Investigation of Bluk and Thin-film Self-assembly Using Discrete Fluorine-containing Block Copolymers

Hai-bing Wu; Sheng-xi Jiang; Rui Tan; Yu-xin Liu; Xue-hui Dong; Zheng-biao Zhang

doi:10.11777/j.issn1000-3304.2023.23200

您当前的位置：

首页 >

文章列表页 >

Investigation of Bluk and Thin-film Self-assembly Using Discrete Fluorine-containing Block Copolymers

Research Article | 更新时间：2024-01-19

- Investigation of Bluk and Thin-film Self-assembly Using Discrete Fluorine-containing Block Copolymers
  增强出版
- Acta Polymerica Sinica Vol. 55, Issue 2, Pages: 142-152(2024)
- 作者机构：
  
  1.苏州大学材料与化学化工学部苏州 215123
  2.华南理工大学前沿软物质学院广州 510640
- 作者简介：
  
  Xue-hui Dong,E-mail: xdong@scut.edu.cn
  Zheng-biao Zhang, E-mail: zhangzhengbiao@suda.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2023.23200
  CLC：
- Published：20 February 2024，
  
  Published Online：27 December 2023，
  
  Received：28 July 2023，
  
  Accepted：06 November 2023
- 稿件说明：
移动端阅览
吴海兵, 蒋胜喜, 谭睿, 刘雨欣, 董学会, 张正彪. 单一分子量含氟嵌段共聚物的本体及薄膜自组装研究. 高分子学报, 2024, 55(2), 142-152

Wu, H. B.; Jiang, S. X.; Tan, R.; Liu, Y. X.; Dong, X. H.; Zhang, Z. B. Investigation of bluk and thin-film self-assembly using discrete fluorine-containing block copolymers. Acta Polymerica Sinica, 2024, 55(2), 142-152
吴海兵, 蒋胜喜, 谭睿, 刘雨欣, 董学会, 张正彪. 单一分子量含氟嵌段共聚物的本体及薄膜自组装研究. 高分子学报, 2024, 55(2), 142-152 DOI： 10.11777/j.issn1000-3304.2023.23200.

Wu, H. B.; Jiang, S. X.; Tan, R.; Liu, Y. X.; Dong, X. H.; Zhang, Z. B. Investigation of bluk and thin-film self-assembly using discrete fluorine-containing block copolymers. Acta Polymerica Sinica, 2024, 55(2), 142-152 DOI： 10.11777/j.issn1000-3304.2023.23200.

摘要

嵌段共聚物导向自组装作为一种自下而上的图案化工艺，受到工业界和学术界的广泛关注. 然而，导向自组装中缺陷率与分子参数之间的关系研究尚不清晰. 本文工作基于模块化合成策略，利用迭代指数增长法并结合巯基-双键的点击反应成功制备了高

低

的单一分子量含氟聚酯嵌段共聚物(

-FPOSS). 单一分子量特征可以排除多分散性对自组装行为的影响. 本体自组装研究表明聚酯嵌段和含氟嵌段具有强相分离驱动力，可以形成特征尺寸小于10 nm的六方柱状相结构(HEX). 在薄膜自组装中，嵌段共聚物经过简单的热退火可以在硅片表面形成平行基底排布的柱状纳米图案. 此外，通过对比研究不同链长单一分子量嵌段共聚物的薄膜组装行为，发现随着嵌段共聚物链长的增长薄膜组装图形缺陷率明显下降，初步揭示了薄膜自组装过程中缺陷形成对嵌段共聚物链长的依赖性.

Abstract

Directed self-assembly of block copolymers has arouse tremendous interest from academy and industry as a bottom-up patterning process to fabricate versatile nanostructures. However

the underlying principles between molecular parameters and defectivities in directed self-assembly are still unambiguous due to the limitations of traditional polydisperse polymer models. Discrete polymer with defined molecular structure and uniform chain length are ideal candidates to reveal the fundamental principles. In this study

based on the modular synthesis strategy

discrete fluorine-containing polyester block copolymers (

-FPOSS) with high

-low

were firstly prepared by iterative exponential growth in combination with the thiol-ene click reaction. Owing to the discrete feature

the influence of polydisperse molecular parameters including composition

molecular weight and distribution on self-assembly behaviors can be completely excluded. Consequently

the impacts of molecular structures on the evolution of phase segregation can be quantitatively revealed. Due to the strong segregation strength

hexagonally packed cylindrical nanostructures (HEX) less than 10 nm can be formed in bulk and the phase stability increases with the chain length of

LA block. In thin-film self-assembly

parallelly oriented cylindrical nanopatterns on Si substrate were clearly identified after brief annealing under vacuum. In addition

through comparative studies of thin-film self-assembly behaviors of discrete block copolymers with different chain lengths

the nanopattern defectivity decreased significantly with the increase of

LA block chain length

which initially revealed the dependence of defect formation on block copolymer chain length in thin-film self-assembly.

