298b Symmetry Breaking in Block Copolymer Thin Films

Eric Cochran1, Gila E. Stein2, Glenn H. Fredrickson2, and Edward Kramer2. (1) Chemical and Biological Engineering, Iowa State University, 1035 Sweeny Hall, Iowa State University, Ames, IA 50011-2230, (2) Materials Research Lab, University of California, Santa Barbara, CA 93106

Recent experiments by Stein and Kramer show that thin films of poly(styrene-b-vinylpyridine) diblock copolymer undergo a discontinuous transformation from hexagonally-close packed spheres to a Fmmm orthorhombic packing as the thickness of the film is increased; beyond the hcp-Fmmm transition, the unit cell deforms to asymptotically approach bcc symmetry, which is preferred in the bulk system. We use a Landau-type theory to construct various scenarios of symmetry-breaking in this system. High resolution SCFT calculations show the nature of the competition between the preferred packing in the bulk and that at the interface. We conclude that character of the transition from thin-film to bulk behavior may be either continuous or discontinuous, depending on the degree of the block copolymer segregation.