Significantly improved giant dielectric properties and enhanced nonlinear coefficient of Ni2+ doped CaCu3Ti4O12/CaTiO3 composites.

CaCu3-xNixTi4O12/CaTiO3 ceramic composites were fabricated using initial Ca2Cu2-xNixTi4O12 compositions (x = 0, 0.05, 0.10, and 0.20) to improve the dielectric properties (DPs) of the CaCu3Ti4O12 ceramics. CaCu3Ti4O12 and CaTiO3 phases were confirmed. Microstructural analysis and Rietveld refinement showed that the Ni2+ dopant might substitute the Cu2+ sites of the CaCu3Ti4O12 structure. The average grain sizes of CaCu3Ti4O12 (4.1-5.6 µm) and CaTiO3 (1.2-1.4 µm) changed slightly with the Ni2+ doping concentration. The best DPs were obtained for the CaCu3-xNixTi4O12/CaTiO3 with x = 0.2. The loss tangent was significantly reduced by an order of magnitude compared to that of the undoped composite, from tanδ∼0.161 to ∼0.016 at 1 kHz, while the dielectric permittivity slightly decreased from ε'∼5.7 × 103 to ∼4.0 × 103. Furthermore, the temperature dependence of ε' could be improved by doping with Ni2+. The improved DPs were caused by the enhanced electrical responses of the internal interfaces, which resulted in enhanced non-Ohmic properties. The largest nonlinear coefficient (α∼7.6) was obtained for the CaCu3-xNixTi4O12/CaTiO3 with x = 0.05. Impedance spectroscopy showed that the CaCu3-xNixTi4O12/CaTiO3 composites consisted of semiconducting and insulating components. The DPs of CaCu3-xNixTi4O12/CaTiO3 were explained based on the space-charge polarization at the active-interfaces.

Colossal dielectric permittivity, reduced loss tangent and the microstructure of Ca1-x Cd x Cu3Ti4O12-2y F2y ceramics.

Ca1-x Cd x Cu3Ti4O12-2y F2y (x = y = 0, 0.10, and 0.15) ceramics were successfully prepared via a conventional solid-state reaction (SSR) method. A single-phase CaCu3Ti4O12 with a unit cell ∼7.393 Šwas detected in all of the studied ceramic samples. The grain sizes of sintered Ca1-x Cd x Cu3Ti4O12-2y F2y ceramics were significantly enlarged with increasing dopant levels. Liquid-phase sintering mechanisms could be well matched to explain the enlarged grain size in the doped ceramics. Interestingly, preserved high dielectric permittivities, ∼36 279-38 947, and significantly reduced loss tangents, ∼0.024-0.033, were achieved in CdF2 codoped CCTO ceramics. Density functional theory results disclosed that the Cu site is the most preferable location for the Cd dopant. Moreover, F atoms preferentially remained close to the Cd atoms in this structure. An enhanced grain boundary response might be a primary cause of the improved dielectric properties in Ca1-x Cd x Cu3Ti4O12-2y F2y ceramics. The internal barrier layer capacitor model could well describe the colossal dielectric response of all studied sintered ceramics.