Citation: 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, ;2018, 0(12): 1548-1557. doi: 10.11777/j.issn1000-3304.2018.18097 shu

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

State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438

Corresponding author: Yi-xin Liu, lyx@fudan.edu.cn
Received Date: 29 March 2018
Revised Date: 24 April 2018
Available Online: 17 July 2018

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 χ_AB, thus making the formation of the bridge structure easier. The decrease of the softness of the brush layer (γ) will enhance these two effects and reduce the energy barrier of the transition state of the defect removal process. In the limit of γ = 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-b-PMMA with a number-average molecular weight of ≈ 5.1 × 10⁴ 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 D_⊥ ≈ 10⁻¹³ cm²/s. The annealing time are estimated to be τ = 91.4 s and 150.9 s for extremely soft confinement (γ = 0) and intermediate soft confinement (γ = 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.
- Block copolymer,
- Thin film,
- Polymer brush,
- Defect removal,
- String method,
- Self-consitent field theory
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