n-channel polymers by design: Optimizing the interplay of solubilizing substituents, crystal packing, and field-effect transistor characteristics in polymeric bithiophene-imide semiconductors

Joseph A. Letizia, Michael R. Salata, Caitlin M. Tribout, Antonio Facchetti*, Mark A. Ratner, Tobin J. Marks

*Corresponding author for this work

Research output: Contribution to journalArticle

228 Scopus citations

Abstract

Electron transporting (n-channel) polymer semiconductors for field-effect transistors are rare. In this investigation, the synthesis and characterization of new electron-depleted N-alkyl-2,2′-bithiophene-3,3′- dicarboximide-based π-conjugated homopolymers and copolymers containing the 2,2′-bithiophene unit are reported. A novel design approach is employed using computational modeling to identify favorable monomer properties such as core planarity, solubilizing substituent tailorability, and appropriate electron affinity with gratifying results. Monomeric model compounds are synthesized to confirm these properties, and a crystal structure reveals a short 3.43 Å π-π stacking distance with favorable solubilizing substituent orientations. A family of 10 homopolymers and bithiophene copolymers is then synthesized via Yamamoto and Stille polymerizations, respectively. Two of these polymers are processable in common organic solvents: the homopolymer poly(N-(2-octyldodecyl)-2,2′-bithiophene-3,3′-dicarboximide) (P1) exhibits n-channel FET activity, and the copolymer poly(N-(2-octyldodecyl)-2, 2′:5′,2″:5″,2‴-quaterthiophene-3, 3′-dicarboximide) (P2) exhibits air-stable p-channel FET operation. After annealing, P1 films exhibit a very high degree of crystallinity and an electron mobility > 0.01 cm2 V-1 s-1 with a current on-off ratio of 107, which is remarkably independent of film-deposition conditions. Extraordinarily, P1 films also exhibit terracing in AFM images with a step height matching the X-ray diffraction d spacing, a rare phenomenon for polymeric organic semiconductors. Another fascinating property of these materials is the air-stable p-channel FET performance of annealed P2 films, which exhibit a hole mobility of ∼0.01 cm2 V-1 s-1 and a current on-off ratio of 107.

Original languageEnglish (US)
Pages (from-to)9679-9694
Number of pages16
JournalJournal of the American Chemical Society
Volume130
Issue number30
DOIs
StatePublished - Jul 30 2008

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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