Influences of substituting of (Ni<sub>1/3</sub>Nb<sub>2/3</sub>)<sup>4+</sup>for Ti<sup>4+</sup>on the phase compositions, microstructures, and dielectric properties of Li<sub>2</sub>Zn[Ti<sub>1−<i>x</i></sub>(Ni<sub>1/3</sub>Nb<sub>2/3</sub>)<sub><i>x</i></sub>]<sub>3</sub>O<sub>8</sub>(0 ≤<i>x</i>≤ 0.3) microwave ceramics
Jiamao Li, Zexing Wang, Yunfeng Guo, Songlin Ran
Abstract
Complex ion substitution is gaining more attention as an appealing method of modifying the structure and performance of microwave ceramics. In this work, Li<sub>2</sub>Zn[Ti<sub>1−<i>x</i></sub>(Ni<sub>1/3</sub>Nb<sub>2/3</sub>)<sub><i>x</i></sub>]<sub>3</sub>O<sub>8</sub> (LZTNN<i>x</i>, 0 ≤ <i>x</i> ≤ 0.3) ceramics were designed based on the complex ion substitution strategy, following the substitution rule of radius and valence to investigate the relationship among phase compositions (containing oxygen vacancies and Ti<sup>3+</sup> ions), microstructures, and microwave dielectric characteristics of the LZTNN<i>x</i> ceramics. The samples maintained a single Li<sub>2</sub>ZnTi<sub>3</sub>O<sub>8</sub> solid solution phase as <i>x</i> ≤ 0.2, whereas the sample of <i>x</i> = 0.3 produced a second phase with the LiNbO<sub>3</sub> structure. The appropriate amount of (Ni<sub>1/3</sub>Nb<sub>2/3</sub>)<sup>4+</sup> substitution could slightly improve the densification of the LZTNN<i>x</i> ceramics due to the formation of the Li<sub>2</sub>ZnTi<sub>3</sub>O<sub>8</sub> solid solution accompanied by a decrease in the average grain size. The presence of a new A<sub>1g</sub> Raman active band at about 848 cm<sup>−1</sup> indicated that local symmetry changed, affecting atomic interactions of the LZTNN<i>x</i> ceramics. The variation of the relative dielectric constant (<i>ε</i><sub>r</sub>) was closely related to the molar volume ionic polarizability (<inline-formula> <math display="inline" id="MA1"><mrow><msubsup><mi>α</mi><mtext>D</mtext><mtext>T</mtext></msubsup></mrow></math></inline-formula>), and the temperature coefficient of the resonant frequency (<i>τ</i><sub>f</sub>) was related to the bond valence (<i>V</i><sub>i</sub>) of Ti. The increase in density, the absence of the Ti<sup>3+</sup> ions and oxygen vacancies, and the reduction in damping behavior were responsible for the decreased dielectric loss. The LZTNN0.2 ceramics sintered at 1120 ℃ exhibited favorable microwave dielectric properties: <i>ε</i><sub>r</sub> = 22.13, quality factor (<i>Q</i>×<i>f</i>) = 97,350 GHz, and <i>τ</i><sub>f</sub> = −18.60 ppm/℃, which might be a promising candidate for wireless communication applications in highly selective electronics.