Highly aligned, large pore ordered mesoporous carbon films by solvent vapor annealing with soft shear

Macroscopic alignment of block copolymer (BCP)-templated mesoporous carbon films is challenging, especially for large pores (>10nm), due to the slow dynamics of the polymer segments that impede re-orientation of the ordered domains. Here, we demonstrate a facile method, solvent vapor annealing with soft shear (SVA–SS), to fabricate unidirectionally aligned, ordered mesoporous carbon films using two different BCP templates, poly(ethylene oxide)-block-poly(n-butyl acrylate) and polystyrene-block-poly(N,N-dimethyl-n-octadecylammonium p-styrenesulfonate), and we illustrate the efficacy of this technique for both cylindrical and spherical morphologies with relatively large accessible pores (≈15nm). This alignment is preserved through the thermopolymerization of resol and carbonization. The alignment of the mesopores impacts several key properties of these carbon films, especially for the unidirectional cylindrical mesostructures. The highly aligned mesoporous carbon films exhibit a more narrow pore size distribution than the analogous unaligned ordered mesoporous carbon as determined by ellipsometric porosimetry. Moreover, the electrical conductivity becomes anisotropic with nearly 40% difference in conductivity between parallel and perpendicular directions of the cylindrical mesopores. In the parallel orientation, the electrical conductivity is over 20% greater than the analogous unoriented (random) films. These results illustrate the applicability of SVA–SS to obtain unidirectional aligned mesoporous carbon films over large areas without additional physical or chemical templating.