A/B-site cosubstituted Ba4Pr28/3Ti18O54 microwave dielectric ceramics with temperature stable and high Q in a wide range

High permittivity Ba₄(Pr_1-xSm_x)_28/3Ti_18-yAl_4y/3O₅₄(0.4≤x ≤ 0.7, 0≤y ≤ 1.5) ceramics were synthesized using a standard solid-state method. The effects of Sm³⁺ substitution into the A-site and Sm³⁺/Al³⁺ cosubstitution into the A/B-sites on the microstructure, crystal structure, Raman spectra, infrared reflectivity (IR) spectra and dielectric characteristics were investigated in a Ba₄Pr_28/3Ti₁₈O₅₄ solid solution. In the ceramic samples of Ba₄(Pr_1-xSm_x)_28/3Ti₁₈O₅₄(0.4≤x ≤ 0.7), Sm³⁺ partial substitution for Pr³⁺ could improve the quality factor (Qf) value and reduce the TCF value. Nevertheless, the quality factor (Qf~10,000GHz) needed further improvement and the TCF values (+12.3~+35.4 ppm/°C) were still too large. Therefore, Al³⁺ was introduced for further optimization of the TCF values and Qf values of the Ba₄(Pr_1-xSm_x)_28/3Ti₁₈O₅₄ ceramics. Sm/Al cosubstitution led to a good combination of high ε_r (ε_r ≥ 70), high Qf (Qf ≥ 12,000 GHz), and near-zero TCF (?10 < TCF < +10 ppm/°C) in a wide range (0.4≤x ≤ 0.7). Infrared reflectivity (IR) spectra indicated that A-TiO₆ vibration modes gave the primary contribution rather than Ti–O bending and stretching modes. The decrease in the degree of B-site cations order could be confirmed by Raman spectra. XPS results demonstrated that the improvement of quality factor (Qf) value was strongly related to the suppression of Ti³⁺. Excellent dielectric properties were achieved in Ba₄(Pr_1-xSm_x)_28/3Ti_18-yAl_4y/3O₅₄ microwave ceramics with x = 0.5 and y = 1.25: ε_r = 72.5, Qf = 13,900GHz, TCF = +1.3 ppm/°C.