Lattice evolution, order transformation, and microwave dielectric properties of the Zn 1 x Li 2 x TiO 3 (0 x 1) system ceramics

Research on doping modification of ZnTiO3 ceramics to enhance microwave dielectric properties has been hindered by poor performance, unclear structure-function mechanisms. To expand the applicability of ZnTiO3 ceramics, this study explores Zn1–xLi2xTiO3 (0 ≤ x ≤ 1) ceramics using a phase engineering strategy. Our findings reveal that the introduction of Li+ into the ZnTiO3 system initiates a multiple phase transition, starting at x = 0.1. Initially, ilmenite ZnTiO3 transforms into a cubic ordered spinel phase (space group P4332). Subsequently, a transition to a disordered spinel phase (space group Fd-3m) occurs at x = 0.5, culminating in the formation of a monoclinic rock salt-structured Li2TiO3 phase. Significantly, two sets of ceramics with near-zero temperature coefficients of resonance frequency (τf) were obtained at x = 0.1 and 0.75. Moreover, the quality factor (Q×f) demonstrated a 4.4-fold increase compared to that of ZnTiO3 ceramics at x = 0.25 (105,013 GHz). Additionally, it was observed that the Ti4+ polarization in Zn1–xLi2xTiO3 ceramics had been underestimated by 11.3-13.3%, causing the measured dielectric constant (εr) exceeding the theoretical dielectric constant (εth). The ionic polarizability of Ti4+ was adjusted to stabilize around 3.29 Å3. Evaluation using multiple methods, including Phillips–Van Vechten–Levine theory, Raman vibrational mode analysis, bond valence, bond energy theory, and octahedral distortion, confirms that the Ti-O bonds within the octahedron predominantly affect εr, the increasing lattice energy (U) contributes to the enhancement of Q×f, and the strengthened Li-O bond energy effectively regulates τf.