Thin films of lamellar poly(styrene-b-methyl methacrylate) (PS-PMMA) block copolymers were prepared on brushed
silicon substrates with a range of thicknesses. The brushes are expected to eliminate preferential interactions at the
substrate, thereby enabling perpendicular domain orientations relative to the interfaces. Using a combination of surface
microscopy and grazing incidence small-angle X-ray scattering, we demonstrate that i) the brushed substrates are weakly
preferential to PMMA; and ii) the average lamellar domain orientation is perpendicular to the substrate, but some
domains are mis-oriented by up to 40º. We propose that PMMA domains deform to increase their contact area at the
slightly preferential substrate, and this behavior drives the formation of out-of-plane defects such as bent or tilted
domains. These outcomes suggest that depth-resolved measurements are needed to fully optimize materials and
processes for block copolymer lithography.
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