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Vapor-solid interfacial reaction and polymerization for wafer-scale uniform and ultrathin two-dimensional organic films

气固界面聚合反应制备晶圆级均匀超薄二维有机薄膜

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Abstract

Chemical vapor deposition is a conventional synthesis method for growing large-scale and high-quality two-dimensional materials, such as graphene, hexagonal boron nitride, and transition-metal dichalcogenides. For organic films, solution-based methods, such as inkjet printing, spin coating, and drop and micro-contact printing, are commonly used. Herein, we demonstrate a general method for growing wafer-scale continuous, uniform, and ultrathin (2–5 nm) organic films. This method is based on a copper (Cu) surface-mediated reaction and polymerization of several equivalent bromine (Br)-containing π-conjugated small molecules (C12S3Br6, C24H4O2Br2, and C24H12Br2N4), in which local surface-mediated polymerization and internal π-π interactions among organic molecules are responsible for the dimension and uniformity control of the thin films. Specifically, the growth rate and morphology of thin films were found to be Cu-facet-dependent, and single-crystal Cu(111) surfaces could improve the uniformity of thin films. In addition, the number of Br groups and size of organic molecules were critical for crystallinity and thin-film formation. This method can be used to fabricate heterostructures, such as organic film/graphene, giving room for various functional materials and device applications.

摘要

本文介绍了一种利用气固界面聚合反应制备大面积均匀超薄二 维有机分子薄膜的新进展. 通常有机分子薄膜的制备多借助于溶液法、 旋涂法等技术, 所制备的薄膜尺寸、 均匀性和厚度可控性较差. 传统的化学气相沉积法在大面积石墨烯、 氮化硼、 过渡金属硫族化合物等二维材料的制备方面应用广泛, 但在有机分子薄膜制备领域却鲜有报道. 本文中, 我们展示了一种基于化学气相沉积生长连续、 均匀、超薄(2–5 nm)的晶圆级多晶有机薄膜的一般方法. 该方法基于铜表面催化的一系列含溴π-共轭小分子的聚合, 其中局部表面聚合和有机分子内部π-π相互作用决定了薄膜的尺寸和均匀性, 研究表明薄膜的生长形貌和速度与铜晶面的类型密切相关, 基于此在Cu(111)表面获得了更为均匀的薄膜. 通过另外两种有机小分子薄膜的制备有效地证明了该方法的可拓展性. 该方法为基于难溶性有机小分子可控制备大面积原子厚度薄膜和相关异质结构, 如有机膜/石墨烯, 及其他功能材料和器件提供了新空间.

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References

  1. Tada H, Saiki K, Koma A. Structural analysis of lead phthalocyanine ultrathin films grown on cleaved faces of alkali halides by reflection high energy electron diffraction. Surf Sci, 1992, 268: 387–396

    Article  CAS  Google Scholar 

  2. Xi M, Bent BE. Mechanisms of the Ullmann coupling reaction in adsorbed monolayers. J Am Chem Soc, 1993, 115: 7426–7433

    Article  CAS  Google Scholar 

  3. Bao Z, Lovinger AJ, Dodabalapur A. Organic field-effect transistors with high mobility based on copper phthalocyanine. Appl Phys Lett, 1996, 69: 3066–3068

    Article  CAS  Google Scholar 

  4. Yanagi H, Morikawa T. Self-waveguided blue light emission in p-sexiphenyl crystals epitaxially grown by mask-shadowing vapor deposition. Appl Phys Lett, 1999, 75: 187–189

    Article  CAS  Google Scholar 

  5. Menard E, Podzorov V, Hur SH, et al. High-performance n- and p-type single-crystal organic transistors with free-space gate dielectrics. Adv Mater, 2004, 16: 2097–2101

    Article  CAS  Google Scholar 

  6. Blake MM, Nanayakkara SU, Claridge SA, et al. Identifying reactive intermediates in the Ullmann coupling reaction by scanning tunneling microscopy and spectroscopy. J Phys Chem A, 2009, 113: 13167–13172

    Article  CAS  Google Scholar 

  7. Sundar VC, Zaumseil J, Podzorov V, et al. Elastomeric transistor stamps: Reversible probing of charge transport in organic crystals. Science, 2004, 303: 1644–1646

