Self-assembly of Diblock Copolymer Films upon Cyclic Solvent Annealing: A Simulation Study

Xie-jun Hu; Jin-long Hao; Zheng Wang; Yu-hua Yin; Run Jiang; Bao-hui Li

doi:10.11777/j.issn1000-3304.2021.21082

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Self-assembly of Diblock Copolymer Films upon Cyclic Solvent Annealing: A Simulation Study

Research Article | 更新时间：2023-12-20

- Self-assembly of Diblock Copolymer Films upon Cyclic Solvent Annealing: A Simulation Study
- ACTA POLYMERICA SINICA Vol. 52, Issue 10, Pages: 1379-1389(2021)
- 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：
  
  Bao-hui Li, E-mail: baohui@nankai.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2021.21082
  CLC：
- Published：20 October 2021，
  
  Published Online：18 August 2021，
  
  Received：13 March 2021，
  
  Revised：23 March 2021，
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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

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