Synthesis and Characterization of Amine-Epoxy-Functionalized Polystyrene-block-Poly(glycidyl methacrylate) to Manage Morphology and Covarying Properties for Self-Assembly

“Click” chemistry modification of a block copolymer to generate A-b-(B-r-C) block-random copolymers (BRCs) has been proven as an effective method to manage covarying properties of a block copolymer, such as the effective interaction parameter (χ_eff) and the surface energy difference of the two blocks (Δγ). Reported herein is a study of the modification of the glycidyl methacrylate block of polystyrene-block-poly(glycidyl methacrylate) (S-b-G) with amine-epoxy “click” chemistry. Three pairs of more polar and less polar secondary amines are selected to modify S-b-G to make a series of lamellae-forming BRCs to determine what ratio of the more polar amine in the random block (φ_C) is necessary to achieve Δγ = 0. The dependence of the χ_eff of each BRC on φ_C is determined from SAXS measurements. For advanced lithography applications, a lamellae-forming BRC with sub-10 nm features and Δγ = 0 is demonstrated. Utilizing the χ_eff – φ_C relationship, a set of BRCs are synthesized from a single S-b-G such that amine-epoxy modification generates disordered, cylindrical, gyroidal, and lamellar morphologies, depending on φ_C.