Is The Oxygen Plasma Cleaning Technique Indicated For Any Electrochemical Purpose?: The Case Of Fto Electrodes

Fluorine-doped tin oxide (FTO) is among the most used transparent conductive oxides (TCOs) in phototovoltaic devices such as photoelectrochemical and solar cells. Preparation of films on these TCOs can be achieved by several deposition techniques including electrodeposition. Among the several cleaning and activation procedures before a thin film deposition there is the oxygen plasma treatment, which has been successfully applied on several kind of substrate materials. Surprisingly, the use of this step on TCOs previously to the electrodeposition of a film is not a usual practice. Here we present a detailed study on the consequences of oxygen plasma process over FTO electrodes that are subsequently employed in several electrochemical reactions of practical importance. Open circuit potential (OCP) measurements from oxygen plasma treated FTO have proven the resorption of ions and/or solvent molecules in aqueous electrolyte following a pseudo-second order kinetic. Electrochemical reactions were quite sensible to the oxygen plasma treatment, even under mild conditions. In all cases FTO become deactivated for such electrochemical processes independently of the plasma set up employed except for metal electrodeposition. Partial recovering of the electrochemical response of FTO in the ferri/ferro system after annealing at 450 °C explains why oxygen plasma process is worthy only for other deposition techniques such as spray pyrolysis where similar temperatures are employed. Electrochemical Impedance Spectroscopy (EIS) analysis revealed a decrease of the majority carrier density (ND). This is mainly attributed to the oxyanion implantation on oxygen vacancies sites during the plasma process thus explaining the loss of activation of FTO. Energy level diagrams reveal the decrease of degeneracy of FTO towards an n-type semiconducting SnO2 film which is also supported by ultraviolet photoelectron spectroscopy (UPS). A band gap energy dependence with the plasma conditions allowed to check the filling of oxygen vacancies on the FTO surface without discard the loss of fluorine. Anodic polarization in acid media proved the impossibility of oxygen vacancies restitution, being the dominating process the partial etching of FTO.