Abstract
In situ ESR spectroelectrochemical studies of poly(3,4-butylenedioxythiophene) (PBuDOT) have been performed, in order to investigate more closely the species responsible for the conductivity of this polymer in the doped state. In the process of electrochemical doping of the polymer, ESR spectra at progressively changed potentials were recorded. Then the subsequent dedoping process was studied accordingly. The results reveal that PBuDOT’s ESR spectroscopic properties are markedly different form its close relative, poly(3,4-etylenedioxythiophene) (PEDOT). Firstly, the potential dependence of the spin concentration displays a clear peak-shaped transient with a gradual decrease at higher oxidation potentials. Similar behaviour is seen for the ΔB pp widths of the ESR signal, indicating that the type of interactions between paramagnetic centres is potential sensitive. The course of the reduction process of the polymer is more or less the reverse of the oxidation one, with only a slight hysteresis of the spin concentration and a barely discernible one of ΔB pp widths being observed. In PBuDOT, as in PEDOT, distinct narrow ESR lines revealing a noteworthy spin concentration in the reduced state of the polymer have also been observed. The presence of these residual spins in the dedoped polymer may indicate that the dedoping process of this polymer is indeed a slow one. The presence of trace amounts of impurities or oxygen may hinder the dedoping process, especially for thicker films.
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Bayer A.G. (1988) Eur Patent 339340
Groenendaal L, Jonas F, Freitag D, Pielartzik H, Reynolds JR (2002) Adv Mater 12:481
Jonas F, Schrader L (1991) Synth Met 41–43:831
Gustafsson JC, Leidberg B, Inganäs O (1994) Solid State Ionics 69:145
Winter I, Reece C, Horms J, Heywang G, Jonas F (1995) Chem Phys 194:207
Heywang G, Jonas F (1992) Adv Mater 4:116
Kumar A, Reynolds JR (1996) Macromolecules 29:7629
Ng SC, Chan HSO, Yu WL (1997) J Mater Sci Lett 16:809
Lima A, Schottland P, Sadki S, Chevrot C (1998) Synth Met 93:33
Welsh DM, Kloeppner LJ, Reynolds JR, Kumar A, Meijer EW (1999) Polym Prepr 40(2):1206
Czardybon A, Lapkowski M (2001) Synth Met 119:161
Dietrich M, Heinze J, Heywang G, Jonas F (1994) J Electroanal Chem 369:87
Welsh DM, Kumar A, Morvant MC, Reynolds JR (1999) Synth Met 102:967
Kumar A, Welsh DM, Morvant MC, Piroux F, Abboud KA, Reynolds JR (1998) Chem Mater 10:896
Czardybon A, Lapkowski M (2003) Synth Met 135–136:27
Chen J, Heeger AJ, Wudl F (1986) Solid State Commun 58:251
Van Haare JA, Havinga EE, Van Dongen JLJ, Janssen RAJ, Cornil J, Bredas JL (1998) Chem Eur J 4:1509
Harima Y, Eguchi T, Yamashita K, Kojama K, Shiotani M (1999) Synth Met 105:121
Harima Y, Kunugi Y, Tang H, Yamashita K, Shiotani M, Ohshita J, Kunai A (2000) Synth Met 113:173
Zotti G, Zecchin S, Schiavon G (2000) Chem Mater 12:2996
Zykwinska A, Domagala W, Lapkowski M (2003) Electrochem Commun 5:603
Lapkowski M, Pron A (2000) Synth Met 110:79
Brédas JL, Street GB (1985) Acc Chem Res 18:309
Harima Y, Kunugi Y, Tang H, Yamashita K, Shiotani M, Ohshita J, Kunai A (2000) Synth Met 113:173
Dkhissi A, Louwet F, Groenendaal L, Beljonne D, Lazzaroni R, Brédas JL (2002) Chem Phys Lett 359:466
Kvarnstöm C, Neugebauer H, Blomquist S, Ahonen HJ, Kankare J, Ivaska A (1999) Electrochim Acta 44:2739
Houze E, Nechtschein M, Pron A (1997) Synth Met 84:981
Wertz JE, Bolton JR (1986) Electron spin resonance. Elementary theory and practical applications. Academic Press, London
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Contribution to the 3rd Baltic Conference on Electrochemistry, Gdansk-Sobieszewo, Poland, 23–26 April 2003
Dedicated to the memory of Harry B. Mark, Jr. (28 February 1934–3 March 2003)
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Zykwinska, A., Domagala, W., Czardybon, A. et al. Investigation of charge carriers in poly(3,4-butylenedioxythiophene) (PBuDOT) by means of ESR spectroelectrochemistry. J Solid State Electrochem 8, 369–375 (2004). https://doi.org/10.1007/s10008-003-0478-5
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DOI: https://doi.org/10.1007/s10008-003-0478-5