Crystal structure of corundum type Mg4(Nb2–xTax)O9 microwave dielectric ceramics with low dielectric loss

New microwave dielectric ceramics, i.e. Mg₄(Nb_2−xTa_x)O₉ (MNT) solid solutions, were synthesized and their microwave dielectric properties and crystal structure were investigated in this study. From the discrete variational Xα (DV-Xα) method, it was found that the Ta–O bonds in the TaO₆ octahedron become more covalent than Nb–O bonds in the NbO₆ octahedron; this result leads to the decrease of the ionicity in the Ta⁵⁺ ion. The dielectric constants of MNT were slightly decreased from 12.4 to 11.5; this result might be due to the covalent interaction of Ta–O bonding. The quality factors of the samples were found to exhibit high value (Q·f≒350 000 GHz for x=2) which is comparable to those of Al₂O₃.     

Effects of (Mg1/3Ta2/3)-substitution for Ti-site on the microwave dielectric properties of Li2MgTiO4 ceramics

Novel high quality factor microwave dielectric ceramics Li₂MgTi_1?x(Mg_1/3Ta_2/3)_xO₄ (0 ≤ x ≤ 0.5) were successfully prepared via a conventional solid-state ceramic route. The effects of isovalent substitutions (Mg_1/3Ta_2/3)⁴⁺ at the Ti-site on the sintering behaviors, microstructures, and microwave dielectric properties of Li₂MgTiO₄ ceramics were investigated in this paper. The sintered samples exhibited the single phase with cubic rock-salt structure belonging to Fm-3m space group in the whole composition range. Rietveld refinement which could be performed by the Fullprof program was taken to explain the effects of (Mg_1/3Ta_2/3)⁴⁺ ion substitution on the crystal structures of Li₂MgTiO₄ ceramics. With the (Mg_1/3Ta_2/3)⁴⁺ content increasing from 0 to 0.5, the quality factor Q·f firstly increased and decreased thereafter, while the dielectric constant ε_r almost linearly decreased. In addition, the τ_f values shifted to positive value with the amount of (Mg_1/3Ta_2/3)⁴⁺ increasing. The best composition appeared to be Li₂MgTi_0.6(Mg_1/3Ta_2/3)_0.4O₄, which showed excellent microwave dielectric properties of ε_r = 15.73, Q·f = 184,000 GHz and τ_f = ? 12.54 ppm/°C. This made the Li₂MgTi_0.6(Mg_1/3Ta_2/3)_0.4O₄ ceramic a very promising candidate for use as a low-loss microwave material.     

Correlation between the structure and modified microwave dielectric characteristics of Zr4+ substituted Ni0.4Zn0.6Ti(1-x)ZrxNb2O8 ceramics

Microwave ceramics are an important classes of materials that are used in microwave communication systems, especially in the area of 5G wireless communication and the internet of things. In this work, to improve the Q×f values and enhance the temperature stability of Ni_0.4Zn_0.6TiNb₂O₈ ceramics, the influence of the substitution of Zr⁴⁺ ions at the Ti site in Ni_0.4Zn_0.6Ti_(1-x)Zr_xNb₂O₈ ceramics was investigated. The Q×f value increases from 32114 GHz to 45733 GHz and the τ_f value changes from 38.1 ppm/°C to 3 ppm/°C with a slight Zr⁴⁺ ion substitution (x = 0.1). Meanwhile, the sample with the Zr⁴⁺ ion substitution (x = 0.3) that was sintered at 1120 °C shows a very high Q×f value of 92078 GHz. Furthermore, the XRD results reveal that the phase and structure of the Ni_0.4Zn_0.6Ti_(1-x)Zr_xNb₂O₈ ceramics change with the different Zr⁴⁺ ion contents. The substitution of the Zr⁴⁺ ion can promote the sintering process for the Ni_0.4Zn_0.6Ti_(1-x)Zr_xNb₂O₈ ceramics and restrain the Ni_0.5Ti_0.5NbO₄ phase formation. The results obtained from Ni_0.4Zn_0.6Ti_(1-x)Zr_xNb₂O₈ ceramics can offer useful information for the study and application of high-frequency microwaves.     

