Solvent and Substrate Induced Synergistic Ordering in Block Copolymer Thin Films

Nanotechnology-based applications of block copolymers (BCPs) require a detailed understanding of microphase separation in thin films during processing. Solvent annealing is a widely employed method for BCP thin films. Quantification of microphase separation is an empirical challenge due to the nature of the buried interface and the scale of temporal dynamics. Several modeling-based approaches have been attempted, but they shed little light on capturing the overall dynamics and interactions that contribute to domain formation in BCP thin films. For the first time, we report in this article a systematic coarse-grained (CG) molecular dynamics (MD) approach that addresses both the ordering and the morphological evolution in solvent swollen thin BCP films. In this study, for an inherently lamellar BCP system, we found that a slight change in relative solvent–block interactions can generate a variety of morphologies including cylindrical, lamellar, and other transient morphologies. In addition, we correlate the...