Defects in the Self-Assembly of Block Copolymers and Their Relevance for Directed Self-Assembly

Block copolymer self-assembly provides a platform for fabricating dense, ordered nanostructures by encoding information in the chemical architecture of multicomponent macromolecules. Depending on the volume fraction of the components and chain topology, these macromolecules form a variety of spatially periodic microphases in thermodynamic equilibrium. The kinetics of self-assembly, however, often results in initial morphologies with defects, and the subsequent ordering is protracted. Different strategies have been devised to direct the self-assembly of copolymer materials by external fields to align and perfect the self-assembled nanostructures. Understanding and controlling the thermodynamics of defects, their response to external fields, and their dynamics is important because applications in microelectronics either require extremely low defect densities or aim at generating specific defects at predetermined locations to fabricate irregular device-oriented structures for integrated circuits. In this review, we discuss defect morphologies of block copolymers in the bulk and thin films, highlighting (a) analogies to and differences from defects in other crystalline materials, (b) the stability of defects and their dynamics, and (c) the influence of external fields.