    Article  CAS  Google Scholar 

  8. Lee HM, Moon H, Kim HS, et al. Abrupt heating-induced high-quality crystalline rubrene thin films for organic thin-film transistors. Org Electron, 2011, 12: 1446–1453

    Article  CAS  Google Scholar 

  9. Oyamada T, Uchiuzou H, Akiyama S, et al. Lateral organic light-emitting diode with field-effect transistor characteristics. J Appl Phys, 2005, 98: 074506

    Article  Google Scholar 

  10. Liu J, Jiang L, Hu W, et al. Monolayer organic field-effect transistors. Sci China Chem, 2019, 62: 313–330

    Article  CAS  Google Scholar 

  11. Xu X, Yao Y, Shan B, et al. Electron mobility exceeding 10 cm2 V−1 s−1 and band-like charge transport in solution-processed n-channel organic thin-film transistors. Adv Mater, 2016, 28: 5276–5283

    Article  CAS  Google Scholar 

  12. Zhang X, Mao J, Deng W, et al. Precise patterning of laterally stacked organic microbelt heterojunction arrays by surface-energy-controlled stepwise crystallization for ambipolar organic field-effect transistors. Adv Mater, 2018, 30: 1800187

    Article  Google Scholar 

  13. Lin Y, Huang Z, Wen X, et al. Steering effect of bromine on intermolecular dehydrogenation coupling of poly(p-phenylene) on Cu(111). ACS Nano, 2020, 14: 17134–17141

    Article  CAS  Google Scholar 

  14. Shu Z, Zhang Q, Zhang P, et al. Preparing two-dimensional crystalline conjugated polymer films by synergetic polymerization and self-assembly at air/water interface. Polym Chem, 2020, 11: 1572–1579

    Article  CAS  Google Scholar 

  15. Wang L, Zhang X, Dai G, et al. High-mobility air-stable n-type field-effect transistors based on large-area solution-processed organic single-crystal arrays. Nano Res, 2017, 11: 882–891

    Article  Google Scholar 

  16. Zhang Y, Jie J, Sun Y, et al. Precise patterning of organic single crystals via capillary-assisted alternating-electric field. Small, 2017, 13: 1604261

    Article  Google Scholar 

  17. Yang L, Wei DC. Semiconducting covalent organic frameworks: A type of two-dimensional conducting polymers. Chin Chem Lett, 2016, 27: 1395–1404

    Article  CAS  Google Scholar 

  18. Wang C, Fu B, Zhang X, et al. Solution-processed, large-area, two-dimensional crystals of organic semiconductors for field-effect transistors and phototransistors. ACS Cent Sci, 2020, 6: 636–652

    Article  CAS  Google Scholar 

  19. Jiang L, Niu T, Lu X, et al. Low-temperature, bottom-up synthesis of graphene via a radical-coupling reaction. J Am Chem Soc, 2013, 135: 9050–9054

    Article  CAS  Google Scholar 

  20. He D, Zhang Y, Wu Q, et al. Two-dimensional quasi-freestanding molecular crystals for high-performance organic field-effect transistors. Nat Commun, 2014, 5: 5162

    Article  CAS  Google Scholar 

  21. Evans AM, Parent LR, Flanders NC, et al. Seeded growth of single-crystal two-dimensional covalent organic frameworks. Science, 2018, 361: 52–57

    Article  CAS  Google Scholar 

  22. Liu K, Qi H, Dong R, et al. On-water surface synthesis of crystalline, few-layer two-dimensional polymers assisted by surfactant monolayers. Nat Chem, 2019, 11: 994–1000

    Article  CAS  Google Scholar 

  23. Zhong Y, Cheng B, Park C, et al. Wafer-scale synthesis of monolayer two-dimensional porphyrin polymers for hybrid superlattices. Science, 2019, 366: 1379–1384

    Article  CAS  Google Scholar 

  24. Toh CT, Zhang H, Lin J, et al. Synthesis and properties of free-standing monolayer amorphous carbon. Nature, 2020, 577: 199–203

    Article  CAS  Google Scholar 

  25. Yao J, Zhang Y, Tian X, et al. Layer-defining strategy to grow two-dimensional molecular crystals on a liquid surface down to the monolayer limit. Angew Chem Int Ed, 2019, 58: 16082–16086

