Measurement and control of oxygen non-stoichiometry in praseodymium-cerium oxide thin films by coulometric titration

Oxygen non-stoichiometry profoundly impacts the electrical, magnetic, and catalytic properties of metal oxide. Limited by the low mass and volume of thin oxide films, conventional quantification methods, such as thermogravimetry, are not directly applicable. While chemical capacitance has been successfully applied to monitor oxygen non-stoichiometry in thin oxide films, detailed a-priori understanding of the defect chemistry is often very helpful in its interpretation. In this study, changes in non-stoichiometry in Pr doped CeO₂ (PCO) thin films are measured by coulometric titration. I-V titration measurements are performed on electrochemical cells, over the temperature range from 550 to 700 ℃, oxygen partial pressure range from 10^-4 to 0.21 atm, and bias range of -50 mV to 50 mV, to extract changes in stoichiometry. The results agree well with values obtained by chemical capacitance, demonstrating the utility in applying coulometric titration to investigate oxygen non-stoichiometry in oxide thin films.