Discovery of hierarchical superstructures in block copolymers by integrating different liquid crystalline interactions.

Hierarchically assembled superstructures of block copolymers are discovered by introduction of the competition of anisotropy attributed from liquid crystalline ordering and nano-phase separation. When the two prototypical fields of liquid crystals (LCs), smectics (S) and nematics (N), are adjoined within the framework of diblock copolymers (S-N) in a variety of precisely tuned compositions, a novel class of superlattices with an interdigitated array of smectic layers between the nearest lamellae or cylinders are observed. This generates unconventional nano-phase separated orthorhombic (Lo) and pseudo-hexagonal (Ho) structures, where the stretched N tethers, projected regularly from the S layers, could transfer the local organization and guide the correlated assembly. This type of superstructure is highly frustrated in reversed cylindrical morphology and absent in S-coil diblock copolymers. The collective interplay of the S and N interactions with nano-phase separation induces the formation of the final complex yet equilibrium structures, providing unprecedented opportunities towards exquisite structural diversity.