Abstract
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.
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