关键词

单一分子量高分子导向自组装含氟嵌段共聚物本体及薄膜自组装光刻

Keywords

Discrete polymerDirected self-assemblyFluorine-containing block copolymerBulk and thin film self-assemblyLithography

references

Wagner C.; Harned, N. Lithography gets extreme. Nat. Photonics, 2010, 4(1), 24-26. doi:10.1038/nphoton.2009.251http://dx.doi.org/10.1038/nphoton.2009.251

Pan D. Z. Directed self-assembly for advanced chips. Nat. Electron., 2018, 1(10), 530-531. doi:10.1038/s41928-018-0152-7http://dx.doi.org/10.1038/s41928-018-0152-7

Huang X. H.; Xiong S. S. Advanced lithography: directed self-assembly. Chin. J. Appl. Chem., 2021, 38, 1029.

Somervell M.; Kitano T. Driving DSA into volume manufacturing. Proc. SPIE, 2015, 942594250Q. doi:10.1117/12.2085776http://dx.doi.org/10.1117/12.2085776

Wan L.; Ruiz R.; Gao H.; Patel K. C.; Albrecht T. R.; Yin J.; Kim J.; Cao Y.; Lin G. Y. The limits of lamellae-forming PS-b-PMMA block copolymers for lithography. ACS Nano, 2015, 9(7), 7506-7514. doi:10.1021/acsnano.5b02613http://dx.doi.org/10.1021/acsnano.5b02613

Zhao Y. E.; Sivaniah E.; Hashimoto T. SAXS analysis of the order-disorder transition and the interaction parameter of polystyrene-block-poly(methyl methacrylate). Macromolecules, 2008, 41(24), 9948-9951. doi:10.1021/ma8013004http://dx.doi.org/10.1021/ma8013004

Russell T. P.; Hjelm, R. P. Jr Seeger, Temperature dependence of the interaction parameter of polystyrene and poly(methyl methacrylate). Macromolecules, 1990, 23(3), 890-893. doi:10.1021/ma00205a033http://dx.doi.org/10.1021/ma00205a033

Matsen M. W.; Bates F. S. Unifying weak- and strong-segregation block copolymer theories. Macromolecules, 1996, 29(4), 1091-1098. doi:10.1021/ma951138ihttp://dx.doi.org/10.1021/ma951138i

Chen Y.; Xiong S. S. Directed self-assembly of block copolymers for sub-10 nm fabrication. Int. J. Extrem. Manuf., 2020, 2(3), 032006. doi:10.1088/2631-7990/aba3aehttp://dx.doi.org/10.1088/2631-7990/aba3ae

Cummins C.; Pino G.; Mantione D.; Fleury G. Engineering block copolymer materials for patterning ultra-low dimensions. Mol. Syst. Des. Eng., 2020, 5(10), 1642-1657. doi:10.1039/d0me00118jhttp://dx.doi.org/10.1039/d0me00118j

Lo T. Y.; Krishnan M. R.; Lu K. Y.; Ho R. M. Silicon-containing block copolymers for lithographic applications. Prog. Polym. Sci., 2018, 77, 19-68. doi:10.1016/j.progpolymsci.2017.10.002http://dx.doi.org/10.1016/j.progpolymsci.2017.10.002

Pino G.; Cummins C.; Mantione D.; Demazy N.; Alvarez-Fernandez A.; Guldin S.; Fleury G.; Hadziioannou G.; Cloutet E.; Brochon C. Design and morphological investigation of high-χ catechol-containing styrenic block copolymers. Macromolecules, 2022, 55(15), 6341-6350. doi:10.1021/acs.macromol.2c00476http://dx.doi.org/10.1021/acs.macromol.2c00476

Mishra A. K.; Lee J.; Kang S.; Kim E.; Choi C.; Kim J. K. Gallol-based block copolymer with a high flory-huggins interaction parameter for next-generation lithography. Macromolecules, 2022, 55(24), 10797-10803. doi:10.1021/acs.macromol.2c01633http://dx.doi.org/10.1021/acs.macromol.2c01633