    Article  CAS  Google Scholar 

  26. Feng G, Jiang J, Zhao Y, et al. A sub-10 nm vertical organic/inorganic hybrid transistor for pain-perceptual and sensitization-regulated nociceptor emulation. Adv Mater, 2020, 32: 1906171

    Article  CAS  Google Scholar 

  27. Liu X, Luo X, Nan H, et al. Epitaxial ultrathin organic crystals on graphene for high-efficiency phototransistors. Adv Mater, 2016, 28: 5200–5205

    Article  CAS  Google Scholar 

  28. Han J, Wang J, Yang M, et al. Graphene/organic semiconductor heterojunction phototransistors with broadband and bi-directional photoresponse. Adv Mater, 2018, 30: 1804020

    Article  Google Scholar 

  29. Yao W, Sun J, Chen J, et al. Controllable preparation and photoelectric applications of two-dimensional in-plane and van der Waals heterostructures. Acta Phys Sin, 2021, 70: 027901

    Article  Google Scholar 

  30. Wang M, Kim M, Odkhuu D, et al. Catalytic transparency of hexagonal boron nitride on copper for chemical vapor deposition growth of large-area and high-quality graphene. ACS Nano, 2014, 8: 5478–5483

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Basic Research Program of China (2016YFA0200101), the National Natural Science Foundation of China (21633012 and 61890940), the Strategic Priority Research Program of the Chinese Academy of Sciences (CAS) (XDB30000000), and the CAS Key Research Program of Frontier Sciences (QYZDY-SSW-SLH029).

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Wenqian Yao  (姚文乾), He Yang  (杨贺), Qingsong Zhang  (张卿菘), Longxian Shi  (施龙献), Jianzhe Sun  (孙健哲), Yunlong Guo  (郭云龙), Lang Jiang  (江浪), Bin Wu  (武斌) & Yunqi Liu  (刘云圻)

  2. Sino-Danish Center for Education and Research, Sino-Danish College, University of Chinese Academy of Sciences, Beijing, 100049, China

    Wenqian Yao  (姚文乾), Longxian Shi  (施龙献) & Yunqi Liu  (刘云圻)

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  1. Wenqian Yao  (姚文乾)
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  2. He Yang  (杨贺)
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  7. Lang Jiang  (江浪)
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  8. Bin Wu  (武斌)
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Contributions

Author contributions Liu Y supervised the project. Liu Y and Wu B designed the experiments and research; Yao W and Yang H performed the experiments; Zhang Q and Shi L provided molecules. Wu B and Yao W wrote the paper. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Bin Wu  (武斌) or Yunqi Liu  (刘云圻).

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Conflict of interest The authors declare that they have no conflict of interest.

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

Wenqian Yao received double BSc degrees from Qingdao University of Science and Technology in polymer materials and economics. In 2017, he became a graduate and doctoral student of Sino-Danish College, University of Chinese Academy of Sciences, under the direction of Prof. Yunqi Liu and Prof. Bin Wu. He received his master’s degree from the University of Copenhagen in 2020. His research interest includes the preparation of 2D materials and their optical and electrical applications.

Bin Wu received his BSc degree in 1994 from Inner Mongolia University, China, and PhD degree in physical chemistry from Peking University in 2002. He joined the Institute of Chemistry, Chinese Academy of Sciences (ICCAS), as an associate professor in 2008 after conducting his postdoctoral research for several years. Currently, he is a professor at ICCAS. His research interest includes the controlled growth of 2D materials and their electronic applications.

Yunqi Liu is a professor at ICCAS. He graduated from Nanjing University in 1975 and received a doctorate degree from Tokyo Institute of Technology, Japan, in 1991. He was selected as an Academician of CAS in 2015 and a member of the Third World Academy of Sciences in 2018. His research interest includes molecular materials and devices, the synthesis and applications of carbon nano-materials, and organic electronics.

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Yao, W., Yang, H., Zhang, Q. et al. Vapor-solid interfacial reaction and polymerization for wafer-scale uniform and ultrathin two-dimensional organic films. Sci. China Mater. 65, 1577–1585 (2022). https://doi.org/10.1007/s40843-021-1918-x

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  • DOI: https://doi.org/10.1007/s40843-021-1918-x

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