Synthesis and Characterization of Methacrylamide‐Based Block Random Copolymers via Amine Functionalization of Polystyrene‐ <i>Block</i> ‐Poly(Pentafluorophenyl Methacrylate) Toward Enhanced Amenability to Manufacturing Criteria in Nanolithography

ABSTRACT Recent interest in manipulating the chemistry of block copolymers (BCPs) to manage the covarying properties necessary to meet manufacturing criteria in nanolithography has resulted in the development and expansion of the A‐ block ‐(B‐ random ‐C) BCP architecture, where the random block allows for the decoupling of thermodynamic and wetting properties. Previous reports of such BCPs have used click chemistry to create the desired random block, but all such instances possess additional functional groups that are susceptible to undesirable side reactions upon annealing, such as cross‐linking and surface grafting. This study reports the substitution reaction of polystyrene‐ block ‐poly(pentafluorophenyl methacrylate) (PS‐ b ‐PPFMA) with primary amines. The resulting methacrylamide structure of the functionalized random block has only an amide linkage between the attached functional group and the polymer backbone, thereby omitting any sources of side reactions within the BCP. The outcomes of this report also demonstrate the enhanced thermal stability of these materials by virtue of their stable amide bonds. A range of random copolymer compositions is assessed to develop BCPs in which the random block has approximately the same surface energy as the PS block. These BCPs can self‐assemble into perpendicular lamellae and are therefore promising candidates for directed self‐assembly.