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The Metallic State of Conducting Polymers: Microwave Dielectric Response and Optical Conductivity

Published online by Cambridge University Press:  16 February 2011

A. J. Epstein
Affiliation:
The Ohio State University, Department of Physics, Columbus, OH 43210–1106
J. Joo
Affiliation:
The Ohio State University, Department of Physics, Columbus, OH 43210–1106
R. S. Kohlman
Affiliation:
The Ohio State University, Department of Physics, Columbus, OH 43210–1106
A. G. Macdiarmid
Affiliation:
University of Pennsylvania, Department of Chemistry, Philadelphia, PA 19104–6323
J. M. Weisinger
Affiliation:
University of Pennsylvania, Department of Chemistry, Philadelphia, PA 19104–6323
Y. Min
Affiliation:
University of Pennsylvania, Department of Chemistry, Philadelphia, PA 19104–6323
J. P. Pouget
Affiliation:
Université Paris Sud, Laboratoire de Physique des Solides (CNRS-URA2), 91405 Orsay, France
J. Tsukamoto
Affiliation:
Toray Industries, Specialty Polymers Laboratory, Shiga 520 Japan
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Abstract

Recent advances in processing of polyaniline and polyacetylene have resulted in a new generation of conducting polymers with higher dc conductivities. We present the temperature (T) dependent microwave frequency dielectric constant, dc conductivity, and Kramers-Kronig analysis of conducting polyaniline and polyacetylene. The low temperature dielectric constant, ε, increases with the square of the x-ray crystalline domain length for preparations of HCl protonated polyaniline. For the highest crystalline polyaniline samples, ε increases dramatically with increasing T, supporting formation of three-dimensional (3-D) coupled “mesoscopic” Metallic regions. A “metallic” negative ε is observed for d,1-camphor sulfonie acid doped polyaniline prepared in m-cresol. Optical studies show a linear increase in reflectivity below 7000 cm-1. Below 600 cm-1 the reflectance increases rapidly. Kramers-Kronig analysis of the ir-visible results are presented. Highly conducting polyaniline is shown to have two plasma frequencies, one at ∼ 1.1 eV involving all the conduction band electrons, and one at ∼0.015 eV (120 cm-1) that is suggested to arise from the most delocalized electrons. The concept of inhomogeneous disorder is introduced. The results for polyaniline are compared to those of highly doped polyacetylene which also show metallic negative ε demonstrating the intrinsic metallic nature of the new generation of conducting polymers.

Type
Research Article
Copyright
Copyright © Materials Research Society 1994

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