A two-step patterning process was developed based on nanosphere lithography and plasma etching to fabricate an array of electrodes with two different gold ring structures: the arrays of Au micro-ring electrode (Au-MRE) and Au covered with polystyrene micro-ring electrode (Au-PS-MRE). The Au-MRE structure was fabricated by etching a monolayer of polystyrene (PS) spheres on indium tin oxide (ITO) surface to generate PS rings on ITO glass. PS rings served as a mask in secondary etching for blocking an interaction of oxygen plasma and ITO surface to create a ring-patterned ITO surface. Then, the PS residue was removed and gold was deposited. The site-selective electrodeposition of gold was carried out and an array of a gold ring structure was formed on the ITO glass. The Au-PS-MRE structure was fabricated by keeping the PS residue from second etching before deposition of gold. The Au-PS-MRE microelectrode was studied by using hexacyanoferrate as an electrochemical probe where it displayed steady state current in cyclic voltammetry. The respective calibration plots were acquired at a working potential of 0.31 V and 0.12 V (vs. Ag/AgCl) for oxidation and reduction reaction, respectively. The sensitivity is as high as 163.4-220.7 μA·mM-1·mm-2 which is larger by a factor of 95-132 compared to a conventional gold film macroelectrode. The detection limit (at a signal-to-noise ratio of 3) is 2.2 μM. This approach thus yields relatively effective and low-cost fabrication without resorting to high resolution instruments. Conceivably, the technique may be used to produce microelectrode arrays on a large scale. Graphical abstract Schematic presentation of a novel fabrication process of micro-ring electrode arrays. Two-step patterning based on nanosphere lithography leads to electrodes with great electrochemical performance. Direct deposition metal in the presence of polystyrene (PS) mask induces the formation of a new structure with arrays of gold covered with PS microring on the indium tin oxide (ITO) coated glass. The microelectrode-like behavior has been achieved using this fabrication process.
Keywords: Cyclic voltammetry; Electrochemical sensor; Electrodeposition; Nanoarray; Nanoelectrode; Nanosphere lithography; Nanostructured patterns; Plasma etching; Surface patterning.