Step-by-step growth of epitaxially aligned polythiophene by surface-confined oligomerization
(Result of the month 07/2010)

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.
Low-coverage EDOT molecules on Cu(110) self-organize into stacks. (A) STM image showing stacks of EDOT molecules on Cu(110) subsequent to a five-minute DIEDOT exposure [V = −365 mV, I = 1.0 nA, (8.9 nm)2. The surrounding bare regions of the Cu(110) substrate exhibit a (1 × 1) symmetry. The positions of the molecules in the stack are shown, as calculated by DFT viewed from (B) the front and (C) the top. The model shows Cu atoms lifted out of the top substrate layer to participate in bonding to the EDOT molecule.
Higher coverages of EDOT results in the formation of a well-organized oligomer overlayer. (A) STM image of this higher-coverage surface reveals doubling and tripling of the stack elements [V = −1.06 V, I = 1.1 nA, (14.4 nm)2. In this image we observe monomer (1), dimer (2), trimer (3), and tetramer (4) stacks, surrounded by a (brighter) region of species in a (2 × 2) reconstruction in a layer above. High resolution STM data and DFT calculated structures are shown for (B) dimer and (C) trimer stacks.


Authors:
J. A. Lipton-Duffin (1,2), J. A. Miwaa,b, M. Kondratenko (2,3), F. Cicoiraa (2), B. G. Sumpterd (4), V. Meunierd (1), D. F. Perepichk (1,2,3) and F. Rosei (1,2)

(1) INRS-ÉMT, Université du Québec, 1650 Boulevard Lionel-Boulet, Varennes, QC J3X 1S2 Canada;
(2) Center for Self-Assembled Chemical Structures and
(3) Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montréal, QC, H3A 2K6 Canada;
(4) Oak Ridge National Laboratory, P.O. Box 2008 MS6367, Oak Ridge, TN 37831-636

Institute web-pages:
http://www.nanofemtolab.qc.ca/
http://www.emt.inrs.ca

Journal:
http://www.pnas.org/cgi/doi/10.1073/pnas/1000726107/

 
This result has been obtained with :
Variable Temperature UHV SPM

 download as pdf

 
 
