Confined crystallization in lamellae forming poly(3-(2′-ethyl)hexylthiophene) (P3EHT) block copolymers

Emily C. Davidson, Bryan S. Beckingham, Victor Ho, Rachel A. Segalman

Research output: Contribution to journalArticlepeer-review

20 Scopus citations


Charge transport in poly(3-alkylthiophene)s (P3AT)s is closely linked to the nanoscale organization of crystallites. Block copolymer morphologies provide an ideal platform to study crystallization as the chain ends are tethered at a known interface in a well-defined geometry. The impact of soft versus hard confinement on P3EHT crystallization was studied using poly(3-(2′-ethyl)hexylthiophene) (P3EHT) containing diblocks with both rubbery poly(methyl acrylate) (PMA) and glassy polystyrene (PS) blocks. Here, P3EHT's lower melting point relative to the commonly studied poly(3-hexylthiophene) (P3HT) facilitated its confined crystallization and makes it an ideal model system. While transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) revealed well-ordered lamellar morphologies both in the melt and post-crystallization for both sets of diblocks, the glassy blocks inhibit confined crystallization of P3EHT relative to rubbery matrix blocks. Analysis of aligned diblocks by both SAXS and wide angle X-ray scattering (WAXS) revealed that the P3EHT chain axis aligns perpendicular to domain interfaces, allowing preferential growth of the alkyl-chain and π-π stacking directions parallel to lamellae. Finally, it was shown that following diblock self-assembly in the melt, crystallite growth drives expansion of microdomains to match the P3EHT contour length. It was concluded that P3EHT chains adopted an extended conformation within confined crystallites due to the rigid nature of polythiophenes relative to flexible chain crystalline polymers.

Original languageEnglish (US)
Pages (from-to)205-215
Number of pages11
JournalJournal of Polymer Science, Part B: Polymer Physics
Issue number2
StatePublished - Jan 15 2016
Externally publishedYes

All Science Journal Classification (ASJC) codes

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


  • block copolymer
  • confined crystallization
  • conjugated polymer
  • polymer crystallization
  • polythiophene


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