The use of random copolymer brushes (polystyrene-r-polymethylmethacrylate – PS-r-PMMA) to ‘neutralise’ substrate surfaces and ordain perpendicular orientation of the microphase separated lamellae in symmetric
polystyrene-b-polymethylmethacrylate (PS-b-PMMA) block copolymers (BCPs) is well known. However, less well known is how the brushes interact with both the substrate and the BCP, and how this
might change during thermal processing. A detailed study of changes in these films for different brush
and diblock PS-b-PMMA molecular weights is reported here. In general, self-assembly and pattern formation is altered little, and a range of brush molecular weights are seen to be effective. However, on
extended anneal times, the microphase separated films can undergo dimension changes and loss of order.
This process is not related to any complex microphase separation dynamics but rather a degradation of
methacrylate components in the film. The data suggest that care must be taken in interpretation of structural
changes in these systems as being due to BCP only effects.