RoM Archive
Step-by-step growth of epitaxially aligned polythiophene by surface-confined oligomerization Step-by-step growth of epitaxially aligned polythiophene by surface-confined oligomerization
(RoM 07/2010)
Pre-Nucleation Dynamics of Organic Molecule Self-Assembly Investigated by PEEM Pre-Nucleation Dynamics of Organic Molecule Self-Assembly Investigated by PEEM
(RoM 06/2010)
Many-body effects in electronic bandgaps of carbon nanotubes measured by scanning tunnelling spectroscopy Many-body effects in electronic bandgaps of carbon nanotubes measured by scanning tunnelling spectroscopy
(RoM 05/2010)
Metal-rich Au-silicide nanoparticles for use in nanotechnology Metal-rich Au-silicide nanoparticles for use in nanotechnology
(RoM 04/2010)
Atomic resolution on the Si (5 5 12) surface Atomic resolution on the Si (5 5 12) surface
(RoM 03/2010)
Transport through a Single Octanethiol Molecule Transport through a Single Octanethiol Molecule
(RoM 02/2010)
Constructing an Array of Anchored Single-Molecule Rotors on Gold Surfaces Constructing an Array of Anchored Single-Molecule Rotors on Gold Surfaces
(RoM 01/2010)
New structural model for the Si(331)-(12x1) surface reconstruction New structural model for the Si(331)-(12x1) surface reconstruction
(RoM 12/2009)
Structure investigation of the (100) surface of the orthorhombic Al<sub>13</sub>Co<sub>4</sub> crystal Structure investigation of the (100) surface of the orthorhombic Al13Co4 crystal
(RoM 11/2009)
qPlus atomic force microscopy of the Si(100) surface: <br>Buckled, split-off, and added dimers qPlus atomic force microscopy of the Si(100) surface:
Buckled, split-off, and added dimers
(RoM 10/2009)
Spatially-resolved, energy-filtered imaging of core level and valence band photoemission of highly p and n doped silicon patterns Spatially-resolved, energy-filtered imaging of core level and valence band photoemission of highly p and n doped silicon patterns
(RoM 09/2009)
Contrast inversion in non-contact atomic force microscopy imaging of C60 molecules Contrast inversion in non-contact atomic force microscopy imaging of C60 molecules
(RoM 08/2009)
Mapping the Electronic Surface Potential of Nanostructured Surfaces Mapping the Electronic Surface Potential of Nanostructured Surfaces
(RoM 07/2009)
Detection of Ga suboxides and their impact on III-V passivation and Fermi-level pinning Detection of Ga suboxides and their impact on III-V passivation and Fermi-level pinning
(RoM 06/2009)
Beam Deflection AFM with QPlus AFMCustomized Beam Deflection AFM with QPlus AFMCustomized
(RoM 05/2009)
Morphological work function dependence of rare-earth disilicide metal nanostructures Morphological work function dependence of rare-earth disilicide metal nanostructures
(RoM 04/2009)
Self-Organized Atomic Gold Chains on Ge(001) Self-Organized Atomic Gold Chains on Ge(001)
(RoM 03/2009)
Electric field response of a vibrationally excited molecule in an STM junction Electric field response of a vibrationally excited molecule in an STM junction
(RoM 02/2009)
Playing Pinball with Atoms Playing Pinball with Atoms
(RoM 01/2009)
C<SUB>60</SUB> / Corannulene on Cu(110) C60 / Corannulene on Cu(110)
(RoM 12/2008)
Thermal and Mechanical Actuation of Single-Molecule Rotors Thermal and Mechanical Actuation of Single-Molecule Rotors
(RoM 11/2008)
High-Resolution STM Imaging and Molecular Modeling High-Resolution STM Imaging and Molecular Modeling
(RoM 10/2008)
Configuration dependent critical nuclei in the self assembly of magic cluster Configuration dependent critical nuclei in the self assembly of magic cluster
(RoM 09/2008)
Panorama View with UHV Gemini Column and External SED Panorama View with UHV Gemini Column and External SED
(RoM 06/2008)
Colour overlay of angular maps from Cu 3d and sp hyprid peaks Colour overlay of angular maps from Cu 3d and sp hyprid peaks
(RoM 05/2008)
Molceular Assembly of Rubrene on a Metal/Metal Oxide Nanotemplate Molceular Assembly of Rubrene on a Metal/Metal Oxide Nanotemplate
(RoM 04/2008)
Temperature-dependent self-assemblies of C<SUB>60</SUB> on (1x2)-Pt (110): an STM/DFT Investigation Temperature-dependent self-assemblies of C60 on (1x2)-Pt (110): an STM/DFT Investigation
(RoM 03/2008)
Stable room temperature molecular assembly of zwitterionic organic dipoles guided by Si(111)-7x7 template effect ** Stable room temperature molecular assembly of zwitterionic organic dipoles guided by Si(111)-7x7 template effect **
(RoM 02/2008)
