Understanding the Reaction Chemistry of 2,2′:5′,2″-Terthiophene Films with Vapor-Deposited Ag, Al, and Ca

Lingzi Sang, Dallas L. Matz, Jeanne E. Pemberton

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5 Scopus citations


The reaction chemistry of vapor-deposited 2,2′:5′,2″-terthiophene (α-3T) solid-state thin films with postdeposited Ag, Al, and Ca is investigated in ultrahigh vacuum using Raman spectroscopy. Vapor-deposited Ag forms nanoparticles on these films and induces considerable surface enhanced Raman scattering (SERS) along with a change in molecular symmetry of adjacent α-3T and formation of Ag-S bonds; no other reaction chemistry is observed. Vapor-deposited Al and Ca undergo chemical reaction with α-3T initiated by metal-to-α-3T electron transfer. For Al, the resulting product is predominantly amorphous carbon through initial radical formation and subsequent decomposition reactions. For Ca, the spectral evidence suggests two pathways: one leading to α-3T polymerization and the other resulting in thiophene ring opening, both initiated by radical formation through Ca-to-α-3T electron transfer. These interfacial reactions reflect the complex chemistry that can occur between low work function metals and thiophene-based oligomers. This reactivity is strongly correlated with metal work function.

Original languageEnglish (US)
Pages (from-to)24290-24298
Number of pages9
JournalJournal of Physical Chemistry C
Issue number43
StatePublished - Oct 29 2015

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • General Energy
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


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