Abstract
Conductive and dielectrical properties of TCNQ anion radical salt (II) and complex salts (III) of were studied. Conductivity and dielectric constant were larger in (III). The dielectric constants of (III) were 70—7000 at 30 kHz—1 MHz at room temperature; they increased with temperature and decreased with increasing frequency and AC field strength. The activation energies of polarization agreed very closely with those of electrical conduction, suggesting the same mechanistic origin for both phenomena. To explain these results, a model has been proposed for the structure of polycation—TCNQ salts—in which the TCNQ molecules are packed randomly in the polycation network and every TCNQ molecule has the possibility of making electrical contact with nearby TCNQ molecules, depending on the degree of the volume content of TCNQ in the material. Eventually, long sequences of TCNQ molecules connecting the two electrodes can arise in this model and these sequences provide electrical conductivity of the materials. Also, isolated shorter sequences are possible in the matrix, and these contribute to the polarization. Thus, the dielectric polarization of the material can be explained by a microscale Maxwell—Wagner polarization mechanism.
Similar content being viewed by others
Article PDF
References
J. E. Katon, “Organic Semiconducting Polymers,” Dekker, New York, N.Y., 1968.
Ya. M. Paushkin, T. P. Vishnyakova, A. F. Lunin, and S. A. Nizova, “Organic Polymeric Semiconductors,” John Wiley and Sons, New York, N.Y., 1974.
R. Rosen and H. A. Pohl, J. Polym. Sci., Part A-1, 4, 1135 (1966).
R. D. Hartman and H. A. Pohl, J. Polym. Sci., Part A-1, 6, 1135 (1968).
J. R. Wyhof and H. A. Pohl, J. Polym. Sci., Part A-2, 8, 1741 (1970).
L. R. Melby, R. L. Harder, W. R. Hertler, W. Mahler, R. E. Benson, and W. E. Mochel, J. Am. Chem. Soc., 84, 3374 (1962).
J. H. Lupinski, K. D. Kopple, and L. J. Hertz, J. Polym. Sci., Part C, 16, 1561 (1967).
K. Mizoguchi, T. Suzuki, E. Tsuchida, and I. Shinohara, Nippon Kagaku Kaishi, 1973, 1760.
K. Nakatani, T. Sakata, and H. Tsubomura, Bull. Chem. Soc. Jpn., 48, 657 (1975).
K. Mizoguchi, T. Suzuki, E. Tsuchida, and I. Shinohara, Nippon Kagaku Kaishi, 1973, 1751.
A. G. Garito and A. J. Heeger, Acc. Chem. Res., 7, 232 (1974).
I. F. Shehegolov, Phys. Stat. Sol., 12, 9 (1972).
A. W. Hanson, Acta Cryst., 19, 610 (1965).
H. Kobayashi, T. Danno, and Y. Saito, Acta Cryst., B29, 2693 (1973).
W. J. Siemons, P. E. Bierstedt, and R. G. Kepler, J. Chem. Phys., 39, 3523 (1963).
O. Maeda, G. Yamaki, and Y. Katayama, Kobunshi Ronbunshu, 32, No. 1, 42 (1975).
K. W. Wagner, Arch. f. Elektrotech., 2, 371 (1914).
K. W. Wagner, Arch. f. Elektrotech., 2, 374 (1914).
K. W. Wagner, Arch. f. Elektrotech., 2, 383 (1914).
P. J. Flory, “Principles of Polymer Chemistry,” Cornell University Press, Ithaca, N.Y., 1953, Chapter 9.
For explaining electrical conductivity of carbon black filled polymers, Flory’s gelation theory was used by Bueche. F. Bueche, J. Appl. Phys., 43, No. 11, 4837 (1972).
R. W. Sillars, J.I.E.E., 80, 378 (1937).
C. M. Huggins and A. H. Sharbaugh, J. Chem. Phys., 38, 393 (1963).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Ikeno, S., Matsumoto, K., Yokoyama, M. et al. Studies of Conductive and Dielectrical Properties of Polymeric Charge-Transfer Complexes. I. Polycation—TCNQ Salts. Polym J 9, 261–273 (1977). https://doi.org/10.1295/polymj.9.261
Issue Date:
DOI: https://doi.org/10.1295/polymj.9.261