Molecular packing of high-mobility diketo pyrrolo-pyrrole polymer semiconductors with branched alkyl side chains

Xinran Zhang, Lee J. Richter, Dean M. Delongchamp*, R. Joseph Kline, Matthew R. Hammond, Iain McCulloch, Martin Heeney, Raja S. Ashraf, Jeremy N. Smith, Thomas D. Anthopoulos, Bob Schroeder, Yves H. Geerts, Daniel A. Fischer, Michael F. Toney

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

384 Scopus citations


We describe a series of highly soluble diketo pyrrolo-pyrrole (DPP)-bithiophene copolymers exhibiting field effect hole mobilities up to 0.74 cm 2 V -1 s -1, with a common synthetic motif of bulky 2-octyldodecyl side groups on the conjugated backbone. Spectroscopy, diffraction, and microscopy measurements reveal a transition in molecular packing behavior from a preferentially edge-on orientation of the conjugated plane to a preferentially face-on orientation as the attachment density of the side chains increases. Thermal annealing generally reduces both the face-on population and the misoriented edge-on domains. The highest hole mobilities of this series were obtained from edge-on molecular packing and in-plane liquid-crystalline texture, but films with a bimodal orientation distribution and no discernible in-plane texture exhibited surprisingly comparable mobilities. The high hole mobility may therefore arise from the molecular packing feature common to the entire polymer series: backbones that are strictly oriented parallel to the substrate plane and coplanar with other backbones in the same layer.

Original languageEnglish (US)
Pages (from-to)15073-15084
Number of pages12
JournalJournal of the American Chemical Society
Issue number38
StatePublished - Sep 28 2011
Externally publishedYes

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry


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