Kinetic Pathway Dependent Supramolecular Nanocomposite Assembly on Patterned Substrates

Block copolymer (BCP)-based supramolecular nanocomposites are promising materials to create hierarchically structured materials and incorporate and organize nanoparticles (NPs). Assembling these materials on lithographically patterned substrates combines the advantages of “bottom-up” and “top-down” assembly to yield materials where the exact ordering and placement of NPs can be controlled. However, for traditional BCP self-assembly on patterned substrates, the width of the underlying pattern must be commensurate with the periodicity of the BCP due to thermodynamic constraints. Here, supramolecular nanocomposites are assembled onto several different geometrically patterned substrates, including lines and concentric circles. On these patterns, incommensurability between the pattern and the supramolecule periodicity was not observed. Instead, the supramolecule self-adjusts to a smaller, non-equilibrium periodicity in the trench. This phenomenon is attributed to the kinetic pathway taken during assembly.