High-Qf value and temperature stable Zn2+-Mn4+ cooperated modified cordierite-based microwave and millimeter-wave dielectric ceramics

Cordierite-based dielectric ceramics with a lower dielectric constant would have significant application potential as dielectric resonator and filter materials for future ultra-low-latency 5G/6G millimeter-wave and terahertz communication. In this article, the phase structure, microstructure and microwave dielectric properties of Mg₂Al_4–2x(Mn_0.5Zn_0.5)_2xSi₅O₁₈ (0 ≤ x ≤ 0.3) ceramics are studied by crystal structure refinement, scanning electron microscope (SEM), the theory of complex chemical bonds and infrared reflectance spectrum. Meanwhile, complex double-ions coordinated substitution and two-phase complex methods were used to improve its Q×f value and adjust its temperature coefficient. The Q×f values of Mg₂Al_4–2x(Mn_0.5Zn_0.5)_2xSi₅O₁₈ single-phase ceramics are increased from 45,000 GHz@14.7 GHz (x = 0) to 150,500 GHz@14.5 GHz (x = 0.15) by replacing Al³⁺ with Zn²⁺-Mn⁴⁺. The positive frequency temperature coefficient additive TiO₂ is used to prepare the temperature stable Mg₂Al_3.7(Mn_0.5Zn_0.5)_0.3Si₅O₁₈-ywt%TiO₂ composite ceramic. The composite ceramic of Mg₂Al_3.7(Mn_0.5Zn_0.5)_0.3Si₅O₁₈-ywt%TiO₂ (8.7 wt% ≤ y ≤ 10.6 wt%) presents the near-zero frequency temperature coefficient at 1225 °C sintering temperature: ε_r = 5.68, Q×f = 58,040 GHz, τ_f = ?3.1 ppm/°C (y = 8.7 wt%) and ε_r = 5.82, Q×f = 47,020 GHz, τ_f = +2.4 ppm/°C (y = 10.6 wt%). These findings demonstrate promising application prospects for 5 G and future microwave and millimeter-wave wireless communication technologies.     

Crystal structure,densification, and microwave dielectric properties of Li3Mg2(Nb(1−x)Mox)O6+x/2 (0 ≤ x ≤ 0.08) ceramics

A novel system Li₃Mg₂(Nb_(1−x)Mo_x)O_6+x/2 (0 ≤ x ≤ 0.08) microwave dielectric ceramics were fabricated by the solid-state method. The charge compensation of Mo⁶⁺ ions substitution for Nb⁵⁺ ions was performed by introducing oxygen ions. The X-ray diffraction patterns and Rietveld refinements indicated Li₃Mg₂(Nb_(1−x)Mo_x)O_6+x/2 ceramics with single phase and orthorhombic structure. Micro-structure and density confirmed that the grain of Li₃Mg₂(Nb_(1-x)Mo_x)O_6+x/2 ceramics grew well. In addition, the permittivity of Li₃Mg₂(Nb_(1−x)Mo_x)O_6+x/2 ceramics with the same trend as density decreased slightly with increasing Mo⁶⁺ ions content. However, the Q*f and τ_f were obviously improved with an appropriate amount of Mo⁶⁺ ions. When x ≤ 0.04, the Q*f was closely related to the bond valence of samples, while when x ≥ 0.06, the Q*f was closely related to the density of samples. The variations of τ_f and oxygen octahedral distortion were the opposite. In conclusions, the Li₃Mg₂(Nb_0.98Mo_0.02)O_6.01 ceramic sintered at 1200°C for 6 hours exhibited outstanding properties: ε_r ~ 15.18, Q*f ~ 116 266 GHz, τ_f ~ −15.71 ppm/^oC.     

Correlations between the structural characteristics and enhanced microwave dielectric properties of V–modified Li3Mg2NbO6 ceramics

Novel low-temperature fired Li₃Mg₂Nb_1-xV_xO₆ (x?=?0.02??0.08) microwave dielectric ceramics were synthetized by the partial substitution of V⁵⁺ ions on the Nb⁵⁺ sites. The effects of V⁵⁺ substitution on structure and microwave dielectric properties were investigated in detail. XRD patterns and Rietveld refinement demonstrated that all of the samples exhibited a single orthorhombic structure. The structural characteristics such as the polarizability, packing fraction and NbO₆ octahedron distortion were determined to establish the correlations between the structure and the microwave dielectric characteristics. The ?_r values presented a tendency similar to that of the polarizability. The high Q×f values were mainly attributed to the effects of the grain sizes and density rather than the packing fraction. The variation in the τ_f values was attributed to NbO₆ octahedron distortion. Notably, the Li₃Mg₂Nb_1-xV_xO₆ (x?=?0.02) ceramics sintered at 900?°C had outstanding microwave dielectric properties: ε_r=?16, Q×f=?131,000?GHz (9.63?GHz), and τ_f=???26?ppm/°C, making these ceramics promising ultralow loss candidates for low temperature co-fired ceramics (LTCC) applications.     

