Step-by-step growth of epitaxially aligned polythiophene by surface-confined oligomerization
Abstract
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-EDOT chains, using the substrate (the 110 facet of copper) simultaneously as template and catalyst for polymerization. Copper acts as promoter for the Ullmann coupling reaction, while the inherent anisotropy of the fcc 110 facet confines growth to a single dimension. High resolution scanning tunneling microscopy (STM) performed under ultra high 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 PEDOT oligomers, which stand on the sulphur 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.
- Authors:
-
- ORNL
- INRS-EMT, Universite du Quebec
- McGill University, Montreal, Quebec
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Center for Nanophase Materials Sciences; Center for Computational Sciences
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 986411
- DOE Contract Number:
- DE-AC05-00OR22725
- Resource Type:
- Journal Article
- Journal Name:
- Proceedings of the National Academy of Sciences
- Additional Journal Information:
- Journal Volume: 107; Journal Issue: 25; Journal ID: ISSN 0027-8424
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; EPITAXY; POLYCYCLIC SULFUR HETEROCYCLES; POLYMERIZATION; COPPER; CATALYTIC EFFECTS; SUBSTRATES; DENSITY FUNCTIONAL METHOD; SCANNING TUNNELING MICROSCOPY
Citation Formats
Sumpter, Bobby G, Meunier, Vincent, Rosei, Federico, Lipton-Duffin, J. A., Miwa, J. A., Kondratenko, M., Cicoira, F., and Perepichka, D. F. Step-by-step growth of epitaxially aligned polythiophene by surface-confined oligomerization. United States: N. p., 2010.
Web.
Sumpter, Bobby G, Meunier, Vincent, Rosei, Federico, Lipton-Duffin, J. A., Miwa, J. A., Kondratenko, M., Cicoira, F., & Perepichka, D. F. Step-by-step growth of epitaxially aligned polythiophene by surface-confined oligomerization. United States.
Sumpter, Bobby G, Meunier, Vincent, Rosei, Federico, Lipton-Duffin, J. A., Miwa, J. A., Kondratenko, M., Cicoira, F., and Perepichka, D. F. Fri .
"Step-by-step growth of epitaxially aligned polythiophene by surface-confined oligomerization". United States.
@article{osti_986411,
title = {Step-by-step growth of epitaxially aligned polythiophene by surface-confined oligomerization},
author = {Sumpter, Bobby G and Meunier, Vincent and Rosei, Federico and Lipton-Duffin, J. A. and Miwa, J. A. and Kondratenko, M. and Cicoira, F. and Perepichka, D. F.},
abstractNote = {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-EDOT chains, using the substrate (the 110 facet of copper) simultaneously as template and catalyst for polymerization. Copper acts as promoter for the Ullmann coupling reaction, while the inherent anisotropy of the fcc 110 facet confines growth to a single dimension. High resolution scanning tunneling microscopy (STM) performed under ultra high 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 PEDOT oligomers, which stand on the sulphur 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.},
doi = {},
url = {https://www.osti.gov/biblio/986411},
journal = {Proceedings of the National Academy of Sciences},
issn = {0027-8424},
number = 25,
volume = 107,
place = {United States},
year = {2010},
month = {1}
}