Wolframite structure Zn1−xCoxZrNb2O8 (x = 0, 0.02, 0.04, 0.06, 0.08, 0.10) ceramics were prepared by the conventional solid state method. The crystal structures were studied via X-ray diffraction, and lattice vibrational modes were obtained by Raman spectroscopy. It could be found that all the A-site (Zn2+/Co2+, Zr4+) and B-site (Nb5+) cations were octahedrally coordinated with oxygen anions from the diagrammatic sketch of the crystal structure. Rietveld refinement was used to analyze the crystal structure and the lattice parameters were obtained. Based on the complex chemical bond theory and lattice parameters, intrinsic factors such as the bond ionicity, lattice energy, bond energy and coefficient of thermal expansion were calculated. Based on the results, Nb–O bonds played an important role in affecting the microwave dielectric proprieties of Zn1−xCoxZrNb2O8 ceramics. Co2+ substitution would affect the crystal structure and influence the microwave dielectric properties. The tendency of the dielectric constant (εr) could be predicted by the polarizability and bond ionicity of Nb–O bonds, and the εr showed the same tendency with Raman shifts of Nb–O vibration modes. The variation of the quality factor (Qf) could be explained by the change of the lattice energy of Nb–O bonds and the full width at half maximum (FWHM) values of Nb-site Raman modes. The temperature coefficient of resonant frequency (τf) showed the same tendency with the bond energy, octahedral distortion and bond valence of Nb–O bonds, and the opposite tendency with the thermal expansion coefficient.
Wolframite-structured Zn 1-x Mg x ZrNb 2 O 8 (0 ≤ x ≤ 0.1) ceramics were synthesized by the conventional solid-state method. The effects of Mg 2+ substitution on the sinter ability, crystal structures and microwave dielectric properties were systematically investigated. The Q·f values increased from 46,800 GHz to 53,400 GHz when the x value increased from 0 to 0.1. Based on the complex chemical bond theory, the intrinsic parameters were calculated to analyze the mechanism of dielectric loss in Zn 0.9 Mg 0.1 ZrNb 2 O 8 . The total lattice energy and bond energy of the Zn 0.9 Mg 0.1 ZrNb 2 O 8 were higher than that of ZnZrNb 2 O 8 , which was corresponding with the decrease of dielectric loss in the wolframite-structured compounds. The dielectric constant ( ε r ) and temperature coefficient of resonant frequency ( τ f ) of Zn 1-x Mg x ZrNb 2 O 8 ceramics were also heavily influenced by the addition of Mg 2+ . Typically, the dense Zn 0.9 Mg 0.1 ZrNb 2 O 8 ceramics sintered at 1200 °C exhibited excellent microwave dielectric properties with ε r = 27.82, Q·f = 53,400 GHz and τ f = −45.82 ppm/°C.
Low-temperature co-fired ceramics technology (LTCC) exhibits enormous superiorities in packaging, integration, and interconnection. However, the complex compositions of low-melting point sintering aids may react with ceramic matrix, which increases the difficulties of phase control and tape casting. In this work, the Li 2 CO 3 –B 2 O 3 –Bi 2 O 3 –SiO 2 (LBBS) sintering aid was adopted to sinter ZnZrNb 2 O 8 ceramics with single phase at low temperatures. The LBBS glass could be used to fabricate pure-phase ZnZrNb 2 O 8 ceramics at a low sintering temperature, promote the grain growth, and increase the densification of ZnZrNb 2 O 8 ceramics. Furthermore, the unit cell volume, NbO 6 octahedral distortion, Raman shift, and FWHM changed along with LBBS addition, thereby affecting the microwave dielectric properties. Remarkably, ZnZrNb 2 O 8 ceramics doped with 0.75 wt.% LBBS at 950°C were chemically compatible with the silver electrode and exhibited excellent microwave dielectric characteristics: ε r = 27.1, Q × f = 54 500 GHz, and τ f = −48.7 ppm/°C, providing candidates for LTCC applications.
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