Physicochemical and Electrochemical Characterization of Electropolymerized Polydopamine Films: Influence of the Deposition Process.

Polydopamine (PDA) is a synthetic eumelanin polymer which is, to date, mostly obtained by dip coating processes. In this contribution, we evaluate the physical and electrochemical properties of electrochemically deposited PDA films obtained by cyclic voltammetry or pulsed deposition. The obtained PDA thin films are investigated with respect to their electrochemical properties, i.e., electron transfer (ET) kinetics and charge transfer resistance using scanning electrochemical microscopy and electrochemical impedance spectroscopy, and their nanomechanical properties, i.e., Young's modulus and adhesion forces at varying experimental conditions, such as applied potential or pH value of the medium using atomic force microscopy. In particular, the ET behavior at different pH values has not to date been investigated in detail for electrodeposited PDA thin films, which is of particular interest for a multitude of applications. Adhesion forces strongly depend on applied potential and surrounding pH value. Moreover, force spectroscopic measurements reveal a significantly higher percentage of polymeric character compared to films obtained by dip coating. Additionally, distinct differences between the two depositions methods are observed, which indicate that the pulse deposition process leads to denser, more cross-linked films.