Atomic Resolution on MgO (100) at T=5K using qPlus Non-Contact AFM mode Atomic Resolution on MgO (100) at T=5K using qPlus Non-Contact AFM mode
(RoM 12/2007)
Atomic Manipulation at Room Temperature Atomic Manipulation at Room Temperature
(RoM 11/2007)
Atom Manipulation at 5 K! Atom Manipulation at 5 K!
(RoM 10/2007)
CaF<SUB>2</SUB> superstructures CaF2 superstructures
(RoM 09/2007)
Influence of the Local Adsorption Environment on the Intra-Molecular Contrast of Organic Molecules in Non-Contact Atomic Force Microscopy Influence of the Local Adsorption Environment on the Intra-Molecular Contrast of Organic Molecules in Non-Contact Atomic Force Microscopy
(RoM 08/2007)
Strong Bonding of single C60 molecules to (1x2)-Pt (110): an STM/DFT Investigation Strong Bonding of single C60 molecules to (1x2)-Pt (110): an STM/DFT Investigation
(RoM 07/2007)
Inner-Tube Chirality Determination for Double-Walled Carbon Nanotubes by Scanning Tunneling Microscopy Inner-Tube Chirality Determination for Double-Walled Carbon Nanotubes by Scanning Tunneling Microscopy
(RoM 06/2007)
Formation of Iron Oxide Nanoparticles and Thin Films on Au(111) Formation of Iron Oxide Nanoparticles and Thin Films on Au(111)
(RoM 05/2007)
Writing image Patterns with FIB Writing image Patterns with FIB
(RoM 04/2007)
STM constant height image a reconstructed Si(111)7x7 surface STM constant height image a reconstructed Si(111)7x7 surface
(RoM 03/2007)
Electrical contact melting on nanoscale Electrical contact melting on nanoscale
(RoM 02/2007)
Imaging XPS with 650 nm Resolution Imaging XPS with 650 nm Resolution
(RoM 01/2007)
Electronic Properties of Self-Organised Poly(3-dodecylthiophene)Monolayers Probe at the Single Chain Scale by Two-Dimensional Scanning Tunneling Spectroscopy Imaging Electronic Properties of Self-Organised Poly(3-dodecylthiophene)Monolayers Probe at the Single Chain Scale by Two-Dimensional Scanning Tunneling Spectroscopy Imaging
(RoM 12/2006)
QPlus Technology for Atomic-Resolution AFM on NaCl at 5K QPlus Technology for Atomic-Resolution AFM on NaCl at 5K
(RoM 11/2006)
Controlling the Kondo effect of an adsorbed magnetic atom by single-molecule chemistry Controlling the Kondo effect of an adsorbed magnetic atom by single-molecule chemistry
(RoM 10/2006)
Visualizing and exploring local electronic structure of a quantum point contact with STM Visualizing and exploring local electronic structure of a quantum point contact with STM
(RoM 09/2006)
Scanning Electron Microscopy with Polarisation Analysis Scanning Electron Microscopy with Polarisation Analysis
(RoM 08/2006)
TOF PEEM TOF PEEM
(RoM 07/2006)
4 Probe with SEM Navigation 4 Probe with SEM Navigation
(RoM 06/2006)
Dendritic to non-dendritic transitions in Au islands Dendritic to non-dendritic transitions in Au islands
(RoM 05/2006)
Highly Resolved STM and Non-Contact AFM on Ag(√3x √3)/Si(111) 7x7 with Omicron VT AFM and Matrix SPM Control System Highly Resolved STM and Non-Contact AFM on Ag(√3x √3)/Si(111) 7x7 with Omicron VT AFM and Matrix SPM Control System
(RoM 04/2006)
Chemical Fingerprinting at the Atomic Level Chemical Fingerprinting at the Atomic Level
(RoM 03/2006)
Molecular superstructures of thermally unstable molecules deposited with the spray-Jet technique on Au(111) surface Molecular superstructures of thermally unstable molecules deposited with the spray-Jet technique on Au(111) surface
(RoM 02/2006)
Spin-Polarised Low Temperature STM Spin-Polarised Low Temperature STM
(RoM 01/2006)
Dynamical oscillation at the α-Sn/Ge(111) surface Dynamical oscillation at the α-Sn/Ge(111) surface
(RoM 12/2005)
NanoESCA with sub-µm spatial XPS resolution in the lab NanoESCA with sub-µm spatial XPS resolution in the lab
(RoM 11/2005)
Quantum Confinement between Self-Organized Pt Nanowires on Ge(001) Quantum Confinement between Self-Organized Pt Nanowires on Ge(001)
(RoM 10/2005)
4 Probe measurements on 4 Probe measurements on "lifted" nanowires
(RoM 09/2005)
Nanoscale gold-fingers Nanoscale gold-fingers
(RoM 08/2005)
Atomic resolved non-contact AFM imaging of Ge/Si(105) surface Atomic resolved non-contact AFM imaging of Ge/Si(105) surface
(RoM 07/2005)
Direct imaging of the atomic structure inside a nanowire by Scanning Tunneling Microscopy Direct imaging of the atomic structure inside a nanowire by Scanning Tunneling Microscopy
(RoM 06/2005)
Dance around the Maypole Dance around the Maypole
(RoM 05/2005)
Charge writing of nanocrystalline SnO<SUB>2</SUB> surfaces Charge writing of nanocrystalline SnO2 surfaces
