Quasi-Two-Dimensional Assembly of Bottlebrush Block Copolymers with Nanoparticles in Ultrathin Films: Combined Effect of Graft Asymmetry and Nanoparticle Size*

Block copolymer guided assembly of nanoparticles leads to the formation of nanocomposites with periodic arrangement of nanoparticles, which are important for applications, such as photonic devices and sensors. However, linear block copolymers offer limited control over the internal arrangement of nanoparticles inside their hosting domains. In contrast, bottlebrush block copolymers possess unique architectural attributes that enable additional ways to control the local organization of nanoparticles. In this work, we studied the co-assembly of 8 and 13 nm gold nanoparticles with three bottlebrush block copolymers differing in the asymmetry of their graft lengths in ultra-confined films, where assembly occurs quasi-two-dimensionally. Our results indicate that graft asymmetry could be used as an additional tool to enhance nanoparticle ordering by forcing them to localize at the center of the domain regardless of their size. This behavior is analyzed in terms of the influence of the graft asymmetry on the average conformations of the blocks.