循环溶剂退火条件下柱状相组成的两嵌段共聚物薄膜自组装行为的模拟研究

胡卨俊; 郝金龙; 王铮; 尹玉华; 蒋润; 李宝会

doi:10.11777/j.issn1000-3304.2021.21082

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循环溶剂退火条件下柱状相组成的两嵌段共聚物薄膜自组装行为的模拟研究

研究论文 | 更新时间：2023-12-20

- 循环溶剂退火条件下柱状相组成的两嵌段共聚物薄膜自组装行为的模拟研究
- Self-assembly of Diblock Copolymer Films upon Cyclic Solvent Annealing: A Simulation Study
- 高分子学报 2021年52卷第10期页码：1379-1389
- 作者机构：
  
  南开大学物理科学学院教育部功能高分子材料重点实验室天津 300071
- 作者简介：
  
  E-mail: baohui@nankai.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣21574071;21774066);21528401, 21829301┫;教育部创新团队发展计划(IRT1257);高等学校学科创新引智111计划(B16027┫项目和外国文化教育专家项目┣G20190002001)
- DOI：10.11777/j.issn1000-3304.2021.21082
  中图分类号：
- 纸质出版日期：2021-10-20，
  
  网络出版日期：2021-08-18，
  
  收稿日期：2021-03-13，
  
  修回日期：2021-03-23，
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胡卨俊,郝金龙,王铮等.循环溶剂退火条件下柱状相组成的两嵌段共聚物薄膜自组装行为的模拟研究[J].高分子学报,2021,52(10):1379-1389.

Hu Xie-jun,Hao Jin-long,Wang Zheng,et al.Self-assembly of Diblock Copolymer Films upon Cyclic Solvent Annealing: A Simulation Study[J].ACTA POLYMERICA SINICA,2021,52(10):1379-1389.
胡卨俊,郝金龙,王铮等.循环溶剂退火条件下柱状相组成的两嵌段共聚物薄膜自组装行为的模拟研究[J].高分子学报,2021,52(10):1379-1389. DOI： 10.11777/j.issn1000-3304.2021.21082.

Hu Xie-jun,Hao Jin-long,Wang Zheng,et al.Self-assembly of Diblock Copolymer Films upon Cyclic Solvent Annealing: A Simulation Study[J].ACTA POLYMERICA SINICA,2021,52(10):1379-1389. DOI： 10.11777/j.issn1000-3304.2021.21082.

摘要

采用蒙特卡洛模拟研究了体相形成柱状相的两嵌段共聚物薄膜在循环溶剂退火条件下的自组装行为. 结果表明，在循环溶剂退火条件下，溶剂蒸发速率、溶剂选择性和有效薄膜厚度与柱状相周期的匹配性都会影响形成垂直柱状结构的表面选择性窗口(

窗口). 当溶剂蒸发速率在一定范围内时，

窗口随蒸发速率的增大而增大. 溶剂对长嵌段的选择性越强，形成垂直柱状结构的

窗口越宽. 当溶胀比约为1.5时的薄膜厚度与柱状相周期不匹配时更利于形成垂直柱状结构. 通过对链节均方位移曲线的分析发现，在循环溶剂退火条件下高分子链节在垂直方向的扩散始终快于平行方向，因此链节优先沿垂直方向聚集，从而促进了垂直柱状结构的形成.循环溶剂退火条件下，

窗口比溶剂退火条件下的宽，同时大幅度减少了退火时间.

