Core–Shell and Zigzag Nanostructures from a Thin Film Silicon-Containing Conformationally Asymmetric Triblock Terpolymer

The self-assembly of multiblock copolymers generates diverse hierarchical nanostructures and greatly extends the range of microdomain geometries beyond those produced by diblock copolymers. We report the synthesis of a conformationally asymmetric ABC triblock terpolymer in which the end blocks are a mesogen-jacketed liquid crystalline polymer and poly­(dimethylsiloxane), respectively, and its self-assembly under mixed solvent vapor annealing forms a range of sphere, cylinder, and perforated lamellar core–shell morphologies, as well as stacked multilevel structures. Sub-7 nm diameter SiO_x nanopatterns were generated by selective plasma etching of the small volume fraction Si-containing core block giving a line/space ratio of ∼1:4. Moreover, the conformational asymmetry of this terpolymer leads to zigzag cylinders on a flat substrate and stable cylinder alignment transverse to template sidewalls within lithographically patterned trenches.