Three-dimensional packing structure and electronic properties of biaxially oriented poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2- b ]thiophene) films

Eunkyung Cho, Chad Risko, Dongwook Kim, Roman Gysel, Nichole Cates Miller, Dag W. Breiby, Michael D. McGehee, Michael F. Toney, R. Joseph Kline, Jean Luc Bredas

Research output: Contribution to journalArticlepeer-review

108 Scopus citations


We use a systematic approach that combines experimental X-ray diffraction (XRD) and computational modeling based on molecular mechanics and two-dimensional XRD simulations to develop a detailed model of the molecular-scale packing structure of poly(2,5-bis (3-tetradecylthiophene-2-yl) thieno[3,2-b]thiophene) (PBTTT-C 14) films. Both uniaxially and biaxially aligned films are used in this comparison and lead to an improved understanding of the molecular-scale orientation and crystal structure. We then examine how individual polymer components (i.e., conjugated backbone and alkyl side chains) contribute to the complete diffraction pattern, and how modest changes to a particular component orientation (e.g., backbone or side-chain tilt) influence the diffraction pattern. The effects on the polymer crystal structure of varying the alkyl side-chain length from C 12 to C 14 and C 16 are also studied. The accurate determination of the three-dimensional polymer structure allows us to examine the PBTTT electronic band structure and intermolecular electronic couplings (transfer integrals) as a function of alkyl side-chain length. This combination of theoretical and experimental techniques proves to be an important tool to help establish the relationship between the structural and electronic properties of polymer thin films.

Original languageEnglish
Pages (from-to)6177-6190
Number of pages14
JournalJournal of the American Chemical Society
Issue number14
StatePublished - Apr 11 2012

Bibliographical note

Funding Information:
The authors would like to thank Mr. Charles Chan for his competent help with the numerical computations. This investigation was supported by National Heart, Lung, and Blood Institute grant HL 16851 and North Atlantic Treaty Organization Travel and Research grant 110-80.

ASJC Scopus subject areas

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


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