Layer-by-Layer Self-Assembly of Polymers with Pairing Interactions.

A molecular theory is introduced to model the layer-by-layer self-assembly (LbL-SA) of polymers with pairing interactions. Our theory provides a general framework to describe nonelectrostatic LbL-SA as the pairing interactions generically describe the formation of bonds between two complementary chemical species, for example, hydrogen donor and acceptor in hydrogen-bonding-LbL or host and guest in host-guest-LbL. The theory predicts fundamental observations related to LbL-SA: (i) phase separation of a mixture of polymers with pairing interactions in bulk solution, (ii) linear increase in film thickness with the number of LbL adsorption steps, (iii) stoichiometry overcompensation after each adsorption step, and (iv) interpenetration of polymer layers. Importantly, this study shows that the minimal requirement for nonelectrostatic LbL is the competition of a pairing interaction and an excluded-volume repulsion. A simple analytical model based on this competition predicts the volume fraction of the layers in good agreement with the numerical predictions of the molecular theory.