Surface modification of indium tin oxide via electrochemical reduction of aryldiazonium cations

The facile deposition of para-substituted aryl films onto indium-tin oxide (ITO) electrodes by the electrochemical reduction of aryl diazonium salts in acetonitrile is reported. For the deposition conditions used in this report, the aryl film thicknesses are on the order of 1-6 nm, suggesting a multilayer structure. Regardless of the functional group on the aryl diazonium cation, (NO2, CO2H, or fluorene) the electrodeposition behavior onto ITO electrodes is similar to that seen on other electrode materials. XPS and UV-vis data support the introduction of organic functional surface groups to ITO. The blocking behavior of the aryl films on ITO toward the Ru(NH3)(6)(3+/2+) redox couple is in agreement with electron transfer through conjugated organic layers. The facile preparation of patterned aryl films with regular-spaced 700 nm voids on ITO is also described. Atomic force microscopy and scanning surface potential microscopy on patterned NO2 aryl films are used to assess the molecular structure and orientation. A 100 mV decrease in the contact potential over NO, aryl films relative to bare ITO suggests that the aryl films are loosely structured as deposited with the NO2 groups oriented at a small angle away from the ITO surface.