Metastable oxygen incorporation into thin film NiO by low temperature active oxidation: Influence on hole conduction

The ability to controllably tune cation valence state and resulting electrical conductivity of transition metal-oxides such as NiO is of great interest for a range of solid state electronic and energy devices and more recently in understanding electron correlation phenomena at complex oxide interfaces. Here, we demonstrate that it is possible to enhance electrical conductivity of NiO thin films by one order of magnitude by photoexcitation and three orders of magnitude by ozone treatment at as low as 310 K. The change occurs within nearly 2000 s and, thereafter, reaches a self-limiting value. A surprising difference is seen at 400 K: ultraviolet photon and ozone treatments cause only a marginal reduction in resistance in the first few minutes and, then, the resistance begins to increase and recovers its original value. This unusual reversal is explained by considering metastable incorporation of oxygen in NiO and oxygen equilibration with the environment. Variation in nickel valence state prior to and after photoexcitation and ozone treatment, investigated by x-ray photoelectron spectroscopy, provides mechanistic insights into resistance trends. This study demonstrates photon-assisted and ozone oxidation as effective low temperature routes to tune the electrical properties as well as metastably incorporate oxygen into oxides with direct influence on electrical conduction properties.