Dielectric spectroscopy for probing the relaxation and charge transport in polypyrrole nanofibers

Abstract

Conductivity relaxation and charge transport mechanisms in polypyrrole (PPy) nanofibers synthesized using a micellar polymerization technique with varying surfactant concentration has been investigated by dielectric relaxation spectroscopy. TEM micrographs depict that the increasing surfactant concentration leads to the reduction of the nanofiber diameter. X-ray diffraction studies show that domain length in the PPy nanofibers decreases with decreasing fiber diameter whereas the strain caused due to dislocations and point defects increases. The permittivity spectra reveal that the relaxation mechanism in PPy nanofibers are dominated by hopping of trapped charges. Two relaxation peaks in the impedance spectra are attributed to the two-phase structure in the PPy nanofibers; the lower frequency peak is ascribed to the phase of oxidized repeat units and the higher frequency peak to the reduced repeat units of PPy nanofibers. The occurrence of relaxation peaks at different frequencies in the impedance and modulus spectra indicates a non-Debye relaxation with a wide distribution of relaxation times. The ac conductivity has been interpreted as a power law of frequency. The decrease of the parameter s with increasing temperature indicates that correlated barrier hopping is the dominant charge transport mechanism. Existence of polarons as major charge carriers has been confirmed by the low values of polaron binding energy.