The electronic transport mechanism in polypyrrole is discussed in terms of Mott variable range hopping (VRH) in samples with a wide range of conductivities and which have been formed using different doping techniques. Samples were synthesized in both aqueous and organic media and samples were either doped during polymerization or dedoped afterwards giving a three order of magnitude range of conductivities at 300 K and a range of sample morphologies. No difference in behavior is observed for materials with different morphologies, suggesting that transport predominantly involves monomer units and occurs independent of structure. The various transport parameters obtained appear reasonable with the exception of the apparent ‘‘hopping attempt frequency,’’ related to the phonon frequency in VRH, some values of which are anomalously high. The density of states at the Fermi level was found to be between 5×1018 and 1×1022 eV−1 cm−3 for a range of samples and the mean hopping distances ranged between 2 and 34 monomer units. The minimum hopping distance of 2 monomer units is consistent with electron delocalization on individual monomer units. An upper limit of conductivity in polypyrrole of no more than 400 S cm−1 is suggested in the limit of the VRH regime in which hopping occurs between adjacent monomer units.

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The conductivity of doped polypyrrole, as high as 100 Scm−1 in freshly prepared samples, falls slowly with time on exposure to atmospheric oxygen. Typically, the fall in conductivity is fairly slow at room temperature, but the process can be accelerated by heating samples and measuring the decrease in conductivity as a function of time. Analysis of the kinetics of this process shows a preliminary, 120 min regime in which a surface adsorption-diffusion mechanism with an activation energy of 0.41 eV appears to mediate. Once a degree of adsorbate saturation is attained subsequent behavior is well described by standard bulk diffusion considerations and is activated at 0.48 eV. We propose a mechanism whereby oxygen adsorption onto the surfaces of the polymer fibrils and diffusion into the interior are respective rate limiting steps in the incorporation of oxygen into the closely cross-linked mesh, blocking conducting pathways.

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