Abstract

Solvent (-vapor) annealing (SA) has been widely used to promote the formation of perpendicularly oriented structures in self-assembly of block copolymer thin films. In SA

as-prepared block copolymer films are exposed to the vapor of solvent to form a swollen and mobile polymer film atop the substrate

and finally the solvent is evaporated. Tranditional SA contains only one swollen-evaporation process

while cyclic solvent annealing (CSA) contains multiple swollen-evaporation processes in a cyclic means. The existence of solvent affects the effective interaction between the blocks

the effective film thickness

the effective surface preference

and the effective volume fractions of the blocks

and hence affects the resulting morphology. The morphologies induced by the presence of solvent may be trapped during the solvent evaporation process. Hence

the resulting morphology after SA/CSA may be quite different from that without SA/CSA treatment. Furthermore

the swollen- evaporation processes in CSA can be designed to facilitate the formation of perpendicularly-orientated structures. In this study

we present our lattice Monte Carlo simulation results of the self-assembly for cylinder-forming diblock copolymer films under CSA. Our simulations are based on the "single-site bond fluctuation" model

and it is assumed that the maximum swelling ratio of the film in each swollen-evaporation cycle decreases linearly with the increase of the cycle number. This assumption ensures that relatively large rearrangement of microdomains occurs when the number of cycles is relatively small

and the resulting characteristic structure can be kept effectively in the following cycles. The results show that the surface preference window (

-window) of perpendicular cylinders is affected by the solvent evaporation rate

solvent selectivity and commensurability between the film thickness and the bulk period. When the solvent evaporation rate is intermediate

the

-window enlarges with increasing it. A stronger solvent selectivity for the majority block as well as dismatch between the film thickness at a swelling ratio of 1.5 and the period of the bulk cylindrical phase enlarges the

-window. By analyzing the mean-square displacements

it is found that the diffusion of the polymer segments in the perpendicular direction is always faster than that in the parallel direction

which leads to that segments are preferentially gathered along the perpendicular direction

and hence promotes the formation of the perpendicular cylinders. Compared with that in the SA treatment for the same system

the

-window of perpendicular cylinders is wider and the annealing time can be greatly reduced under CSA treatment.

关键词

嵌段共聚物循环溶剂退火取向柱状相

Keywords

Block copolymerCyclic solvent (vapor) annealingOrientationCylindrical phase

references

Bates F S, Fredrickson G H. Annu Rev Phys Chem, 1990, 41(1): 525-557. doi:10.1146/annurev.pc.41.100190.002521http://dx.doi.org/10.1146/annurev.pc.41.100190.002521

Kim S H, Misner M J, Xu T, Kimura M, Russell T P. Adv Mater, 2004, 16(3): 226-231. doi:10.1002/adma.200304906http://dx.doi.org/10.1002/adma.200304906

Darling S B. Prog Polym Sci, 2007, 32(10): 1152-1204. doi:10.1016/j.progpolymsci.2007.05.004http://dx.doi.org/10.1016/j.progpolymsci.2007.05.004

Zhang Xinghua(张兴华), Yan Dadong(严大东). Acta Polymerica Sinica(高分子学报), 2014, (8): 1041-1047

Li Zhaolei(李照磊), Zhou Dongshan(周东山), Hu Wenbing(胡文兵). Acta Polymerica Sinica(高分子学报), 2016, (9): 1179-1197

Li Xiaoxia(李小霞), Gu Mengxin(谷梦鑫), Zhang Liangshun(张良顺), Lin Jiaping(林嘉平). Acta Polymerica Sinica(高分子学报), 2020, 51(11): 1257-1266

Glass R, Mller M, Spatz J P. Nanotechnology, 2003, 14(10): 1153-1160. doi:10.1088/0957-4484/14/10/314http://dx.doi.org/10.1088/0957-4484/14/10/314

Stoykovich M P, Kang H, Daoulas K C, Liu G, Liu C C, de Pablo J J, Müller M, Nealey P F. ACS Nano, 2007, 1(3): 168-175. doi:10.1021/nn700164phttp://dx.doi.org/10.1021/nn700164p

Jeong S-J, Kim J Y, Kim B H, Moon H-S, Kim S O. Mater Today, 2013, 16(12): 468-476. doi:10.1016/j.mattod.2013.11.002http://dx.doi.org/10.1016/j.mattod.2013.11.002

Ulbricht M. Polymer, 2006, 47(7): 2217-2262. doi:10.1016/j.polymer.2006.01.084http://dx.doi.org/10.1016/j.polymer.2006.01.084

