Templated Self-Assembly of a PS-<i>Branch</i>-PDMS Bottlebrush Copolymer

The self-assembly of block copolymers (BCPs) with novel architectures offers tremendous opportunities in nanoscale patterning and fabrication. Here, the thin film morphology, annealing kinetics, and topographical templating of an unconventional Janus-type “PS-<i>branch</i>-PDMS” bottlebrush copolymer (BBCP) are described. In the Janus-type BBCP, each segment of the bottlebrush backbone connects two immiscible side chain blocks. Thin films of a Janus-type BBCP with <i>M</i>_n = 609 kg/mol exhibited 22 nm period cylindrical microdomains with long-range order under solvent vapor annealing, and the effects of as-cast film thickness, solvent vapor pressure, and composition of the binary mixture of solvent vapors are described. The dynamic self-assembly process was characterized using in situ grazing-incidence X-ray scattering. Templated self-assembly of the BBCP within lithographically patterned substrates was demonstrated, showing distinct pattern orientation and dimensions that differ from conventional BCPs. Self-consistent field theory is used to elucidate details of the templated self-assembly behavior within confinement