The Chain Flexibility Effects on the Self-assembly of Diblock Copolymer in Thin Film
arXiv:2211.04714 · doi:10.1021/acs.macromol.2c02292
Abstract
We investigate the effects of chain flexibility on the self-assembly behavior of symmetric diblock copolymers (BCPs) when they are confined as a thin film between two surfaces. Employing worm-like chain (WLC) self-consistent field theory, we study the relative stability of parallel (L) and perpendicular (L) orientations of BCP lamellar phases, ranging in chain flexibility from flexible Gaussian chains to semi-flexible and rigid chains. For flat and neutral bounding surfaces (no surface preference for one of the two BCP components), the stability of the L lamellae increases with chain rigidity. When the top surface is flat and the bottom substrate is corrugated, increasing the surface roughness enhances the stability of the L lamellae for flexible Gaussian chains. However, an opposite behavior is observed for rigid chains, where the L stability decreases as the substrate roughness increases. We further show that as the substrate roughness increases, the critical value of the substrate preference, , corresponding to an L-to-L transition, decreases for rigid chains, while it increases for flexible Gaussian chains. Our results highlight the physical mechanism of tailoring the orientation of lamellar phases in thin-film setups. This is of importance, in particular, for short (semi-flexible or rigid) chains that are in high demand in emerging nanolithography and other industrial applications.