Adsorption of multiblock copolymers onto a chemically heterogeneous surface: A model of pattern recognition

We present a statistical mechanical model, which is used to investigate the adsorption behavior of two-letter (AB) copolymers on chemically heterogeneous surfaces. The surfaces with regularly distributed stripes of two types (A and B) and periodic multiblock copolymers (AℓBℓ)x are studied. It is assumed that A(B)-type segments selectively adsorb onto A(B)-type stripes. It is shown that the adsorption strongly depends on the copolymer sequence distribution and the arrangement of selectively adsorbing regions on the surface. The polymer-surface binding proceeds as a two-step process. At the first step, the copolymer having short blocks adsorbs onto the surface as an effective homopolymer, which does not feel chemical pattern. At the second step, when the polymer-surface attraction is sufficiently strong, the adsorbed chain adjusts its equilibrium conformation to reach the perfect bound state, thereby demonstrating ability for pattern recognition. The key element of this mechanism is the redistribution of strongly adsorbed copolymer diblocks AℓBℓ, which behave as surfactants, between multiple AB interfaces separating A and B stripes on the adsorbing surface. Such redistribution is accompanied by a well-pronounced decrease in the system entropy. We have found that marked pattern recognition is possible for copolymers with relatively short blocks at high polymer/surface affinities, beyond the adsorption threshold.