Optimized phase compositions and microwave dielectric properties of low loss Ca2Sn2Al2O9-based ceramics by M4+ substitution

The traditional solid-state reaction method was used to prepare Ca₂Sn_2−xM_xAl₂O₉ (M = Ti, Zr, and Hf) ceramics. Then, the impact of an M⁴⁺ substitution of Sn⁴⁺ on the phase transition, crystal structural parameter, and microwave dielectric properties of Ca₂Sn_2−xM_xAl₂O₉ (0 ≤ x ≤ 0.4) ceramics were investigated. Ti⁴⁺ could not replace the Sn⁴⁺ of Ca₂Sn₂Al₂O₉ due to its small ionic radius, and the Al-based second phases of Ca₂Sn_2−xTi_xAl₂O₉ ceramics were confirmed by the X-ray diffractometer and EDS map scanning results. With the Zr⁴⁺ and Hf⁴⁺ substitutions of Sn⁴⁺, the SnO₂ and CaSnO₃ second phases of Ca₂Sn₂Al₂O₉ ceramic were inhibited, and the Ca₂Sn_2−xM_xAl₂O₉ (M = Zr and Hf) (0.05 ≤ x ≤ 0.2) single-phase ceramics with orthorhombic structure (Pbcn space group) were obtained. New MO₂ (M = Zr and Hf) and CaAl₂O₄ second phases appeared in the Ca₂Sn_2−xM_xAl₂O₉ (M = Zr and Hf) (0.3 ≤ x ≤ 0.4) ceramics, and their contents increased gradually with the increase in x. The Ca₂Sn_2−xM_xAl₂O₉ (M = Zr and Hf) (0.05 ≤ x ≤ 0.2) ceramics exhibited high Q × f because of their pure phase compositions, and the Q × f of Ca₂Sn₂Al₂O₉ ceramic was improved to 77 800 GHz (12.6 GHz) in the Ca₂Sn_1.9Zr_0.1Al₂O₉ ceramic. The Q × f values of Ca₂Sn_2−xM_xAl₂O₉ single-phase ceramics were mainly controlled by r_c (Sn/M–O) and r_c (Al–O). The τ_f values of single-phase Ca₂Sn_2−xM_xAl₂O₉ ceramics were related to octahedral distortions. The Zr⁴⁺ and Hf⁴⁺ substitution of Sn⁴⁺ optimized the phase compositions and microwave dielectric properties of the Ca₂Sn_2−xM_xAl₂O₉ ceramics, and the Ca₂Sn_1.9Zr_0.1Al₂O₉ ceramic sintered at optimal temperature exhibited excellent microwave dielectric properties (ε_r = 8.67, Q × f = 77 800 GHz at 12.6 GHz and τ_f = −69.8 ppm/°C).