Effects of Zr4+ and Hf4+ substitution on the structure and dielectric response of Ba4Sm9.33Ti18O54 ceramics

Microwave dielectric ceramics with high relative permittivity (εr) are commonly used for the miniaturation of microwave devices. The dielectric loss mechanism of microwave dielectric ceramics, as well as the property modification, has been a concerned topic among scholars. Herein, the lattice structure, defects, and broadband dielectric response of Zr4+ and Hf4+ substituted Ba4Sm9.33Ti18O54 (BST) ceramics are systematically examined. The negative temperature coefficient of resonant frequency (τf) of BST ceramics can be tuned to near zero via ion substitution, owing to the Sm2Ti2O7 second phase with a large positive τf. Optimal microwave dielectric properties of εr = 81.3, Q × f = 10,800 GHz, and τf = −4.6 ppm/°C are achieved. The lattice vibration behavior and defect concentration are analyzed by Raman spectra and thermally stimulated depolarization currents (TSDC), respectively. The increasing volume of the unit cell and TiO6 octahedra, which is because of the large-radius substitution ions, leads to an increase in lattice vibration damping factor and the generation of more oxygen vacancies (VO∙∙). Therefore, the dielectric losses in the microwave and terahertz (THz) bands increase after substitution. Meanwhile, the low-frequency dielectric losses at high temperatures also increase due to the weak restraint of carriers by the lattice. The broadband loss mechanism of Zr4+ and Hf4+ substituted BST ceramics related to lattice vibration and defects might be referenced for developing low-loss dielectric ceramics.