PNNL

Abstract

Minute changes in oxygen concentration in complex oxides even of the order of ~0.001% can significantly influence functional properties ranging from onset of superconductivity to colossal dielectric constant and ferroic response. In this letter, we report on direct experimental measurement of enhanced oxygen incorporation into ultra-thin oxide films at room temperature under gentle UV photon exposure. Oxygen concentration changes in nanoscale yttria-doped-zirconia (YDZ) films grown on Ge substrate were quantified using the 16O(d,p)17O nuclear reaction. The oxygen concentration was consistently ~ 3 % larger in UV irradiated YDZ films compared to as-grown YDZ films and can be kinetically controlled. Possible incorporation mechanisms are discussed. This suggests a novel approach to modulate oxygen concentration in complex oxides. There is tremendous interest in the science and applications of ultra-thin oxide films, such as electrolyte membranes for solid oxide fuel cells 1, high-dielectric constant (high-?) oxides for metal-oxide-semiconductor (MOS) devices 2 and multi-ferroics 3. In addition, thin film oxides also serve as model systems to investigate space charge effects on carrier transport and strongly correlated phenomena such as phase transitions. An overarching problem of central importance is the controlled synthesis of oxide films and how they impact functional properties. Particularly, the role of oxygen vacancies or non-stoichiometry has been found to be crucial in this regard. Examples include large magneto resistance effect and metal-to-insulator transition introduced by reducing oxygen stoichiometry of poly crystalline La0.67Ba0.33MnOz 3, nonsuperconducting-to-superconducting transformation by minute amount of oxygen incorporation upon annealing YBa2Cu3O7-??(YBCO)?films 4, and blue light emission at room temperature in oxygen deficient SrTiO3 (STO) 5, 6. These studies revealed broad spectra of properties with subtle changes (e.g., of the order of ~0.01% to introduce semiconductor-to-metal transition in SrTiO3)7 in oxygen-related defects, thereby it is extremely important to develop an understanding of oxygen concentration in thin films.