Dependence of thin polystyrene films stability on the thickness of grafted polystyrene brushes

We investigate the stability of thin polystyrene (PS) films on chemically identical grafted brushes of various thickness and grafting density. We observe an essential influence of the brush thickness on the stability of the PS films. For brushes with a thickness of 20-35 nm no de-wetting of the PS film occurs, while considerably thicker or thinner PS brushes lead to de-wetting of the PS top layer. We suggest that in the thin brush-like layers, the unfavorable interactions with underlying silica favor de-wetting. The tendency to de-wet is reduced once the brush is sufficiently thick to insulate the free PS layer from the surface. Beyond that point, the de-wetting process speeds up as the brush becomes thicker and has a higher grafting density with a substantial increase of the interfacial tension between the brush and the free polymer.