Influence of doping anion on electrochemical and physical properties of polyselenienyl thiophene polymer

doi:10.1016/S0379-6779(97)80043-4

Synthetic Metals

Volume 82, Issue 2, 15 September 1996, Pages 111-117

https://doi.org/10.1016/S0379-6779(97)80043-4 Get rights and content

Abstract

The effect of counter ions on electrochemical and physical properties of polyselenienyl thiophene (PSeT) films was investigated. sThe films were prepared by anodic oxidation of selenienyl thiophene in acetonitrile using PF₆, ClO₄, BF₄ and CF₃SO₃ as the doping anion. Electrochemical characterization of these films using the same electrolyte as that used for electrosynthesis shows that their electrochemical properties are mainly controlled by the anion. The influence of the electrolyte on the morphology and the conductivity of PSeT films has been analysed. We have demonstrated an anion effect that can be related to the size of the counter ion. Fourier transform infrared (FT-IR) spectra of polymer with various doping species have been obtained. The bands specific to each doping species are distinctly observable for the doped PSeT films.

References (29)

G. Tourillon et al.
J. Electroanal. Chem.
(1982)
E. Ruckenstein et al.
Synth. Met.
(1991)
V. Peulon et al.
Synth. Met.
(1993)
V. Peulon et al.
Synth. Met.
(1995)
D.A. Kaplin et al.
Polymer
(1995)
M. Akimoto et al.
Synth. Met.
(1986)
S. Hotta et al.
Synth. Met.
(1984/1985)
S.D. Ross
Spectrochim. Acta
(1962)
C. Zhong et al.
Synth. Met.
(1990)
M. Yamaura et al.
Synth. Met.
(1988)

T. Shimidzu et al.

J. Electroanal. Chem.

(1987)

M. Iseki et al.

Synth. Met.

(1991)

E.M. Geniès et al.

Synth. Met.

(1984)

P. Marque et al.

J. Electroanal. Chem.

(1987)

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Influence of doping anion on electrochemical and physical properties of polyselenienyl thiophene polymer

Abstract

J. Electroanal. Chem.

Synth. Met.

Synth. Met.

Synth. Met.

Polymer

Synth. Met.

Synth. Met.

Spectrochim. Acta

Synth. Met.

Synth. Met.

J. Electroanal. Chem.

Synth. Met.

Synth. Met.

J. Electroanal. Chem.