Jo S.; Jeon S.; Kim H.; Ryu C. Y.; Lee S.; Ryu D. Y. Balanced interfacial interactions for fluoroacrylic block copolymer films and fast electric field directed assembly. Chem. Mater., 2020, 32(22), 9633-9641. doi:10.1021/acs.chemmater.0c03251http://dx.doi.org/10.1021/acs.chemmater.0c03251

Li X. M.; Li J.; Wang C. X.; Liu Y. Y.; Deng H. Fast self-assembly of polystyrene-b-poly(fluoro methacrylate) into sub-5 nm microdomains for nanopatterning applications. J. Mater. Chem. C, 2019, 7(9), 2535-2540. doi:10.1039/c8tc06480fhttp://dx.doi.org/10.1039/c8tc06480f

Jo S.; Jeon S.; Jun T.; Park C.; Ryu D. Y. Fluorine-containing styrenic block copolymers toward high χ and perpendicular lamellae in thin films. Macromolecules, 2018, 51(18), 7152-7159. doi:10.1021/acs.macromol.8b01325http://dx.doi.org/10.1021/acs.macromol.8b01325

Nakatani R.; Takano H.; Chandra A.; Yoshimura Y.; Wang L.; Suzuki Y.; Tanaka Y.; Maeda R.; Kihara N.; Minegishi S.; Miyagi K.; Kasahara Y.; Sato H.; Seino Y.; Azuma T.; Yokoyama H.; Ober C. K.; Hayakawa T. Perpendicular orientation control without interfacial treatment of RAFT-synthesized high-χ block copolymer thin films with sub-10 nm features prepared via thermal annealing. ACS Appl. Mater. Interfaces, 2017, 9(37), 31266-31278. doi:10.1021/acsami.6b16129http://dx.doi.org/10.1021/acsami.6b16129

Li X. M.; Deng H. Poly(2-vinylpyridine)-b-poly(fluorinated methacrylate) block copolymers forming 5 nm domains containing metallocene. ACS Appl. Polym. Mater., 2020, 2(8), 3601-3611. doi:10.1021/acsapm.0c00608http://dx.doi.org/10.1021/acsapm.0c00608

Cummins C.; Mantione D.; Cruciani F.; Pino G.; Demazy N.; Shi Y. L.; Portale G.; Hadziioannou G.; Fleury G. Rapid self-assembly and sequential infiltration synthesis of high χ fluorine-containing block copolymers. Macromolecules, 2020, 53(15), 6246-6254. doi:10.1021/acs.macromol.0c01148http://dx.doi.org/10.1021/acs.macromol.0c01148

Hillmyer M. A.; Lodge T. P. Synthesis and self-assembly of fluorinated block copolymers. J. Polym. Sci. Poly. Chem., 2002, 40(1), 1-8. doi:10.1002/pola.10074http://dx.doi.org/10.1002/pola.10074

Zhu S. X.; Edmonds W. F.; Hillmyer M. A.; Lodge T. P. Synthesis and self-assembly of highly incompatible polybutadiene-poly(hexafluoropropylene oxide) diblock copolymers. J. Polym. Sci. Poly. Phys., 2005, 43(24), 3685-3694. doi:10.1002/polb.20621http://dx.doi.org/10.1002/polb.20621

Wang C. X.; Li X. M.; Deng H. Synthesis of a fluoromethacrylate hydroxystyrene block copolymer capable of rapidly forming sub-5 nm domains at low temperatures. ACS Macro Lett., 2019, 8(4), 368-373. doi:10.1021/acsmacrolett.9b00178http://dx.doi.org/10.1021/acsmacrolett.9b00178

Ren Y.; Lodge T. P.; Hillmyer M. A. Synthesis, characterization, and interaction strengths of difluorocarbene-modified polystyrene-polyisoprene block copolymers. Macromolecules, 2000, 33(3), 866-876. doi:10.1021/ma9917085http://dx.doi.org/10.1021/ma9917085

Takahashi H.; Laachi N.; Delaney K. T.; Hur S. M.; Weinheimer C. J.; Shykind D.; Fredrickson G. H. Defectivity in laterally confined lamella-forming diblock copolymers: thermodynamic and kinetic aspects. Macromolecules, 2012, 45(15), 6253-6265. doi:10.1021/ma300993xhttp://dx.doi.org/10.1021/ma300993x

Herr D. J. C. Directed block copolymer self-assembly for nanoelectronics fabrication. J. Mater. Res., 2011, 26(2), 122-139. doi:10.1557/jmr.2010.74http://dx.doi.org/10.1557/jmr.2010.74