Structural dependence of microwave dielectric performance of wolframite structured Mg1-xCaxZrNb2O8 ceramics: Crystal structure,microstructure evolution,Raman analysis and chemical bond theory

Wolframite-structured Mg_1-xCa_xZrNb₂O₈ (0?0.1) ceramics were synthesized through a solid-state procedure. Crystal refinement indicates a pure Mg_1-xCa_xZrNb₂O₈ ceramic with a wolframite structure. Ca²⁺ substitution led to the redshift of the Ag mode at approximately 896 cm^?1. Additionally, Ca²⁺ substitution could promote grain growth and contribute to microstructure evolution from a polyhedral shape to a rod shape. According to chemical bond theory, an appropriate Ca²⁺ concentration can increase NbO bond iconicity and NbO bond lattice energy, which contributed to the great improvement in the dielectric constant and Q × f value. Additionally, the τ_f value was affected by the bond valence and thermal expansion coefficient of the MgO bond. The Mg_1-xCa_xZrNb₂O₈ (x = 0.04) ceramics exhibited great improvement in the Q × f value: ε_r = 25.21, Q × f = 116,000 GHz (@7.17 GHz) and τ_f = ?24.4 ppm/°C, which provides enormous potential for future millimeter-wave applications.     

Effects of W6+ substitution on crystal structure and microwave dielectric properties of Li3Mg2NbO6 ceramics

Li₃Mg₂(Nb_1-xW_x)O_6+x/2 (0 ≤ x ≤ 0.08) ceramics were synthesized by the solid-state reaction route. The effects of W⁶⁺ substitution on the phase composition, microstructure and microwave dielectric properties of Li₃Mg₂NbO₆ ceramics were investigated systematically. The XRD results showed that all the samples formed a pure solid solution in the whole doping range. The SEM iamges and relative density revealed the dense structure of Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics. The relationship between the crystal structure and dielectric properties of Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics was researched through polarizability, average bond valence, and bond energy. The substitution of W⁶⁺ for Nb⁵⁺ in Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics significantly promoted the Q × f values. In addition, the increase of W⁶⁺ content improved the thermal stability of the Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics. The Li₃Mg₂(Nb_0.94W_0.06)O_6.03 ceramics sintered at 1175 °C for 6h possessed excellent properties: ε_r ~ 15.82, Q × f ~ 124,187 GHz, τ_f ~ −18.28 ppm/°C.     

Influence of Ti4+ substitution for Ta5+ on the crystal structure,Raman spectra,and microwave dielectric properties of Ba3Ta4-4xTi4+5xO21 ceramics

This paper systematically investigated the influence of Ti⁴⁺ substitution for Ta⁵⁺ on the phase composition and microwave dielectric properties of Ba₃Ta_4-4xTi_4+5xO₂₁ (x = 0.1, 0.2, and 0.3) ceramics with hexagonal tungsten bronze-like structures. X-ray diffraction and Rietveld refinement results indicated that single-phase Ba₃Ta₄Ti₄O₂₁ could be obtained only with the x values of 0.1 and 0.2, and a secondary phase was detected at an x value of 0.3. The valence state of Ba₃Ta_4-4xTi_4+5xO₂₁ (x = 0.2) ceramics was analyzed through X-ray photoelectron spectroscopy. Increasing Ti⁴⁺/Ta⁵⁺ ratios could reduce sintering temperature and improve the microwave dielectric properties of Ba₃Ta_4-4xTi_4+5xO₂₁ solid solutions. However, the dielectric properties, particularly the quality factor, of Ba₃Ta_4-4xTi_4+5xO₂₁ ceramics deteriorated severely as a result of oxygen vacancy defects caused by the transition of the valence state from Ti⁴⁺ to Ti³⁺ when x = 0.2 and the coexistence of the secondary phase when x = 0.3. Infrared reflectivity spectroscopy was performed to explore the intrinsic dielectric properties of Ba₃Ta_4-4xTi_4+5xO₂₁ (x = 0.1) ceramics. The measured and extrapolated microwave dielectric properties of Ba₃Ta_4-4xTi_4+5xO₂₁ (x = 0.1) ceramics sintered at 1240 °C for 6 h were ε_r ~ 46.5, Q × f = 13,900 GHz, τ_f ~ +49.4 ppm/°C, and ε_r ~ 44, Q × f = 34,850 GHz.     

