We present electronic transport studies of the aging process in naphtalene–sulfonate-doped polypyrrole. They include in situ conductivity measurements as a function of the aging time up to 1 month, and conductivity and thermoelectric power measurements in the temperature range 300–15 K for different aging times at 120 °C in room atmosphere. We show that while the short-aging-time decay of the conductivity may be accounted for by a law of the type ${\mathrm{\sigma }}_0$-σ(${\mathit{t}}_{\mathit{a}}$)∝√${\mathit{t}}_{\mathit{a}}$, the long-aging-time evolution is well described by a stretched exponential, σ=${\mathrm{\sigma }}_0$exp[-(${\mathit{t}}_{\mathit{a}}$/τ${)}^{1/2}$]. Moreover, two distinct temperature dependences have been identified: (i) σ=${\mathrm{\sigma }}_0$exp[-(${\mathit{T}}_0$/T${)}^{1/2}$] for aged samples and (ii) σ=${\mathrm{\sigma }}_0$exp[-${\mathit{T}}_1$/T+${\mathit{T}}_0$] for as-synthesized or lightly aged samples. The thermal variation of the thermoelectric power can be described by the following law: S(T)=AT+B+C/T, where the relative weight of the linear term, A, appears to be a decreasing function of the aging time. All the results are comprehensively explained in terms of conducting grains separated by insulating barriers in which the conduction is controlled by a hopping process of the charge carriers between the grains. The aging phenomenon is found to consist of a decrease of the grain size, in parallel with a broadening of the barriers, as in a corrosion process. As the aging time increases, the size of the conducting grains decreases and then goes below a critical value that is responsible for a crossover in the transport mechanism and therefore in the time dependence of the conductivity as experimentally observed. In the aged samples, this model leads to the existence of a single expression that accounts for both the temperature and the aging-time dependences of the conductivity, i.e., lnσ(${\mathit{t}}_{\mathit{a}}$,T)∝-(${\mathit{t}}_{\mathit{a}}$/T${)}^{1/2}$. © 1996 The American Physical Society.

• Received 26 June 1995

DOI:https://doi.org/10.1103/PhysRevB.53.4509