Step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction

J. A. Lipton-Duffin, J. A. Miwa, M. Kondratenko, F. Cicoira, B. G. Sumpter, V. Meunier, D. F. Perepichk, F. Rosei

Research output: Contribution to journalArticlepeer-review

109 Scopus citations


One of the great challenges in surface chemistry is to assemble aromatic building blocks into ordered structures that are mechanically robust and electronically interlinked - i.e., are held together by covalent bonds. We demonstrate the surface-confined growth of ordered arrays of poly(3,4-ethylenedioxythiophene) (PEDOT) chains, by using the substrate (the 110 facet of copper) simultaneously as template and catalyst for polymerization. Copper acts as promoter for the Ullmann coupling reaction, whereas the inherent anisotropy of the fcc 110 facet confines growth to a single dimension. High resolution scanning tunneling microscopy performed under ultrahigh vacuum conditions allows us to simultaneously image PEDOT oligomers and the copper lattice with atomic resolution. Density functional theory calculations confirm an unexpected adsorption geometry of the PEDOToligomers, which stand on the sulfur atom of the thiophene ring rather than lying flat. This polymerization approach can be extended to many other halogen-terminated molecules to produce epitaxially aligned conjugated polymers. Such systems might be of central importance to develop future electronic and optoelectronic devices with high quality active materials, besides representing model systems for basic science investigations.

Original languageEnglish (US)
Pages (from-to)11200-11204
Number of pages5
JournalProceedings of the National Academy of Sciences of the United States of America
Issue number25
StatePublished - Jun 22 2010

All Science Journal Classification (ASJC) codes

  • General


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