Direct Observation on Spin-Coating Process of PS-b-P2VP Thin Films
- Hiroki Ogawa ,
- Mikihito Takenaka ,
- Tsukasa Miyazaki ,
- Akihiko Fujiwara ,
- Byeongdu Lee ,
- Keisuke Shimokita ,
- Eiji Nishibori , and
- Masaki Takata
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† Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
‡ Japan Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo, Hyogo 679-5198, Japan
§ Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
∥ Nitto Denko Corporation, 1-1-2, Shimohozumi, Ibaraki, Osaka 567-8680, Japan
⊥ Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
# Center for Integrated Research in Fundamental Science and Engineering, Tsukuba Research Center for Interdisciplinary Materials Science, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan
% RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo, Hyogo 679-5148, Japan
*E-mail [email protected]; Tel +81-774-38-3143; Fax +81-774-38-3146 (H.O.).
Abstract
We studied the structural development of symmetric poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) block copolymers during spin-coating using in situ grazing incidence small-angle X-ray scattering (GISAXS) measurements. During the spin-coating process, after the formation of the micelles in dilute solution, the selective solvent induced two kinds of the morphological transition. First, the disordered spherical micelles were transformed into a BCC lattice of spheres of which the (110) plane was oriented perpendicularly to the substrate surface. Second, further evaporation induced a transition from spheres on the BCC lattice into cylindrical structures. The orientation of the cylinders perpendicular to the substrate surface was induced by solvent convection perpendicular to the substrate, which occurs during rapid solvent evaporation. After this transition, vitrification of PS and P2VP prevented any further transition from cylinders to the more thermodynamically stable lamellar structures, as are generally observed as the bulk equilibrium state.
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