Versatile Reactive Gradient Block Copolymer System for Highly Robust Nanopatterns With Spontaneous Vertical Orientation

Abstract Vertically oriented patterns with desired physicochemical properties fabricated via directed self‐assembly of high‐χ block copolymers (BCPs) are critical for enhancing device performance, particularly in semiconductors. However, the lack of chemical structural tunability and challenges in vertically orienting the conventional high‐χ BCPs have impeded practical applications. This study introduces poly(methyl methacrylate‐ block ‐(pentafluorophenyl acrylate‐ gradient ‐styrene)), a novel reactive polymer gradient‐random block containing BCP (GRC‐BCP) system. This unique system provides structural expandability through post‐polymerization modifications. Moreover, using the tailored gradient block structure, vertically oriented patterns can be realized on diverse substrates without surface neutralization. Vertically oriented patterns with precisely controlled linewidths ranging from 7 to 13 nm are successfully achieved in organosilicon and organotin GRC‐BCPs, synthesized via this system. Furthermore, this work demonstrates that the organosilicon GRC‐BCP can be applied as a highly robust photoresist height enhancer for extreme ultraviolet lithography. After Si deep etching, this work obtains Si patterns with an aspect ratio of 5.78 at 13 nm half‐pitch, line edge roughness of 1.05 nm, and line width roughness of 1.66 nm. Offering efficient synthesis and broad utility, the reactive polymer GRC‐BCP system is expected to be expanded to various applications as a platform material where vertically oriented patterns with applicable functionalities are essential.