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

Title: Step-by-step growth of epitaxially aligned polythiophene by surface-confined oligomerization

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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:

Sumpter, Bobby G ^[1]; Meunier, Vincent ^[1]; Rosei, Federico ^[2]; Lipton-Duffin, J. A. ^[2]; Miwa, J. A. ^[2]; Kondratenko, M. ^[3]; Cicoira, F. ^[2]; Perepichka, D. F. ^[3]

ORNL
INRS-EMT, Universite du Quebec
McGill University, Montreal, Quebec

Publication Date:: 2010-01-01

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.

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                    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.

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                    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.

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@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}

}

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