Maeda R.; Hayakawa T.; Ober C. K. Dual mode patterning of fluorine-containing block copolymers through combined top-down and bottom-up lithography. Chem. Mater., 2012, 24(8), 1454-1461. doi:10.1021/cm300093ehttp://dx.doi.org/10.1021/cm300093e

Hu T. Y.; Ren Y. Z.; Li W. H. Annihilation kinetics of an interacting 5/7-dislocation pair in the hexagonal cylinders of AB diblock copolymer. Macromolecules, 2022, 55(17), 7583-7593. doi:10.1021/acs.macromol.2c01403http://dx.doi.org/10.1021/acs.macromol.2c01403

Hu T. Y.; Ren Y. Z.; Li W. H. Impact of molecular asymmetry of block copolymers on the stability of defects in aligned lamellae. Macromolecules, 2021, 54(17), 8024-8032. doi:10.1021/acs.macromol.1c01192http://dx.doi.org/10.1021/acs.macromol.1c01192

Hur S. M.; Thapar V.; Ramírez-Hernández A.; Khaira G.; Segal-Peretz T.; Rincon-Delgadillo P. A.; Li W. H.; Müller M.; Nealey P. F.; de Pablo J. J. Molecular pathways for defect annihilation in directed self-assembly. Proc. Natl. Acad. Sci. U. S. A., 2015, 112(46), 14144-14149. doi:10.1073/pnas.1508225112http://dx.doi.org/10.1073/pnas.1508225112

Nagpal U.; Müller M.; Nealey P. F.; de Pablo J. J. Free energy of defects in ordered assemblies of block copolymer domains. ACS Macro Lett., 2012, 1(3), 418-422. doi:10.1021/mz200245shttp://dx.doi.org/10.1021/mz200245s

Li W. H.; Nealey P. F.; de Pablo J. J.; Müller M. Defect removal in the course of directed self-assembly is facilitated in the vicinity of the order-disorder transition. Phys. Rev. Lett., 2014, 113(16), 168301. doi:10.1103/physrevlett.113.168301http://dx.doi.org/10.1103/physrevlett.113.168301

Hu T. Y.; Ren Y. Z.; Zhang L. S.; Li W. H. Impact of architecture of symmetric block copolymers on the stability of a dislocation defect. Macromolecules, 2021, 54(2), 773-782. doi:10.1021/acs.macromol.0c01654http://dx.doi.org/10.1021/acs.macromol.0c01654

Li J. J.; Rincon-Delgadillo P. A.; Suh H. S.; Mannaert G.; Nealey P. F. Understanding kinetics of defect annihilation in chemoepitaxy-directed self-assembly. ACS Appl. Mater. Interfaces, 2021, 13(21), 25357-25364. doi:10.1021/acsami.1c03830http://dx.doi.org/10.1021/acsami.1c03830

Bates C. M.; Maher M. J.; Janes D. W.; Ellison C. J.; Willson C. G. Block copolymer lithography. Macromolecules, 2014, 47(1), 2-12. doi:10.1021/ma401762nhttp://dx.doi.org/10.1021/ma401762n

Lynd N. A.; Meuler A. J.; Hillmyer M. A. Polydispersity and block copolymer self-assembly. Prog. Polym. Sci., 2008, 33(9), 875-893. doi:10.1016/j.progpolymsci.2008.07.003http://dx.doi.org/10.1016/j.progpolymsci.2008.07.003

Duan S. H.; Yang X. J.; Yang Z.; Liu Y. X.; Shi Q. N.; Yang Z. L.; Wu H. B.; Han Y. E.; Wang Y. Q.; Shen H.; Huang Z. H.; Dong X. H.; Zhang Z. B. A versatile synthetic platform for discrete oligo- and polyesters based on optimized protective groups via iterative exponential growth. Macromolecules, 2021, 54(23), 10830-10837. doi:10.1021/acs.macromol.1c01498http://dx.doi.org/10.1021/acs.macromol.1c01498

Huang Z. H.; Shi Q. N.; Guo J.; Meng F. Y.; Zhang Y. J.; Lu Y. T.; Qian Z. F.; Li X. P.; Zhou N. C.; Zhang Z. B.; Zhu X. L. Binary tree-inspired digital dendrimer. Nat. Commun., 2019, 10, 1918. doi:10.1038/s41467-019-09957-6http://dx.doi.org/10.1038/s41467-019-09957-6

Huang Z. H.; Zhao J. F.; Wang Z. M.; Meng F. Y.; Ding K. S.; Pan X. Q.; Zhou N. C.; Li X. P.; Zhang Z. B.; Zhu X. L. Combining orthogonal chain-end deprotections and thiol-maleimide Michael coupling: engineering discrete oligomers by an iterative growth strategy. Angew. Chem. Int. Ed., 2017, 56(44), 13612-13617. doi:10.1002/anie.201706522http://dx.doi.org/10.1002/anie.201706522

