Molecular and microdomain orientation in semicrystalline block copolymer thin films by directional crystallization of the solvent and epitaxy

Chealmin Park, Claudio De Rasa, Bernard Lotz, Lewis J. Fetters, Edwin L. Thomas

Research output: Contribution to journalArticlepeer-review

36 Citations (Scopus)


The directional crystallization of crystallizable of crystalline blocks onto the surface of crystalline substrates in semicrystalline block copolymers, control both molecular chain orientation of the crystalline block and the microdomain structure of the block copolymer. Thin film of semicrystalline polystyrene-block-poly(ethylene-alt-propylene)-block-polyethylene (PS/PEP/PE) ferpolymer and polystyrene-block-polyethylene (PS/PE) diblock copolymer, which both contain crystallizable polyethylene (PE) blocks, have been patterned-using benzoic acid (BA) and anthracene (AN) as crystallizable solvents. The directional crystallization induces orientation of the microdomains and epitaxy, due to the crystallographic matching of unit cells between the crystalline. PE blocks and the crystalline organic substrates, resulting in the development of highly aligned crystalline PE blocks. The orientation of the PE crystals onto the substrate is evidenced by selected area electron diffraction and bright field transmission electron microscope images. In the case of the PS/PEP/PE terpolymer, the process induces the PS cylinders to align parallel to the b axis of the BA crystals. Long crystalline PE lamellae are oriented edge-on on the BA surface, with the b axis of PE parallel to the b axis of BA, and parallel to the PS cylinders. In the case of the PS/PE diblock copolymer the PE cylinders are oriented perpendicular to substrate, packed on a hexagonal lattice. Each cylinder contains precisely one crystalline PE lamella oriented edge-on on the substrate. When BA is used, the PE lamellae inside cylinders are oriented with the b axis parallel to the b axis of BA crystals. When AN is used, due to the different epitaxial relationship between PE block and AN crystals, the PE lamellae are oriented along two equivalent directions, with the c axis parallel to the [110] and [110] direction of AN crystals.

Original languageEnglish
Pages (from-to)1514-1523
Number of pages10
JournalMacromolecular Chemistry and Physics
Issue number12
Publication statusPublished - 2003 Aug 18

All Science Journal Classification (ASJC) codes

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry


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