Lo, M.; Pires, R.; Diaw, K.; Gningue-Sall, D.; Oturan, M.A.; Aaron, J.-J.; Chehimi, M.M. Diazonium Salts: Versatile Molecular Glues for Sticking Conductive Polymers to Flexible Electrodes. Surfaces2018, 1, 43-58.
Lo, M.; Pires, R.; Diaw, K.; Gningue-Sall, D.; Oturan, M.A.; Aaron, J.-J.; Chehimi, M.M. Diazonium Salts: Versatile Molecular Glues for Sticking Conductive Polymers to Flexible Electrodes. Surfaces 2018, 1, 43-58.
Adhesion of polymers to surfaces is of upmost importance in timely applications such as protective coatings, biomaterials, sensors, new power sources and soft electronics. In this context, this work examines the role of molecular interactions in the adhesion of polypyrrole thin films to flexible Indium Tin Oxide (ITO) electrodes grafted with aryl layers from various diazonium salts, namely 4-carboxybenzenediazonium (ITO-CO2H), 4-sulfonicbenzenediazonium (ITO-SO3H), 4-N,N dimethylbenzenediazonium (ITO-N(CH3)2), 4-aminobenzenediazonium (ITO-NH2), 4-cyanobenzenediazonium (ITO-CN) and 4-N-phenylbenzenediazonium (ITO-NHPh). It was demonstrated that PPy thin layers were adherent to these surfaces, whereas adhesion failure was noted on bare ITO, following simple solvent washing or sonication. Adhesion of the polypyrrole was investigated in terms of the hydrophilic/hydrophobic character of the underlying aryl layer as probed by contact angle measurements. It was found that sulfonic acid doped polypyrrole (PPy-BSA) thin films were preferably deposited on the most hydrophobic surfaces. More importantly, the redox properties and electrochemical impedance of PPy were closely related to the hydrophobic character of the aryl layers. This work demonstrates that diazonium compounds are unique molecular glues for conductive polymers, and permit to tune their interfacial properties. With diazonium-based robust, architectured interfaces, one can design high performance materials for e.g.sensors, printed soft electronics and flexible thermoelectrics.
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