Improved microstructure and significantly enhanced dielectric properties of Al3+/Cr3+/Ta5+ triple-doped TiO2 ceramics by Re-balancing charge compensation

Abstract

The charge compensation mechanism and dielectric properties of the (Al_xCr_0.05−x)Ta_0.05Ti_0.9O₂ ceramics were studied. The mean grain size slightly changed with the increase in the Al³⁺/Cr³⁺ ratio, while the porosity was significantly reduced. The dielectric permittivity of the co-doped Cr_0.05Ta_0.05Ti_0.9O₂ ceramic was as low as ε′∼ 10³, which was described by self-charge compensation between Cr³⁺–Ta⁵⁺, suppressing the formation of Ti³⁺. Interestingly, ε′ can be significantly increased (6.68 × 10⁴) by re-balancing the charge compensation via triple doping with Al³⁺ in the Al³⁺/Cr³⁺ ratio of 1.0, while a low loss tangent (∼0.07) was obtained. The insulating grains of [Cr_0.05³⁺Ta_0.05⁵⁺]Ti_0.9⁴⁺O₁₂ has become the semiconducting grains for the triple-doped Al_x³⁺[Cr_0.05−x³⁺Ta_0.05−x⁵⁺][Ta_x⁵⁺Ti_x³⁺Ti_0.9+x⁴⁺]O_12+3x/2. Considering an insulating grain with low ε′ of the Cr_0.05Ta_0.05Ti_0.9O₂ ceramic, the electron-pinned defect-dipoles and interfacial polarization were unlikely to exist supported by the first principles calculations. The significantly enhanced ε′ value of the triple-doped ceramic was primarily contributed by the interfacial polarization at the interface between the semiconducting and insulating parts, which was supported by impedance spectroscopy. This research gives an underlying mechanism on the charge compensation in the Al³⁺/Cr³⁺/Ta⁵⁺-doped TiO₂ system for further designing the dielectric and electrical properties of TiO₂-based ceramics for capacitor applications.