Ongoing efforts in materials science have resulted in linear block copolymer systems that generate nanostructures via the phase separation of immiscible blocks; however, such systems are limited with regard to their domain miniaturization and lack of orientation control. We overcome these limitations through the bicyclic topological alteration of a block copolymer system. Grazing incidence X-ray scattering analysis of nanoscale polymer films revealed that bicyclic topologies achieve 51.3-72.8% reductions in domain spacing when compared against their linear analogue, which is more effective than the theoretical predictions for conventional cyclic topologies. Moreover, bicyclic topologies achieve unidirectional orientation and a morphological transformation between lamellar and cylindrical domains with high structural integrity. When the near-equivalent volume fraction between the blocks is considered, the formation of hexagonally packed cylindrical domains is particularly noteworthy. Bicyclic topological alteration is therefore a powerful strategy for developing advanced nanostructured materials for microelectronics, displays, and membranes.
Keywords: grazing incidence X-ray scattering; phase separated nanostructures; thin film morphology; topological alteration; topological block copolymers; unidirectional orientation.