Directing block copolymer self-assembly with permanent magnets: Photopatterning microdomain alignment and generating oriented nanopores

Magnetic fields are useful for directing block copolymer (BCP) self-assembly, but to date such a field alignment has required large fields (>5 T) necessitating the use of superconducting magnets. We report an approach that circumvents this limitation by introducing labile reactive mesogens into a liquid crystalline (LC) BCP based on a norbornene backbone with a poly(lactide) minority block that forms hexagonally packed cylinders. The free mesogens co-assemble with the smectic A mesophase of the BCP and enable alignment at fields as low as 0.5 T. The remarkable field response originates from the combined effects of enhanced mobility and decreased segregation strength, and the presence of large micron-scale grains in the system. We demonstrate a robust alignment of mesogen-blended samples using simple permanent magnets. The etching of poly(lactide) yields nanoporous films, while the spatially selective microdomain immobilization by UV-induced crosslinking through a photomask provides a versatile mechanism for creating alignment patterns. We anticipate that the nanoporous materials as generated here may find application in membrane fabrication or BCP lithography, while the ability to spatially pattern alignment is promising for the design of mechanical metamaterials exploiting the shape memory effect of LC elastomers

Controlling orientational order in block copolymers using low-intensity magnetic fields.

The interaction of fields with condensed matter during phase transitions produces a rich variety of physical phenomena. Self-assembly of liquid crystalline block copolymers (LC BCPs) in the presence of a magnetic field, for example, can result in highly oriented microstructures due to the LC BCP's anisotropic magnetic susceptibility. We show that such oriented mesophases can be produced using low-intensity fields (4 T) and superconducting magnets required to date. Low-intensity field alignment is enabled by the addition of labile mesogens that coassemble with the system's nematic and smectic A mesophases. The alignment saturation field strength and alignment kinetics have pronounced dependences on the free mesogen concentration. Highly aligned states with orientation distribution coefficients close to unity were obtained at fields as small as 0.2 T. This remarkable field response originates in an enhancement of alignment kinetics due to a reduction in viscosity, and increased magnetostatic energy due to increases in grain size, in the presence of labile mesogens. These developments provide routes for controlling structural order in BCPs, including the possibility of producing nontrivial textures and patterns of alignment by locally screening fields using magnetic nanoparticles