, Volume 31, Issue 9, pp 1250-1259

Deviations from bulk morphologies in thin films of block copolymer/additive binary blends

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Deviations from bulk morphologies in thin films of binary blends of alkyne-functionalized diblock copolymer poly(ethylene oxide)-block-poly(n-butyl methacrylate-random-propargyl methacrylate) (PEO-b-P(nBMA-r-PgMA)) and Rhodamine B azide are reported, where thermal click reaction between the two components leads to microphase separated morphologies. Both in the bulk and in thin films, increasing the azide loading ratio resulted in the transition from a lamellar microdomain morphology to a hexagonally packed cylindrical mircodomain morphology. However, in thin films the lamellae-cylinder transition was observed at a different azide loading ratio, which was determined by film thickness. As a result, significant deviations from the bulk morphology were observed. These results indicate that surface interactions and confined geometry can play an important role in dictating the morphology in thin films of BCP/additive binary blends.

This work was financially supported by the Department of Energy Office of Basic Energy Science under Contract No. DEFG02-96ER45612(XW, TPR design of experiments, synthesis of BCP) and the NSF-supported Materials Research Science and Engineering Center and the NSF-supported Center for Hierarchical Manufacturing at University of Massachusetts Amherst(XS, WG, assistance with the GISAXS measurements). Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357. Use of the Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.
Invited paper dedicated to the memory of Prof. Bingzheng Jiang