Effect of co-substitution of nitrogen and fluorine in BaTiO3 on ferroelectricity and other properties.

BaTiO3, with both nitrogen and fluorine substituted for oxygen, has been prepared and the properties of the doped material with the composition BaTiO2:8N0:1F0:1 have been studied. The color of the sample changes to light green on doping, accompanying a broad visible absorption band with its edge at 2.5 eV. The first-order ferroelectric transition changes to a broad transition on doping along with a decrease in the dielectric constant. We have examined the local structure, electronic structure and polar lattice dynamical properties of N and F co-substituted BaTiO3 using first-principles density functional theory-based calculations and derived the mechanism of the diffuse ferroelectric transition observed here with a broad peak in the temperature-dependent dielectric response. The calculated Born charges clearly reveal a strong disparity in the interaction of N, O and F with Ti: N being the most ferro-active, with a highly anomalous charge, and F being the least active, with an almost nominal charge. This originates from an electronic structure in which the top-most valence band is constituted of the 2p states of N, while the electronic states of F lie deep in the energy band, resulting in a local structure with short covalent Ti–N and long ionic Ti–F bonds. Disorder in these hetero ferro-active anions leads to a relaxor-like diffuse phase transition and a reduction in polarization. Calculations confirm the reduction of 0.65 eV in the bandgap of BaTiO3, which changes from indirect to direct type.