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

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

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
Volume119
Issue number43
DOIs
StatePublished - Oct 29 2015

Fingerprint

Thiophenes
Metals
Vapors
Thiophene
vapors
chemistry
thiophenes
electron transfer
Electrons
vacuum spectroscopy
Amorphous carbon
Ultrahigh vacuum
metals
Surface chemistry
Oligomers
Raman spectroscopy
Raman scattering
Chemical reactions
Polymerization
oligomers

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Understanding the Reaction Chemistry of 2,2′ : 5′,2″-Terthiophene Films with Vapor-Deposited Ag, Al, and Ca. / Sang, Lingzi; Matz, Dallas L.; Pemberton, Jeanne E.

In: Journal of Physical Chemistry C, Vol. 119, No. 43, 29.10.2015, p. 24290-24298.

Research output: Contribution to journalArticle

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AB - 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.

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