This tutorial review gives a brief introduction to impedance spectroscopy and discusses how it has been used to provide insight into charge transport through conducting polymers, particularly when the polymers are used as electrodes for solution studies or the design of electrodes for biomedical applications. As such it provides both an introduction to the topic and references to both classic and contemporary work for the more advanced reader.
The impedance behavior of semiconducting polymer film electrodes based on poly(3,4-ethylenedioxythiophene) (PEDOT) in combination with a series of anionic dopants has been investigated using electrochemical impedance spectroscopy (EIS) over the frequency range from 0.1 Hz to 100 kHz. Films were electrodeposited on gold-coated Pt wire electrodes from a nonaqueous solution containing 3,4-ethylenedioxythiophene (EDOT). EIS results reveal that, under the optimal synthesis conditions, PEDOT electrodes consistently exhibit low, frequency-independent impedance over a wide frequency range (from ∼10 Hz to 100 kHz). These results suggest that the behavior originates from the two-layer homogeneous morphology of the film. A model for conduction in the films that is supported by experimental evidence is proposed, and EIS data for electrodes produced under a variety of electropolymerization conditions are presented.
Stimulation and recording of the in vivo electrical activity of neurons are critical functions in contemporary biomedical research and in treatment of patients with neurological disorders. The electrodes presently in use tend to exhibit short effective lifespans due to degradation of signal transmission resulting from the tissue response at the electrode-brain interface, and the signal throughput suffers most at the low frequencies relevant for biosignals. To overcome these limitations, new electrode designs to minimize tissue responses, including conducting polymers have been explored. Here we report the short-term histocompatibility and signal throughput results comparing platinum and conducting polymer modified platinum electrodes in a Sprague-Dawley rat model. Two of the polymers tested elicited significantly decreased astrocyte responses relative to platinum. These polymers also showed improved signal throughput at low frequencies and comparable signal to noise ratios during targeted intracranial electroencephalograms (EEG). These results suggest that conducting polymer electrodes may present viable alternatives to the metal electrodes that are currently in use.
Conducting polymers constitute a class of materials for which electrochemical and electron transport properties are a function not only of their chemical identity but also of their complex morphology. In this paper, we investigate and compare the frequency dependence behavior of the impedance of poly(3,4-ethylenedioxythiophene), or PEDOT, and that of poly(3,4-ethylenedioxypyrrole), or PEDOP, which are doped with a series of polyatomic anions during electrodeposition. We also contrast the behavior of PEDOT on Pt|Au, Pt, glassy carbon, and gold. Initial results for polycarbazole, PCz, electrodes are, in addition, included. Deposition parameters were adjusted to produce morphologically similar films for PEDOT, PEDOP, and PCz. In doing so, we have been successful in producing frequency-independent impedance behavior similar to that previously reported for PEDOT on Pt|Au. Although the impedance behavior of these polymers appears to be primarily determined by morphological features, the impact of counterion identity (beyond ionic charge transport) is also discussed. These studies suggest that choice of polymer/dopant combination and electrodeposition parameters can be manipulated to tune the impedance characteristics of electrodes, thereby optimizing them for capacitive or faradaic charge injection, or some combination of the two.
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