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Conducting polymers show attractive characteristics as electrode materials for micro-electrochemical energy storage (MEES). However, there is a lack of characterization techniques to study conjugated/conducting polymer-based nanostructured electrodes. Here, scanning electrochemical microscopy (SECM) is introduced as a new technique for in situ characterization and acceleration of degradation processes of conducting polymers. Electrodes of PEDOT:PSS on flat silicon, silicon nanowires (SiNWs) and silicon nanotrees (SiNTrs) are analyzed by SECM in feedback mode with approach curves and chronoamperometry. The innovative degradation method using SECM reduces the time required to locally degrade polymer samples to a few thousand seconds, which is significantly shorter than the time usually required for such studies. The degradation rate is modeled using Comsol Multiphysics. The model provides an understanding of the phenomena that occur during degradation of the polymer electrode and describes them using a mathematical constant A 0 and a time constant τ., (© 2022 Wiley-VCH GmbH.)

The simple and elegant Buchwald-Hartwig cross-coupling reaction has been used to synthesise a designed range of new aniline-based tetramers in one step, and without the need for protecting groups. Variation of the central aromatic ring has provided the opportunity to carefully tune the optoelectronic properties in this series, thus enabling a structure-activity relationship study by using a range of photophysical and electrochemical techniques. As a result, the long-proposed sequences of electron-electron (EE) and electron-chemical (EC) processes that support the complex redox and proton-transfer reactions involved in the well-known switching of redox states of poly- and oligo(aniline)s are revealed here for the first time. We also present the initial results from time-dependent DFT calculations to clarify the optoelectronic behaviour of these oligomers. The dc-conductivity measurements of conducting thin films of this series, doped with the prototypical poly(aniline) protonating agent D,L-camphor-10-sulfonic acid (CSA), externally plasticised with triphenyl phosphate (TPP), and processed from m-cresol (MC) solutions, are also presented., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)