Modification of indium - Tin oxide electrodes with thiophene copolymer thin films: Optimizing electron transfer to solution probe molecules

F. Saneeha Marrikar, Michael Brumbach, Dennis H. Evans, Ariel Lebrón-Paler, Jeanne E Pemberton, Ronald J. Wysocki, Neal R Armstrong

Research output: Contribution to journalArticle

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Abstract

We describe the modification of indium-tin oxide (ITO) electrodes via the chemisorption and electropolymerization of 6-{2,3-dihydrothieno[3,4-b]-1.4- dioxyn-2-yl methoxy}hexanoic acid (EDOTCA) and the electrochemical co-polymerization of 3,4-ethylenedioxythiophene (EDOT) and EDOTCA to form ultrathin films that optimize electron-transfer rates to solution probe molecules. ITO electrodes were first activated using brief exposure to strong haloacids, to remove the top ̃8 nm of the electrode surface, followed by immediate immersion into a 50:50 EDOT/EDOTCA comonomer solution. Potential step electrodeposition for brief deposition times was used to grow copolymer films of thickness 10-100 nm. The composition of these copolymer films was characterized by solution depletion studies of the monomers and atomic force microscopy (AFM), X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy (reflection-absorption infrared spectroscopy (RAIRS)) of the product films. The spectroscopic data suggest that the composition of the copolymer approaches 80% EDOTCA when electropolymerization occurs from concentrated (10 mM) solutions. AFM characterization shows that electrodeposited poly(EDOT)/poly(EDOTCA) (PEDOT/PEDOTCA) films are quite smooth, with texturing on the nanometer scale. RAIRS studies indicate that these films consist of a combination of EDOTCA units with noninteracting -COOH groups and adjacent hydrogen-bonded -COOH groups. The EDOTCA-containing polymer chains appear to grow as columnar clusters from specific regions, oriented nearly vertically to the substrate plane. As they grow, these columnar clusters overlap to form a nearly continuous redox active polymer film. ITO activation and formation of these copolymer films enhances the electroactive fraction of the electrode surface relative to a nonactivated, unmodified "blocked" ITO electrode. Outer-sphere solution redox probes (dimethylferrocene) give standard rate coefficients, ks ≥ 0.4 cm·-1, at 10 nm thick copolymer films of PEDOT/PEDOTCA, which is 3 orders of magnitude greater than that on the unmodified ITO surface and approaches the values for k s seen on clean gold surfaces.

Original languageEnglish (US)
Pages (from-to)1530-1542
Number of pages13
JournalLangmuir
Volume23
Issue number3
DOIs
StatePublished - Jan 30 2007

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Thiophenes
Thiophene
thiophenes
Tin oxides
indium oxides
Indium
tin oxides
copolymers
electron transfer
Copolymers
Thin films
Electrodes
Molecules
electrodes
Electrons
probes
thin films
molecules
Electropolymerization
Absorption spectroscopy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Colloid and Surface Chemistry

Cite this

Modification of indium - Tin oxide electrodes with thiophene copolymer thin films : Optimizing electron transfer to solution probe molecules. / Marrikar, F. Saneeha; Brumbach, Michael; Evans, Dennis H.; Lebrón-Paler, Ariel; Pemberton, Jeanne E; Wysocki, Ronald J.; Armstrong, Neal R.

In: Langmuir, Vol. 23, No. 3, 30.01.2007, p. 1530-1542.

Research output: Contribution to journalArticle

Marrikar, F. Saneeha ; Brumbach, Michael ; Evans, Dennis H. ; Lebrón-Paler, Ariel ; Pemberton, Jeanne E ; Wysocki, Ronald J. ; Armstrong, Neal R. / Modification of indium - Tin oxide electrodes with thiophene copolymer thin films : Optimizing electron transfer to solution probe molecules. In: Langmuir. 2007 ; Vol. 23, No. 3. pp. 1530-1542.
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N2 - We describe the modification of indium-tin oxide (ITO) electrodes via the chemisorption and electropolymerization of 6-{2,3-dihydrothieno[3,4-b]-1.4- dioxyn-2-yl methoxy}hexanoic acid (EDOTCA) and the electrochemical co-polymerization of 3,4-ethylenedioxythiophene (EDOT) and EDOTCA to form ultrathin films that optimize electron-transfer rates to solution probe molecules. ITO electrodes were first activated using brief exposure to strong haloacids, to remove the top ̃8 nm of the electrode surface, followed by immediate immersion into a 50:50 EDOT/EDOTCA comonomer solution. Potential step electrodeposition for brief deposition times was used to grow copolymer films of thickness 10-100 nm. The composition of these copolymer films was characterized by solution depletion studies of the monomers and atomic force microscopy (AFM), X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy (reflection-absorption infrared spectroscopy (RAIRS)) of the product films. The spectroscopic data suggest that the composition of the copolymer approaches 80% EDOTCA when electropolymerization occurs from concentrated (10 mM) solutions. AFM characterization shows that electrodeposited poly(EDOT)/poly(EDOTCA) (PEDOT/PEDOTCA) films are quite smooth, with texturing on the nanometer scale. RAIRS studies indicate that these films consist of a combination of EDOTCA units with noninteracting -COOH groups and adjacent hydrogen-bonded -COOH groups. The EDOTCA-containing polymer chains appear to grow as columnar clusters from specific regions, oriented nearly vertically to the substrate plane. As they grow, these columnar clusters overlap to form a nearly continuous redox active polymer film. ITO activation and formation of these copolymer films enhances the electroactive fraction of the electrode surface relative to a nonactivated, unmodified "blocked" ITO electrode. Outer-sphere solution redox probes (dimethylferrocene) give standard rate coefficients, ks ≥ 0.4 cm·-1, at 10 nm thick copolymer films of PEDOT/PEDOTCA, which is 3 orders of magnitude greater than that on the unmodified ITO surface and approaches the values for k s seen on clean gold surfaces.

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