Electrical Conductivity, Thermoelectric Power, and Equilibration Kinetics of Nb-Doped TiO₂

Abstract

This work considers the equilibration kinetics of Nb-doped TiO2 single crystal (0.066 atom % Nb) during oxidation and reduction within a wide range of temperature (1073-1298 K) and oxygen activity (10(-14)-10(5) Pa). The associated semiconducting properties were determined using simultaneous measurements of both electrical conductivity and thermoelectric power. It is shown that the chemical diffusion coefficient in the strongly reducing regime, p(O2) < 10(-5) Pa, is 4 orders of magnitude larger than that in the reducing and oxidizing regimes, 10 Pa < p(O2) < 22 kPa. The derived theoretical model considers the gas/solid kinetics for the TiO2/O2 system in terms of two diffusion regimes: the fast regime related to fast defects (oxygen vacancies and titanium interstitials) and leading to quasi-equilibrium, and the slow regime associated with slow defects (titanium vacancies) resulting in the gas/solid equilibrium. It has been shown that incorporation of donor-type elements, such as niobium, and imposition of oxygen activity above a certain critical value, results in a substantial reduction in the concentration of high mobility defects and leads to slowing down the equilibration kinetics. In consequence, the fast kinetic regime is not observed. Comparison of the kinetic data for Nb-doped TiO2 single crystal (this work) and polycrystalline Nb-doped TiO2 (reported before) indicates that the gas/solid kinetics for the polycrystalline specimen at higher oxygen activities is rate controlled by the transport of oxygen within individual grains.