Direct Writing and Characterization of Three-Dimensional Conducting Polymer PEDOT Arrays

Direct writing is an effective and versatile technique for three-dimensional (3D) fabrication of conducting polymer (CP) structures. It is precisely localized and highly controllable, thus providing great opportunities for incorporating CPs into microelectronic array devices. Herein we demonstrate 3D writing and characterization of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonate (PEDOT:PSS) pillars in an array format, by using an in-house-constructed variant of scanning ion conductance microscopy (SICM). CP pillars with different aspect ratios were successfully fabricated by optimizing the writing parameters: pulling speed, pulling time, concentration of the polymer solution, and the micropipette tip diameter. Especially, super high aspect ratio pillars of around 7 μm in diameter and 5000 μm in height were fabricated, indicating a good capability of this direct writing technique. Additions of an organic solvent and a cross-linking agent contribute to a significantly enhanced water stability of the pillars, critical if the arrays were to be used in biologically relevant applications. Surface morphologies and structural analysis of CP pillars were characterized by scanning electron microscopy and Raman spectroscopy, respectively. Electrochemical properties of the individual pillars of different heights were examined by cyclic voltammetry using a double-barrel micropipette as an electrochemical cell. Exceptional mechanical properties of the pillars, such as high flexibility and robustness, were observed when bent by applying a force. The 3D pillar arrays are expected to provide versatile substrates for functionalized and integrated biological sensing and electrically addressable array devices.