Dielectric properties and microstructural behaviour of B-site calcium-doped barium titanate ceramics

Dielectric properties and microstructural behaviour of Ba_1–xSr_xTi_1–yCa_yO_3–y ceramics, where strontium and calcium were doped on the barium and titanium sites, respectively, within the range 0x0.24 and 0y0.05, were investigated. Calcium addition decreased the tetragonality,c/a, increased the unit cell volume, and lowered the Curie temperature, which were all attributed to the occupancy of Ca²⁺ ions on titanium sites. When sintered at a low oxygen partial pressure of 10^–9 MPa, a resistivity higher than 10¹¹ cm was maintained for the formulations containing B-site calcium substitution more than 0.5 mol %. With increasing the amount of calcium addition, the Curie peak was depressed and completely broadened for the compositions with calcium addition more than 3 mol %, where the average grain size was smaller than 1 m. Co-firing with nickel electrodes in a reducing atmosphere also depressed the Curie peak and inhibited the grain growth due to the diffusion of nickel into the dielectrics.