Yang S Y, Ryu I, Kim H Y, Kim J K, Russell T P. Adv Mater, 2006, 18(6): 709-712. doi:10.1002/adma.200501500http://dx.doi.org/10.1002/adma.200501500

Phillip W A, O'Neill B, Rodwogin M, Hillmyer M A, Cussler E L. ACS Appl Mater Interfaces, 2010, 2(3): 847-853. doi:10.1021/am900882thttp://dx.doi.org/10.1021/am900882t

Thurn-Albrecht T, Steiner R, Derouchey J, Stafford C M, Huang E, Bal M, Tuominen M, Hawker C J, Russell T P. Adv Mater, 2000, 12(11): 787-791. doi:10.1002/(sici)1521-4095(200006)12:11<787::aid-adma787>3.0.co;2-1http://dx.doi.org/10.1002/(sici)1521-4095(200006)12:11<787::aid-adma787>3.0.co;2-1

Wang Q, Nealey P F, de Pablo J J. Macromolecules, 2001, 34(10): 3458-3470. doi:10.1021/ma0018751http://dx.doi.org/10.1021/ma0018751

Gu X, Gunkel I, Hexemer A, Gu W, Russell T P. Adv Mater, 2014, 26(2): 273-281. doi:10.1002/adma.201302562http://dx.doi.org/10.1002/adma.201302562

Nandan B, Vyas M K, Böhme M, Stamm M. Macromolecules, 2010, 43(5): 2463-2473. doi:10.1021/ma901693chttp://dx.doi.org/10.1021/ma901693c

Yu B, Li B H, Jin Q, Ding D, Shi A C. Soft Matter, 2011, 7(21): 10227-10240. doi:10.1039/c1sm05947ehttp://dx.doi.org/10.1039/c1sm05947e

Mansky P, DeRouchey J, Russell T P, Mays J, Pitsikalis M, Morkved T, Jaeger H. Macromolecules, 1998, 31(13): 4399-4401. doi:10.1021/ma980299uhttp://dx.doi.org/10.1021/ma980299u

Knoll A, Horvat A, Lyakhova K S, Krausch G, Sevink G J A, Zvelindovsky A V, Magerle R. Phys Rev Lett, 2002, 89(3): 035501. doi:10.1103/physrevlett.89.035501http://dx.doi.org/10.1103/physrevlett.89.035501

Bae J, Cha S H. Polymer, 2014, 55(8): 2014-2020. doi:10.1016/j.polymer.2014.02.054http://dx.doi.org/10.1016/j.polymer.2014.02.054

Kan D, He X. Soft Matter, 2016, 12(19): 4449-4456. doi:10.1039/c5sm03154khttp://dx.doi.org/10.1039/c5sm03154k

Hüttner S, Sommer M, Chiche A, Krausch G, Steiner U, Thelakkat M. Soft Matter, 2009, 5(21): 4206-4211. doi:10.1039/b907147dhttp://dx.doi.org/10.1039/b907147d

Sinturel C, Vayer M n, Morris M, Hillmyer M A. Macromolecules, 2013, 46(14): 5399-5415. doi:10.1021/ma400735ahttp://dx.doi.org/10.1021/ma400735a

Paradiso S P, Delaney K T, García-Cervera C J, Ceniceros H D, Fredrickson G H. ACS Macro Lett, 2014, 3(1): 16-20. doi:10.1021/mz400572rhttp://dx.doi.org/10.1021/mz400572r

Berezkin A V, Papadakis C M, Potemkin I I. Macromolecules, 2016, 49(1): 415-424. doi:10.1021/acs.macromol.5b01771http://dx.doi.org/10.1021/acs.macromol.5b01771

Hao J, Wang Z, Wang Z, Yin Y, Jiang R, Li B H, Wang Q. Macromolecules, 2017, 50(11): 4384-4396. doi:10.1021/acs.macromol.7b00200http://dx.doi.org/10.1021/acs.macromol.7b00200

