Theoretical Study on Defect Removal in Block Copolymer Thin Films under Soft Confinement

Jun-qing Song; Yi-xin Liu; Hong-dong Zhang

doi:10.11777/j.issn1000-3304.2018.18097

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Theoretical Study on Defect Removal in Block Copolymer Thin Films under Soft Confinement

Research Article | 更新时间：2021-01-26

- Theoretical Study on Defect Removal in Block Copolymer Thin Films under Soft Confinement
- Acta Polymerica Sinica Vol. 0, Issue 12, Pages: 1548-1557(2018)
- 作者机构：
  
  聚合物分子工程国家重点实验室复旦大学高分子科学系　上海 200438
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2018.18097
  CLC：
- Published：2018-12，
  
  Received：29 March 2018，
  
  Revised：24 April 2018，
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Jun-qing Song, Yi-xin Liu, Hong-dong Zhang. Theoretical Study on Defect Removal in Block Copolymer Thin Films under Soft Confinement. [J]. Acta Polymerica Sinica 0(12):1548-1557(2018)
DOI：

Jun-qing Song, Yi-xin Liu, Hong-dong Zhang. Theoretical Study on Defect Removal in Block Copolymer Thin Films under Soft Confinement. [J]. Acta Polymerica Sinica 0(12):1548-1557(2018) DOI： 10.11777/j.issn1000-3304.2018.18097.

摘要

理解缺陷消除机理对于制备无缺陷的长程有序嵌段共聚物薄膜至关重要. 本文利用弦方法结合自洽平均场理论研究了接枝均聚物高分子刷在AB两嵌段共聚物垂直层薄膜的偶极位错缺陷消除中发挥的作用. 研究发现，高分子刷的“浸润效应”和“重排效应”能够降低

的有效值，增大跳跃扩散的扩散系数，进而促进“桥连”结构的形成. 并且，接枝高分子刷的基底表面的“硬度”越小，以上2种效应越显著，越能进一步降低缺陷消除过程中形成“桥连”结构这一关键步骤的能垒.

Abstract

Understanding the defect removal process is crucial for the fabrication of defect-free self-assembled structures in block copolymer thin films. In this study

the removal of the dislocation dipole defect in thin films of perpendicular lamellar block copolymers on substrates modified by grafting polymers has been extensively studied. As revealed in previous studies

the " bridge” structure

which converts the slow hopping diffusion of block copolymer chains to fast interfacial diffusion

is a key factor to understand the mechanism of the defect removal process. Polymer grafting onto substrates is a widely accepted way to control domain orientation and fabricate surface pattern for directed self-assembly (DSA). However

the role of the grafted polymers on defect removal is unclear. In this study

the string method coupled with the self-consistent field theory (SCFT) is used to explore the influence of grafted polymers on the removal of a dislocation dipole in lamellar-froming thin films assembled by symmetric AB diblock copoymers. It is found that the " immersion effect” and the " rearrangement effect” introduced by the grafted polymers can facilitate the hopping diffusion of the block copolymer chains through reducing the effective

thus making the formation of the bridge structure easier. The decrease of the softness of the brush layer (

) will enhance these two effects and reduce the energy barrier of the transition state of the defect removal process. In the limit of

= 0

the bridge structure is found to already exist in the dislocation dipole near the brush layer

leading to a diminishing energy barrier of the removal process. Using the symmetric PS-

-PMMA with a number-average molecular weight of ≈ 5.1 × 10

at 195 °C as an example

we estimated the annealing time required to eliminate the dislocation dipole by assuming the diffusion coefficient of the hopping diffusion of block copolymers being

⊥

≈ 10

−13

/s. The annealing time are estimated to be

= 91.4 s and 150.9 s for extremely soft confinement (

= 0) and intermediate soft confinement (

= 30)

respectively. During the defect removal process

the brush layer will redistribute its density along the normal and the lateral directions of the substrate in response to the structural evolution of the thin film due to the " rearrangement effect”. Thus

the morphology of the brush layer reflects the microstructure of the thin film near the bottom substrate.

关键词

嵌段共聚物薄膜高分子刷缺陷消除弦方法自洽平均场理论方法

Keywords

Block copolymerThin filmPolymer brushDefect removalString methodSelf-consitent field theory

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College of Chemical Engineering, Fuzhou University

College of Materials Science and Engineering, Nanjing Tech University

State Key Laboratory of Materials-Oriented Chemical Engineering

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Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, Center for Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University

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