Herein, we report the cooperative self-assembly of nanoparticles and block copolymers at the air-water interface, which can generate highly uniform and readily transferable composite films with tunable nanoscale architecture and functionalities. Interestingly, the incorporation of nanoparticles significantly affects the self-assembly of block copolymers at the interface. The nanoparticle-induced morphology change occurs through distinct mechanisms depending on the volume fraction of the hydrophobic block. For block copolymers with a relatively small hydrophobic volume fraction, the morphology transition occurs through the nanoparticle-induced swelling of a selective block. When the hydrophobic volume fraction is large enough, added nanoparticles promote the breath figure assembly, which generates uniform honeycomb-like porous structures with unusual nanoscale periodicity. This approach is generally applicable to various types of nanoparticles, constituting a simple one-step method to porous thin films with various functionalities.
Keywords: block copolymer; breath figure; interface; nanoparticle; porous; self-assembly.