American Chemical Society
ma2c02552_si_001.pdf (1.46 MB)

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

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journal contribution
posted on 2023-03-28, 15:10 authored by Hongbo Feng, Chang-Geun Chae, Christopher Eom, Gordon S. W. Craig, Stuart J. Rowan, Paul F. Nealey
“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 (χeff) 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 (φC) is necessary to achieve Δγ = 0. The dependence of the χeff of each BRC on φC 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 χeff – φC 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 φC.