Directed Self-Assembly by Sparsely Prepatterned Substrates with Self-Responsive Polymer Brushes.

ABSTRACT

The guiding pattern in the chemoepitaxially directed self-assembly (DSA) of block copolymers is often fabricated by periodically functionalizing homogeneously random copolymer brushes tethered on a substrate. The prepatterned copolymer brushes constitute a soft penetrable surface, and their two components can in principle locally segregate in response to the overlying self-assembly process of block copolymers. To reveal how the self-responsive behavior of the copolymer brushes affects the directing effect, we develop a dissipative particle dynamics model to explicitly include the prepatterned polymer brushes and implement it to simulate the DSA of a cylinder-forming diblock copolymer melt on the sparse pattern of polymer brushes. Through large-scale dynamic simulations, we identify the windows of the content of the random copolymer, the film thickness, and the diameter of the patterned spot, for the formation of perfectly ordered hexagonal patterns composed of perpendicular cylinders. Our dynamic simulations reveal that the random copolymer brushes grafted on the unpatterned area exhibit a remarkable self-responsive ability with respect to the self-assembly of the diblock copolymers overlying them, which may widen the effective window of the content of the random copolymer. Within the processing windows of these key parameters, defect-free patterns are successfully achieved both in simulations and in experiments with sizes as large as a few micrometers for 4-fold density multiplications. This work demonstrates that highly efficient computer simulations based on an effective model can provide helpful guidance for experiments to optimize the critical parameters and even may promote the application of DSA.