Structural evolution and microwave dielectric properties of CaTiO3–La(Mg2/3Nb1/3)O3 ceramics

(1 − x)CaTiO3–xLa(Mg2/3Nb1/3)O3 (CT–LMN; x = 0–1.0) solid solutions were prepared by a solid‐state reaction method. A phase transition from a disordered orthorhombic (Pbnm) structure to a 1:1 ordered monoclinic (P21/n) structure was observed when x increased from 0.5 to 0.6. Some new parameters, such as ionic polarizability in a polyhedron and ionic packing fraction in a polyhedron, were defined to explain the structure–property relationships of CT–LMN ceramics based on the Rietveld refinement results. The measured dielectric constant (εr‐mea) decreased monotonically with B‐site ionic polarizability in the [BO6] octahedron (αDT(B)/V[B]$\alpha _{\rm{D}}^{\rm{T}}( {\rm{B}} )/{V_{[ {\rm{B}} ]}}$) when the x value increased from 0 to 1.0. The quality factor (Qf) was dominated by the packing fraction of B‐site cations in the [BO6] octahedron (PF[B]), and both presented an increasing trend. The temperature coefficient of resonant frequency (τf) decreased from +588.5 to −79.7 ppm/°C, and it was highly correlated to the tolerance factor (t), αDT(B)/αDT(B)V[B]V[B]${{\alpha _D^T( {\rm{B}} )} \mathord{/ {\vphantom {{\alpha _D^T( {\rm{B}} )} {{V_{[ {\rm{B}} ]}}} \kern-\nulldelimiterspace} {{V_{[ {\rm{B}} ]}}}$ and PF[B]. The highest Qf value is obtained at x = 1.0 when sintered at 1600°C for 10 h with εr = 23.65 ± 0.2, Qf = 33517 ± 2000 GHz (@7.8 GHz), and τf = −79.7 ± 2.0 ppm/°C. Moreover, a near‐zero τf value was achieved at x = 0.4 with εr = 43.52 ± 0.2, Qf = 17239 ± 2000 GHz (@5.2 GHz), and τf = −10.2 ± 2.0 ppm/°C.