Shi Q. N.; Miao T. F.; Lu J. Q.; Hu L. H.; Huang X. M.; Wang Z.; Piao M. H.; Huang Z. H.; Zhang Z. B. Cascaded encryption/decryption using digital polymer toward high-level information security. Giant, 2023, 15, 100172. doi:10.1016/j.giant.2023.100172http://dx.doi.org/10.1016/j.giant.2023.100172

Shi Q. N.; Miao T. F.; Liu Y. X.; Hu L. H.; Yang H.; Shen H.; Piao M. H.; Huang Z. H.; Zhang Z. B. Fabrication and decryption of a microarray of digital dithiosuccinimide oligomers. Macromol. Rapid Commun., 2022, 43(9), 2200029. doi:10.1002/marc.202200029http://dx.doi.org/10.1002/marc.202200029

Chen Y. D.; Huang Z. H.; Zhang Z. B. Recent advances in the synthesis of discrete oligomers and polymers: chemistry, strategy and technology. Sci. China Chem., 2022, 65(6), 1007-1009. doi:10.1007/s11426-022-1223-yhttp://dx.doi.org/10.1007/s11426-022-1223-y

van Genabeek B.; de Waal B. F. M.; Gosens M. M. J.; Pitet L. M.; Palmans A. R. A.; Meijer E. W. Synthesis and self-assembly of discrete dimethylsiloxane-lactic acid diblock co-oligomers: the dononacontamer and its shorter homologues. J. Am. Chem. Soc., 2016, 138(12), 4210-4218. doi:10.1021/jacs.6b00629http://dx.doi.org/10.1021/jacs.6b00629

Sun Y. X.; Tan R.; Ma Z. A.; Gan Z. H.; Li G.; Zhou D. D.; Shao Y.; Zhang W. B.; Zhang R.; Dong X. H. Discrete block copolymers with diverse architectures: resolving complex spherical phases with one monomer resolution. ACS Cent. Sci., 2020, 6(8), 1386-1393. doi:10.1021/acscentsci.0c00798http://dx.doi.org/10.1021/acscentsci.0c00798

Ma Z. A.; Zhou D. D.; Xu M. A.; Gan Z. H.; Zheng T. Y.; Wang S. A.; Tan R.; Dong X. H. Discrete linear-branched block copolymer with broken architectural symmetry. Macromolecules, 2023, 56(3), 833-840. doi:10.1021/acs.macromol.2c02529http://dx.doi.org/10.1021/acs.macromol.2c02529

Gan Z. H.; Zhou D. D.; Ma Z. A.; Xu M. A.; Xu Z. Q.; He J. W.; Zhou J. J.; Dong X. H. Local chain feature mandated self-assembly of block copolymers. J. Am. Chem. Soc., 2023, 145(1), 487-497. doi:10.1021/jacs.2c10761http://dx.doi.org/10.1021/jacs.2c10761

Zhou D. D.; Xu M. A.; Ma Z. A.; Gan Z. H.; Tan R.; Wang S. A.; Zhang Z. B.; Dong X. H. Precisely encoding geometric features into discrete linear polymer chains for robust structural engineering. J. Am. Chem. Soc., 2021, 143(44), 18744-18754. doi:10.1021/jacs.1c09575http://dx.doi.org/10.1021/jacs.1c09575

Mabry J.; Vij A.; Iacono S.; Viers B. Fluorinated polyhedral oligomeric silsesquioxanes (F-POSS). Angew. Chem. Int. Ed., 2008, 47(22), 4137-4140. doi:10.1002/anie.200705355http://dx.doi.org/10.1002/anie.200705355

Views

207

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Crystallization Kinetics of Precisely Synthesized Discrete Oligo(γ-butyrolactone)s

Related Author

Xue-hui Dong

Ao Feng

Su-hua Duan

Xiao-huan Cao

Rui Tan

Zhi-hao Huang

Xiao-hua Zhang

Related Institution

South China Advanced Institute for Soft Matter Science and Technology, School of Molecular Science and Engineering, South China University of Technology

Center for Soft Condensed Matter Physics and Interdisciplinary Research

School of Physical Science and Technology, Soochow University

Postal code：100190
Tel：010-62588927 Email：gfzxb@iccas.ac.cn
Technical support is provided by Beijing Founder electronics co., LTD 京ICP备05002797号-8 京公网安备11010802024621
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.

⁰