Quantum chemical analysis of electronic structure and n- and p-type charge transport in perfluoroarene-modified oligothiophene semiconductors

Sharon E. Koh, Bernard Delley, Julia E. Medvedeva, Antonio Facchetti, Arthur J. Freeman, Tobin J. Marks, Mark A. Ratner

Research output: Contribution to journalArticle

44 Citations (Scopus)


Density-functional theory (DFT) is employed to investigate the structural, electronic, and transport properties of several isomeric fluoroarene- oligothiophene-based semiconductors. Three oligothiophene systems varying in the perfluoroarene group positions within the molecule are studied to understand the electronic structure leading to the observed mobility values and to the n- or p-type behavior in these structures. Analyses of both intermolecular interactions in dimers and extended interactions in crystalline structures afford considerable insight into the electronic properties and carrier mobilities of these materials, as well as the polarity of the charge carriers. From the calculated carrier effective masses, we find that sterically governed molecular planarity plays a crucial role in the transport properties of these semiconductors. Our calculations correlate well with experimentally obtained geometries, highest-occupied molecular orbital (HOMO)/lowest-unoccupied molecular orbital (LUMO) energies, and the experimental carrier mobility trends among the systems investigated.

Original languageEnglish
Pages (from-to)24361-24370
Number of pages10
JournalJournal of Physical Chemistry B
Issue number48
Publication statusPublished - Dec 7 2006


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this