Paradiso S P, Delaney K T, García-Cervera C J, Ceniceros H D, Fredrickson G H. Macromolecules, 2016, 49(5): 1743-1751. doi:10.1021/acs.macromol.5b02107http://dx.doi.org/10.1021/acs.macromol.5b02107

Hong S W, Huh J, Gu X, Lee D H, Jo W H, Park S, Xu T, Russell Thomas P. Proc Natl Acad Sci USA, 2012, 109(5): 1402-1406. doi:10.1073/pnas.1115803109http://dx.doi.org/10.1073/pnas.1115803109

Liu G, Ramirez-Hernandez A, Yoshida H, Nygard K, Satapathy D K, Bunk O, de Pablo J J, Nealey P F. Phys Rev Lett, 2012, 108(6): 065502. doi:10.1103/physrevlett.108.065502http://dx.doi.org/10.1103/physrevlett.108.065502

Ramírez-Hernández A, Suh H S, Nealey P F, de Pablo J J. Macromolecules, 2014, 47(10): 3520-3527. doi:10.1021/ma500411qhttp://dx.doi.org/10.1021/ma500411q

Peng M, Ma S, Hu J, Wang R. Soft Matter, 2015, 11(33): 6642-6651. doi:10.1039/c5sm01334hhttp://dx.doi.org/10.1039/c5sm01334h

Zhang Jingxue(张景雪), Wu Jiaping(吴佳坪), Wang Qiang(王强), Li Baohui(李宝会). Acta Polymerica Sinica(高分子学报), 2021, 52(1): 102-112

Zhu Ziting(朱子霆), Gao Huanhuan(高欢欢), Hu Wenbing(胡文兵). Acta Polymerica Sinica(高分子学报), 2017, (9): 1471-1478. doi:10.11777/j.issnl000-3304.2017.17055http://dx.doi.org/10.11777/j.issnl000-3304.2017.17055

Zheng Lingfei(郑玲飞), Wang Zheng(王铮), Yin Yuha(尹玉华), Jiang Run(蒋润), Li Baohui(李宝会). Acta Polymerica Sinica(高分子学报), 2019, 50(9): 60-69

Liu Zhiyao (刘志瑶), Wang Zheng(王铮), Yin Yuha(尹玉华), Jiang Run(蒋润), Li Baohui(李宝会). Acta Polymerica Sinica(高分子学报), 2019, 50(11): 96-104

Han Zhengwei(韩政伟), Sun Pingchuan(孙平川), Li Baohui(李宝会), Jin Qinghua(金庆华), Ding Datong(丁大同). Acta Polymerica Sinica(高分子学报), 2006, (4): 593-596

Kirkpatrick S, Gelatt C D, Vecchi M P. Science, 1983, 220(4598): 671-680. doi:10.1126/science.220.4598.671http://dx.doi.org/10.1126/science.220.4598.671

Yu B, Sun P, Chen T, Jin Q, Ding D, Li B, Shi A C. Phys Rev Lett, 2006, 96(13): 138306. doi:10.1103/physrevlett.96.138306http://dx.doi.org/10.1103/physrevlett.96.138306

Carmesin I, Kremer K. Macromolecules, 1988, 21(9): 2819-2823. doi:10.1021/ma00187a030http://dx.doi.org/10.1021/ma00187a030

Larson R G. J Chem Phys, 1989, 91(4): 2479-2488. doi:10.1063/1.457007http://dx.doi.org/10.1063/1.457007

Hao Jinlong(郝金龙), Wang Zhan(汪湛), Wang Zheng(王铮), Yin Yuhua(尹玉华), Jiang Run(蒋润), Li Baohui(李宝会). Acta Polymerica Sinica(高分子学报), 2017, (11): 1841-1850

Son J G, Gotrik K W, Ross C A. ACS Macro Lett, 2012, 1(11): 1279-1284. doi:10.1021/mz300475ghttp://dx.doi.org/10.1021/mz300475g

Tang Q, Müller M, Li C Y, Hu W. Phys Rev Lett, 2019, 123(20): 207801. doi:10.1103/physrevlett.123.207801http://dx.doi.org/10.1103/physrevlett.123.207801

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