Electrodeposited composite of poly-3,4-ethylenedioxythiophene with fullerenol photoactive in the near-IR range

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Abstract

The electrochemical polymerization of 3,4-ethylenedioxythiophene in the presence of a water-soluble Na+-containing fullerene with hydroxyl groups was studied. Spectral methods for monitoring the progress of electrosynthesis have shown that during the polymerization of 3,4-ethylenedioxythiophene, fullerenol is included in the film composition, regardless of the fullerenol concentrations used in the synthesis. The electronic structure, morphology, spectroelectrochemical, electrochemical properties and near-IR photoconductivity of composite films of poly-3,4-ethylenedioxythiophene with fullerenol were studied for the first time. A mechanism of photoconductivity has been proposed, related to the fact that during photoexcitation of the composite, electron transfer from the polaron (bipolaron) state of poly-3,4-ethylenedioxythiophene to the LUMO level of fullerenol increases the concentration of photogenerated charge carriers.

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About the authors

O. L. Gribkova

Institute of Physical Chemistry and Electrochemistry named after A.N. Frumkin RAS

Author for correspondence.
Email: oxgribkova@gmail.com
Russian Federation, Moscow

I. R. Sayarov

Institute of Physical Chemistry and Electrochemistry named after A.N. Frumkin RAS

Email: oxgribkova@gmail.com
Russian Federation, Moscow

V. A. Kabanova

Institute of Physical Chemistry and Electrochemistry named after A.N. Frumkin RAS

Email: oxgribkova@gmail.com
Russian Federation, Moscow

A. A. Nekrasov

Institute of Physical Chemistry and Electrochemistry named after A.N. Frumkin RAS

Email: oxgribkova@gmail.com
Russian Federation, Moscow

A. R. Tameev

Institute of Physical Chemistry and Electrochemistry named after A.N. Frumkin RAS

Email: tameev@elchem.ac.ru
Russian Federation, Moscow

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Supplementary files

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2. Fig. 1. Structure (a) [8] and electronic absorption spectrum (b) of a 0.00034 M aqueous solution of NaFl in a 0.1-cm cuvette.

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3. Fig. 2. Cyclic voltammogram during deposition of PEDOT film from an aqueous solution of 0.01 M EDOT and 0.00067 M NaFl. The first and every fifth subsequent cycle are shown.

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4. Fig. 3. Change in potential during GS electropolymerization of 0.01 M EDOT in aqueous solutions of NaFl with concentrations, M: 0.00017 (1), 0.00034 (2), 0.00067 (3) and 0.0014 (4).

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5. Fig. 4. Electronic absorption spectra of the PEDOT film formed on the working electrode during the polymerization of EDOT in the GS mode at a current density of 0.05 mA/cm2 in a 0.00034 M aqueous solution of NaFl. The optical path in the solution is 1.6 cm.

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6. Fig. 5. Change in absorption at 700 nm (a) and 400 nm (b) during HS deposition of PEDOT hybrid films in the presence of NaFl at concentrations, M: 0.00017 (1), 0.00034 (2), 0.00067 (3), 0.0014 (4), and in a 0.1 M aqueous solution of NaClO4 (5).

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7. Fig. 6. Electronic absorption spectra in air of PEDOT composite films electrodeposited in aqueous solutions of NaFl at concentrations, M: 0.00017 (1), 0.00034 (2), 0.00067 (3), 0.0014 (4), and in a 0.1 M aqueous solution of NaClO4 (5).

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8. Fig. 7. Electron absorption spectra at fixed potentials of the PEDOT – NaFl composite film, measured in 0.5 M NaClO4 aqueous solution.

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9. Fig. 8. Cyclic voltammograms of the PEDOT – NaFl composite film measured in 0.2 M Bu4NPF6 electrolyte in acetonitrile.

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10. Fig. 9. AFM images of the surfaces of PEDOT films obtained on an FTO electrode in the presence of NaFl (a) and NaClO4 (b).

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11. Fig. 10. Diagram of electron levels of PEDOT and NaFl molecules (Fig. 8) participating in the absorption of photons in the IR region of the spectrum. Blue arrows show the excitation of an electron from the ground level to the level of a polaron or bipolaron with transfer to the LUMO level of the electron acceptor – fullerenol. The levels of polarons and bipolarons are given according to calculations [15].

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