Reversible potentiometric oxygen sensors based on polymeric and metallic film electrodes

Various materials and sensor configurations that exhibit reversible potentiometric responses to the partial pressure of oxygen at room temperature in neutral pH solution are examined. In one arrangement, platinum electrodes are coated with plasticized poly(vinyl chloride) films doped with a cobalt(II) tetraethylene pentamine complex. For such sensors, potentiometric oxygen response is attributed to a mixed potential originating from the underlying platinum electrode surface as well as a change in redox potential of the Co(II)-tetren-doped film as the complex binds oxygen reversibly. The response due to the platinum surface is prolonged by the presence of the Co(II)-tetren/PVC film. Alternately, thin films of metallic copper, electrochemically deposited on platinum and/or sputtered or vapor deposited on a single crystal silicon substrate, may be used for reversible oxygen sensing. The long-term reversibility and potentiometric stability of such copper film-based sensors is enhanced (up to 1 month) by preventing the formation of cuprous oxide on the surfaces via the application of an external nonpolarizing cathodic current through the working electrode or by specifically using sputtered copper films that have [100] preferred crystal structures as determined by X-ray diffraction. The implications of these findings in relation to fabricating analytically useful potentiometric oxygen sensors are discussed.