Systematic tuning of the conduction mechanisms in ferroelectric thin films.

We have investigated the macroscopic and microscopic properties of large sets of Ba0.7Sr0.3TiO3 thin films including several substitution rates of manganese. Thanks to a high degree of control of the processing parameters at each stage we have been able to find a link between the dc leakage current and the low and high frequency dielectric permittivity and losses. We supplemented these macroscopic observations with in depth investigations of the defect states through x-ray photoelectron spectroscopy. We found that both the leakage current and the extrinsic dielectric parameters arise from a large density of charged point defects related to oxygen vacancies. At the outer surfaces of the films, the density of such charged defects is so high that it can raise the Fermi level to close to the conduction band. Such degradation of the films' performance can be relieved by appropriate manganese substitution for the titanium host ions. Such doping is able to move back the Fermi level to close to the center of the bandgap thus changing the conduction process from interfacial Schottky to bulk Poole Frenkel and decreasing the extrinsic losses. This beneficial effect was already inferred in ceramics and thin films but we have established a clear link between the macroscopic parameters and the microscopic defect state. This model can be transferred to many high permittivity oxides.