Self-assembly, molecular ordering, and charge mobility in solution-processed ultrathin oligothiophene films

Amanda R. Murphy, Paul C. Chang, Priscilla VanDyke, Jinsong Liu, Jean Frechet*, Vivek Subramanian, Dean M. DeLongchamp, Sharadha Sambasivan, Daniel A. Fischer, Eric K. Lin

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

65 Scopus citations


Symmetrical α,ω-substituted quarter-(T4), penta-(T5), sexi-(T6), and heptathiophene (T7) oligomers containing thermally removable aliphatic ester solubilizing groups were synthesized, and their UV-vis and thermal characteristics were compared. Spun-cast thin films of each oligomer were examined with atomic force microscopy and near-edge X-ray absorption fine structure spectroscopy to evaluate the ability of the material to self-assemble from a solution-based process while maintaining complete surface coverage. Films of the T5-T7 oligomers self-assemble into crystalline terraces after thermal annealing with higher temperatures required to affect this transformation as the size of the oligomers increases. A symmetrical α,ω-substituted sexithiophene (T6-acid) that reveals carboxylic acids after thermolysis was also prepared to evaluate the effect of the presence of hydrogen-bonding moieties. The charge transport properties for these materials evaluated in top-contact thin film transistor devices were found to correlate with the observed morphology of the films. Therefore, the T4 and the T6-acid performed poorly because of incomplete surface coverage after thermolysis, while T5-T7 exhibited much higher performance as a result of molecular ordering. Increases in charge mobility correlated to increasing conjugation length with measured mobilities ranging from 0.02 to 0.06 cm 2/(V·s). The highest mobilities were measured when films of each oligomer had an average thickness between one and two monolayers, indicating that the molecules become exceptionally well-ordered during the thermolysis process. This unprecedented ordering of the solution-cast molecules results in efficient charge mobility rarely seen in such ultrathin films.

Original languageEnglish (US)
Pages (from-to)6033-6041
Number of pages9
JournalChemistry of Materials
Issue number24
StatePublished - Nov 29 2005

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry


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