Equilibrium surface composition of diblock copolymers

Abstract

The surface composition of a series of symmetric diblock copolymers of polystyrene (PS) and polymethylmethacrylate (PMMA) was studied using x-ray photoelectron spectroscopy (XPS). Each copolymer was composed of N segments where N ranged from 270 to 5200. At large N, where the system is highly segregated, the surface is composed only of PS, the lower surface energy component. For smaller N, where the system is in the weak segregation limit, both the PS and PMMA segments coexist at the surface. The surface excess ψ1 of PS in the weak segregation limit is well described by ψ1 = α - βN-1/2, in good agreement with mean field predictions. The constants α and β depend on the interactions between the unlike segments on the copolymer chain and on the surface energy differences between the components. We also show that the strength of the segmental interactions in the vicinity of the surface are weaker than those in the bulk. © 1990 American Institute of Physics.