weimer, P.; Khodkov, T.; Goossens, S.; Taniguchi, T.; Watanabe, K.; Livreri, P.; Koppens, F. H. L.; et al. ACS Nano 2019, 13 (8), 8926. doi: 10.1021/acsnano.9b02621

  32. [32]

      Matsumae, T.; Fujino, M.; Suga, T. ECS J. Solid State Sci. Technol. 2017, 6 (8), 512. doi: 10.1149/2.0111708jss

  33. [33]

      Song, Y. Q.; Gao, Y. Q.; Liu, X. T.; Ma, J.; Chen, B. H.; Xie, Q.; Gao, X.; Zheng, L. M.; Zhang, Y.; Ding, Q. J.; et al. Adv. Mater. 2022, 34 (1), 2105851. doi: 10.1002/adma.202105851

  34. [34]

      Lin, Y. C.; Lu, C. C.; Yeh, C. H.; Jin, C. H.; Suenaga, K.; Chiu, P. W. Nano Lett. 2012, 12 (1), 414. doi: 10.1021/nl203733r

  35. [35]

      Matsumae, T.; Koehler, A. D.; Greenlee, J. D.; Anderson, T. J.; Baumgart, H.; Jernigan, G. G.; Hobart, K. D.; Kub, F. J. ECS J. Solid State Sci. Technol. 2015, 4 (7), 190. doi: 10.1149/2.0031507jss

  36. [36]

      Lui, C. H.; Liu, L.; Mak, K. F.; Flynn, G. W.; Heinz, T. F. Nature 2009, 462 (7271), 339. doi: 10.1038/nature08569

  37. [37]

      Hu, Z. N.; Zhao, Y. X.; Zou, W. T.; Lu, Q.; Liao, J. H.; Li, F. F.; Shang, M. P.; Lin, L.; Liu, Z. F. Adv. Funct. Mater. 2022, 32 (42), 2203179. doi: 10.1002/adfm.202203179

  38. [38]

      Chang, Z.; Yang, R.; Wei, Y. J. Mech. Phys. Solids 2019, 132, 103697. doi: 10.1016/j.jmps.2019.103697

  39. [39]

      Lee, J. E.; Ahn, G.; Shim, J.; Lee, Y. S.; Ryu, S. Nat. Commun. 2012, 3, 1024. doi: 10.1038/ncomms2022

  40. [40]

      Petrone, N.; Dean, C. R.; Meric, I.; Van der Zande, A. M.; Huang, P. Y.; Wang, L.; Muller, D.; Shepard, K. L.; Hone, J. Nano Lett. 2012, 12 (6), 2751. doi: 10.1021/nl204481s

  41. [41]

      Banszerus, L.; Schmitz, M.; Engels, S.; Dauber, J.; Oellers, M.; Haupt, F.; Watanabe, K.; Taniguchi, T.; Beschoten, B.; Stampfer, C. Sci. Adv. 2015, 1 (6), 1500222. doi: 10.1126/sciadv.1500222

  42. [42]

      Pezzini, S.; Miseikis, V.; Pace, S.; Rossella, F.; Watanabe, K.; Taniguchi, T.; Coletti, C. 2D Mater. 2020, 7 (4), 041003. doi: 10.1088/2053-1583/aba645

  43. [43]

      Wang, L.; Meric, I.; Huang, P. Y.; Gao, Q.; Gao, Y.; Tran, H.; Taniguchi, T.; Watanabe, K.; Campos, L. M.; Muller, D. A.; et al. Science 2013, 342 (6158), 614. doi: 10.1126/science.1244358

  44. [44]

      Du, X.; Skachko, I.; Barker, A.; Andrei, E. Y. Nat. Nanotechnol. 2008, 3 (8), 491. doi: 10.1038/nnano.2008.199

  45. [45]

      Ki, D. K.; Morpurgo, A. F. Nano Lett. 2013, 13 (11), 5165. doi: 10.1021/nl402462q

  46. [46]

      Lee, W. H.; Park, Y. D. Adv. Mater. Interfaces 2018, 5, 1700316. doi: 10.1002/admi.201700316

  47. [47]

      Lee, W. H.; Park, J.; Kim, Y.; Kim, K. S.; Hong, B. H.; Cho, K. Adv. Mater. 2011, 23 (30), 3460. doi: 10.1002/adma.201101340

  48. [48]

      Gammelgaard, L.; Caridad, J. M.; Cagliani, A.; Mackenzie, D. M. A.; Petersen, D. H.; Booth, T. J.; Boggild, P. 2D Mater. 2014, 1 (3), 035005. doi: 10.1088/2053-1583/1/3/035005

•