Effect of Sintering on Grain Boundary Microstructure and Electrical Properties of CaCu_3Ti_4O_(12) Ceramics

CaCu3Ti4O12 ceramic with a giant dielectric constant was synthesized by sol-gel method and sintered in three different sintering conditions： 1 035 ℃ for 48 h, 1 080 ℃ for 3 h and 48 h. The phase of the ceramics, the element distribution, the valance state of Ti ions at grain boundaries, and the electrical properties were characterized via X-ray diffraction（XRD）, energy dispersive X-ray analysis（EDAX）, X-ray photoelectron spectroscopy（XPS）, electrical conduction and dielectric measurement. The results demonstrate that the grain-boundary microstructure and the electrical properties are influenced by sintering conditions： 1 By raising sintering temperature, the Cu-rich and Ti-poor grain boundary was formed and grain resistivity was decreased. 2 By prolonging sintering time, the content of Ti3＋ near the grain boundary increased, leading to the decrease of the grain-boundary resistivity and the increase of the activation energy at grain boundary. The ceramic, sintering at 1 080 ℃ for 48 h, exhibited a small grain resistivity（60.5 ＊cm）, a large grain-boundary activation energy（0.42 e V）, and a significantly enhanced dielectric constant（close to 1×105 at a low frequency of 1×103 Hz）. The results of electrical properties accord with the internal boundary layer capacitor model for explaining the giant dielectric constant observed in Ca Cu3Ti4O12 ceramics.

Small Rb^+ Doping in CaCu_3Ti_4O_(12)——A Possible Approach to Reduce Dielectric Loss

Ca1-xRbxCu3Ti4O12 （x=0, 0.01, 0.02 and 0.03） ceramics were synthesized by the sol-gel method. Doping Rb＋ reduces dielectric loss, which reaches minimum when x=0.02. By measuring properties of electrical conduction, larger leakage current density and height of grain-boundary Sehottky potential barrier （φB） were found in the doped samples, and φB became maximum when x=0.02. These results are attributed to the increase in the amount of oxygen vacancies and the formation of Cu-rich/Ti-poor grain-boundary layers, and it can be concluded that the dielectric loss in CCTO ceramic can be reduced by manipulating the composition and electrical properties of grain boundary.

Dielectric Properties and Electrical Conductivity of CaCu_3Ti_4O_(12) Ceramics Doped with Zr^(4+)

CaCu3Ti4O12 （CCTO） ceramics doped with Zr^4＋ were prepared. Effects of Zr^4＋ on microstructure, dielectric properties and conduction behavior of CaCaCu3Ti4O12 （x=0, 0.05, 0.10, 0.20） ceramics were studied in the frequency range of 10-10^6 Hz. Grain size and dielectric loss of Zr^4＋-doped CCTO ceramic decreased compared with pure CCTO. The loss tangent （tang） of CaCu3Ti4O12 （x=0.20） ceramic droped to 0.05 at a frequency of 1 kHz, which was reduced by 55% compared with pure CCTO ceramic. The mechanism effect of electrical conductivity on dielectric loss of ZP^4＋-doping CCTO ceramics was also discussed.

Enhanced Dielectric Response in Mg-doped CaCu_3Ti_4O_(12) Ceramics

CaCu3Ti4O12 ceramics substituted by Mg for Ca were prepared by the solid state reaction method. The crystal structures, microstructures, and dielectric properties of the Ca1-xMgxCu3Ti4O12 ceramics were investigated. At lower doping concentrations, the substitution of Mg for Ca caused a decreased lattice constant, while at higher doping concentrations, some of the Mg dopants started to replace Ti and resulted in an increased lattice constant, and some could also replace Cu due to the similar ion radius between Mg and Cu ions. Mg doping was found to promote the grain growth of Ca1-xMgxCu3Ti4O12 ceramics during sintering. Grain boundary resistance of the Ca1-xMgxCu3Ti4O12 ceramics was found to be increased by Mg doping. Enhanced dielectric properties was observed in the Ca1-xMgxCu3Ti4O12 ceramics with x=0.05 for the frequency range from i kHz to 20 kHz. For other doping concentrations, the dielectric losses of Ca1-xMgxCu3Ti4O12 ceramics were generally lowered.