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

Sumpter, Bobby G; Meunier, Vincent; Rosei, Federico; Lipton-Duffin, J. A.; Miwa, J. A.; Kondratenko, M.; Cicoira, F.; Perepichka, D. F.

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

Full Record
Other Related Research

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 (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). National Center for Computational Sciences (NCCS)

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.

Copy to clipboard


                    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.

Copy to clipboard


                    Sumpter, Bobby G, Meunier, Vincent, Rosei, Federico, Lipton-Duffin, J. A., Miwa, J. A., Kondratenko, M., Cicoira, F., and Perepichka, D. F.. 2010.  
        "Step-by-step growth of epitaxially aligned polythiophene by surface-confined oligomerization".  United States.

Copy to clipboard


                    
@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}

}

Copy to clipboard

Journal Article:

Other availability

Find in Google Scholar

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

Atomic structure of interphase boundary enclosing bcc precipitate formed in fcc matrix in a Ni-Cr alloy

Journal Article Furuhara, T; Wada, K; Maki, T - Metallurgical Transactions, A

The atomic structure of the interphase boundary enclosing body-centered cubic (bcc) lath-shape precipitates formed in the face-centered cubic (fcc) matrix of a Ni-45 mass pct Cr alloy was examined by means of conventional and high-resolution transmission electron microscopy (HRTEM). Growth ledges were observed on the broad faces of the laths. The growth ledge terrace (with the macroscopic habit plane {approximately}(112){sub fcc}//(23{bar 1}){sub bcc}) contains a regular array of structural ledges whose terrace is formed by the (111){sub fcc}//(110){sub bcc} planes. A structural ledge has an effective Burgers vector corresponding to an a/12[1{bar 2}1]{sub fcc} transformation dislocation in the fcc {yields}more »« less
https://doi.org/10.1007/BF02670668
BTA inhibition mechanism on clean Cu(110) surface by ultraviolet photoemission spectroscopy (UPS) and scanning tunneling microscope (STM)

Conference Cho, K; Park, Y; Kuk, Y; ...

Adsorption and film growth of the Benzotriazole (BTA) on a copper (110) surface were investigated by the angle-resolved ultra-violet photoemission (UPS), and scanning tunneling microscope (STM). Coverage dependence of the BTA adsorbed structure on the Cu (110) surface exhibited well-ordered c(4 x 2)structure by STM image and sharp low-energy electron diffraction (LEED) pattern. Further deposition of BTA on monolayer film, polymerized BTA images were observed while a sharp LEED pattern changed to a c(4 x 2). In a good agreement with STM results, UPS spectra of BTA film by coverage dependence showed that BTA adsorbed flat up to 1 monolayermore »« less
The structure and reactivity of adsorbates on stepped Rh and Pt surfaces investigated by LEED, HREELS, TPD, XPS and STM

Technical Report Batteas, J

Defects on surfaces such as steps play an important role in surface chemistry. In order to obtain an understanding of the influence of steps in surface chemical reactions, the structure and reactivity of small molecules (O{sub 2}, CO, H{sub 2}S, and C{sub 2}H{sub 4}) on atomically stepped surfaces of RH and Pt have been investigated. The detailed structures of CO and oxygen bonded to the Rh(110) surface were determined. The CO molecules bond near the short bridge sites with the CO molecular axis tilted approximately 24{degree} from the surface normal. Oxygen atoms are bound asymmetrically in the 3-fold fcc hollow-sitesmore »« less
https://doi.org/10.2172/125019

Full Text Available
{ital Ab} {ital initio} calculations of energies and self-diffusion on flat and stepped surfaces of Al and their implications on crystal growth

Journal Article Stumpf, R; Scheffler, M - Physical Review, B: Condensed Matter

Using density-functional theory we investigate properties of Al(111), Al(100), Al(110), and stepped Al(111) surfaces, including formation energies of surfaces, steps, adatoms, and vacancies. For adsorption and diffusion of Al on flat regions of Al(111) surfaces hcp site is energetically slightly preferred over the fcc site. Energy barrier for self-diffusion on Al(111) is very low (0.04 eV). Close to either of the two sorts of close packed, monoatomic steps on Al(111), Al adatoms experience indirect attraction of {approx_lt} 0.1 eV with the step edge, which has a range of several atomic spacings and is of electronic origin. At the lower stepmore »« less
https://doi.org/10.1103/PhysRevB.53.4958
Polythiophene thin films by surface-initiated polymerization: Mechanistic and structural studies

Journal Article Youm, Sang; Hwang, Euiyong; Chavez, Carlos; ... - Chemistry of Materials

The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g., spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of presynthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. Herein, we describe themore »« less
Cited by 3
https://doi.org/10.1021/acs.chemmater.6b01957

Full Text Available

Similar Records