One-dimensional self-confinement promotes polymorph selection in large-area organic semiconductor thin films

Gaurav Giri, Ruipeng Li, Detlef Matthias Smilgies, Erqiang Li, Ying Diao, Kristina M. Lenn, Melanie Chiu, Debora W. Lin, Ranulfo A. Allen, Julia A. Reinspach, Stefan C B Mannsfeld, Sigurdur T Thoroddsen, Paulette Clancy, Zhenan Bao, Aram Amassian

Research output: Contribution to journalArticlepeer-review

121 Scopus citations


A crystal's structure has significant impact on its resulting biological, physical, optical and electronic properties. In organic electronics, 6,13(bis-triisopropylsilylethynyl)pentacene (TIPS-pentacene), a small-molecule organic semiconductor, adopts metastable polymorphs possessing significantly faster charge transport than the equilibrium crystal when deposited using the solution-shearing method. Here, we use a combination of high-speed polarized optical microscopy, in situ microbeam grazing incidence wide-angle X-ray-scattering and molecular simulations to understand the mechanism behind formation of metastable TIPS-pentacene polymorphs. We observe that thin-film crystallization occurs first at the air-solution interface, and nanoscale vertical spatial confinement of the solution results in formation of metastable polymorphs, a one-dimensional and large-area analogy to crystallization of polymorphs in nanoporous matrices. We demonstrate that metastable polymorphism can be tuned with unprecedented control and produced over large areas by either varying physical confinement conditions or by tuning energetic conditions during crystallization through use of solvent molecules of various sizes. © 2014 Macmillan Publishers Limited.
Original languageEnglish (US)
JournalNature Communications
Issue number1
StatePublished - Apr 16 2014

ASJC Scopus subject areas

  • General Biochemistry, Genetics and Molecular Biology
  • General Chemistry
  • General Physics and Astronomy


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