(RoM 04/2005)
Surface Structure of Icosahedral Al-Cu-Fe quasicrystal Surface Structure of Icosahedral Al-Cu-Fe quasicrystal
(RoM 03/2005)
Adsorption of Acetone at the Ge(100)-2x1 Semiconductor Interface Adsorption of Acetone at the Ge(100)-2x1 Semiconductor Interface
(RoM 02/2005)
Low Current STM image of a P3DDT film Low Current STM image of a P3DDT film
(RoM 01/2005)
Inelastic Electron Tunneling Spectroscopy on Decanthiol at Elevated Temperatures Inelastic Electron Tunneling Spectroscopy on Decanthiol at Elevated Temperatures
(RoM 12/2004)
MFM image taken at a Co/Pt multilayer surface MFM image taken at a Co/Pt multilayer surface
(RoM 11/2004)
Magnetic NOT - Gate (MFM) Magnetic NOT - Gate (MFM)
(RoM 10/2004)
Atomically resolved MnSi island grown on a Si(100)-(2 x 1) substrate Atomically resolved MnSi island grown on a Si(100)-(2 x 1) substrate
(RoM 09/2004)
Scanning Tunneling Spectroscopy on MgB<SUB>2</SUB> at low Temperatures and High Magnetic Fields Scanning Tunneling Spectroscopy on MgB2 at low Temperatures and High Magnetic Fields
(RoM 08/2004)
Pseudomorphic Growth of a Single Element Quasiperiodic Ultrathin Film on a Quasicrystal Substrate Pseudomorphic Growth of a Single Element Quasiperiodic Ultrathin Film on a Quasicrystal Substrate
(RoM 07/2004)
Exploring the Mechanism of Molecular Chirality Transfer via STM Exploring the Mechanism of Molecular Chirality Transfer via STM
(RoM 06/2004)
In situ High-resolution XPS study of thermal reactions of methyl on Ni(111) In situ High-resolution XPS study of thermal reactions of methyl on Ni(111)
(RoM 05/2004)
In situ High-Temperature STM Studies of Surface Dynamics on Atomically Smooth TiN(001) and TiN(111) In situ High-Temperature STM Studies of Surface Dynamics on Atomically Smooth TiN(001) and TiN(111)
(RoM 04/2004)
Work Function Imaging of Semiconductor Surfaces Using Ultrahigh Vacuum Kelvin Probe Force Microscopy Work Function Imaging of Semiconductor Surfaces Using Ultrahigh Vacuum Kelvin Probe Force Microscopy
(RoM 03/2004)
Self-organised, one dimensional Pt nanowires on Ge(001) Self-organised, one dimensional Pt nanowires on Ge(001)
(RoM 02/2004)
Segregation of molecular overlayers with different structures on a metal surface Segregation of molecular overlayers with different structures on a metal surface
(RoM 01/2004)
The SPA-LEED picture taken at an out-of-phase energy of 128 eV The SPA-LEED picture taken at an out-of-phase energy of 128 eV
(RoM 12/2003)
Oxidised Sb crystals on HOPG Oxidised Sb crystals on HOPG
(RoM 11/2003)
Spin Polarized Tunneling Induced Luminescence Microcopy (SP-TILM) Spin Polarized Tunneling Induced Luminescence Microcopy (SP-TILM)
(RoM 10/2003)
Standing waves on Au(111) Standing waves on Au(111)
(RoM 09/2003)
PEEM+IEF: Fermi surface of Cu(001) PEEM+IEF: Fermi surface of Cu(001)
(RoM 08/2003)
Coloured SEM images Coloured SEM images
(RoM 07/2003)
Constant current STM image of a GaAs (110) surface Constant current STM image of a GaAs (110) surface
(RoM 05/2003)
Easter Bunny Easter Bunny
(RoM 04/2003)
Manipulation on the atomic scale Manipulation on the atomic scale
(RoM 01/2003)
icosahedral AlPdMn quasicrystal surface icosahedral AlPdMn quasicrystal surface
(RoM 12/2002)
SEM in UHV on Insulators SEM in UHV on Insulators
(RoM 11/2002)
The structure of NaCl (100) and KCl (100) single crystal surfaces The structure of NaCl (100) and KCl (100) single crystal surfaces
(RoM 10/2002)
Single-molecule reaction and characterization by vibrational excitation Single-molecule reaction and characterization by vibrational excitation
(RoM 09/2002)
Coronene on Ag(111) Investigated by LEED and STM in UHV Coronene on Ag(111) Investigated by LEED and STM in UHV
(RoM 07/2002)
Two-dimensional imaging of electronic wavefunctions in carbon nanotubes Two-dimensional imaging of electronic wavefunctions in carbon nanotubes
(RoM 06/2002)
Scanning Kelvin Probe Microscopy with VT Beam Deflection AFM Scanning Kelvin Probe Microscopy with VT Beam Deflection AFM
(RoM 05/2002)
Spontaneous Assembly of Perfectly Ordered Identical-Size Nanocluster Arrays Spontaneous Assembly of Perfectly Ordered Identical-Size Nanocluster Arrays
(RoM 04/2002)
Selfassembled quasi periodic Bi nanostructures Selfassembled quasi periodic Bi nanostructures
(RoM 03/2002)
Oxygen adsorption on Al(111): low transient mobility Oxygen adsorption on Al(111): low transient mobility
(RoM 02/2002)
High Resolution Solid State UPS High Resolution Solid State UPS
(RoM 01/2002)