Directed Self-Assembly of an Acid-Responsive Block Copolymer for Hole-Shrink Process and Pattern Transfer

Directed self-assembly (DSA) of polystyrene-block-poly (methyl methacrylate) (PS-<i>b</i>-PMMA) has garnered substantial interest for semiconductor manufacturing, particularly for fabricating contact holes and vias. However, its application is limited by the low etch selectivity between the PS and PMMA domains. Here, we report an acid-responsive block copolymer, PS-N=CH-PMMA, incorporating a Schiff base (-N=CH-) linkage between the two blocks to impart acid sensitivity. The copolymer is synthesized via aldehyde-terminated PMMA (PMMA-CHO) precursors and is fully compatible with conventional thermal annealing workflows used for PS-<i>b</i>-PMMA. Uniform thin films with vertically oriented cylindrical domains were obtained, which could be directly converted into high-fidelity PS masks through acetic acid immersion without UV exposure. Graphoepitaxial DSA in 193i pre-patterned templates produced shrink-hole patterns with reduced critical dimension (CD) and improved local CD uniformity (LCDU). The shrink-hole CD was tunable by varying PMMA-CHO molecular weights. XPS confirmed selective cleavage of Schiff base linkages at the PS/PMMA interface under acidic conditions, while Ohta-Kawasaki simulations indicated interfacial wetting asymmetry governs etch fidelity and residual layer formation. Pattern transfer into TEOS layers was achieved with minimal CD loss. Overall, the acid-cleavable BCP enables scalable, high-fidelity nanopatterning with improved etch contrast, tunable process windows, and seamless integration into existing PS-<i>b</i>-PMMA lithography platforms.