Journal of Chemical Physics, Vol.101, No.4, 3367-3377, 1994
Microphase Separation in Thin-Films of the Symmetrical Diblock-Copolymer Melt
By means of Monte Carlo simulations of a lattice model, microphase separation transition of symmetric diblock-copolymer melts confined in the thin-film geometry between parallel hard walls is studied. We impose a surface field which acts repulsively only on one of the two species, to stabilize lamellar order parallel to the surfaces. However, interplay between two characteristic lengths, that is, the natural thickness of the lamellar l and the thickness of the film D, causes complicated behavior. In case that the two lengths are compatible with each other, clear lamellar order parallel to the surfaces is observed at temperatures lower than the bulk transition temperature, as expected. On the other hand, tilted or deformed lamellar structure, or even coexistence of lamellae in different orientations are found in cases of strong conflict. In both cases, lamellae are fully established. Even at temperature higher than the bulk transition temperature, weak order is induced by the surface field, and a gradual transition between such surface-induced order and bulklike order is observed. Film thickness and temperature dependence of the ordered structure is discussed, as well as a density reduction near the walls and in the interfaces between the segregated regions.
Keywords:SURFACE-INDUCED ORIENTATION;BLOCK-COPOLYMERS;MONTE-CARLO;NEUTRON REFLECTIVITY;MORPHOLOGY;MICRODOMAINS;POLYSTYRENE;CONSTRAINTS;MICROSCOPY;POLYMERS