Three-phase borate solid solution with low sintering temperature,high-quality factor,and low dielectric constant

The sintering and microwave dielectric properties of a ceramic material based on the mixing of Mg₃B₂O₆ and Zn₃B₂O₆ have been widely studied using first-principles calculations and experimental solid-state reactions. Characterization methods include the Network Analyzer, X-ray, Raman diffraction, scanning electron microscopy, energy-dispersive spectroscopy, and differential-thermal and thermo-mechanical analyzer. The increasing amount of Mg²⁺ results in the appearance of Mg₂B₂O₅ and ZnO, and the mutual substitution (Mg²⁺ and Zn²⁺) phenomenon has emerged in Zn₃B₂O₆ and Mg₂B₂O₅. The mechanisms have been explained with the help of DFT calculations. The bond parameters and electron distributions of the ZnO₄ tetrahedron and MgO₆ octahedron have been modified due to substitution. The sintering, substitution, and phase formation properties have been analyzed quantitatively through the energy parameters. The best dielectric properties were obtained for x = 0.20 sintered at 950°C, ε_r = 6.47, Q × f = 89 600 GHz (15.2 GHz), τ_f = −48.6 ppm/°C, relative density = 96.7%. The mixing of Zn₃B₂O₆ and Mg₃B₂O₆ ceramics is a feasible method to obtain a ceramic with low sintering temperature and excellent dielectric properties.     

Lattice structure analysis and optimised microwave dielectric properties of LiAl1-x(Zn0.5Si0.5)xO2 solid solutions

Low-permittivity LiAl_1-x(Zn_0.5Si_0.5)_xO₂ microwave dielectric ceramics were prepared by the solid-state reaction method. Single-phase LiAlO₂ solid solutions with a tetragonal structure were achieved at x ≤ 0.12. Partial substitution of [Zn_0.5Si_0.5]³⁺ for Al³⁺ could improve the microstructure and prevent from absorbing moisture of pure LiAlO₂ ceramics, which slightly increases their relative permittivity (ε_r). The quality factor (Q × f) and temperature coefficient of resonant frequency (τ_f) were closely related to the crystallinity and cation disorder of the B-site characterized by the full width at half-maximum of B₁⁽¹⁾ –mode assigned to Li–O–Al stretching. The optimum microwave dielectric properties (ε_r = 6.12, Q × f = 56986 GHz and τ_f = -122 ppm/°C) were obtained in the sample with x = 0.02 sintered at 1300 °C.     

Weak ferroelectricity and low-permittivity microwave dielectric properties of Ba2Zn(1+x)Si2O(7+x) ceramics

Ba₂Zn_(1+x)Si₂O_(7+x) ceramics were prepared using the conventional solid-state method at 1200 °C for 3 h in air. Apart from the previously reported Ba₂Zn_(1+x)Si₂O_(7+x) (x = 0) with a monoclinic structure (C 2/c), the end-member compositions at x = −1 and 1 exhibit single-phase β-BaSiO₃ with an orthorhombic structure (P2₁2₁2₁) and BaZnSiO₄ with a hexagonal structure (P6₃), and possess a coexistence of weak ferroelectricity and low-permittivity microwave dielectric properties. A reduction in Zn²⁺ content mainly decreases the intensity of the ε_r anomaly peak at lower temperature and increases the ε_r (or frequency) stability against temperature. The Zn²⁺-rich BaZnSiO₄ phase has a τ_f value of −181 ppm/°C, whereas the τ_f value of Zn²⁺-free BaSiO₃ phase decreases to −35.4 ppm/°C. The Zn²⁺ deficiency in Ba₂ZnSi₂O₇ composition could inhibit the presence of BaZnSiO₄ phase and improve the τ_f value, whereas excessive Zn²⁺ cations prompt the formation of the BaZnSiO₄ phase to deteriorate significantly the τ_f value.     

Influence of Cr3+ substitution for Mg2+ on the crystal structure and microwave dielectric properties of CaMg1-xCr2x/3Si2O6 ceramics

The CaMg_1-xCr_2x/3Si₂O₆ (0?≤?x?≤?0.1) microwave dielectric ceramics were synthesized via conventional solid state reaction. In this study, the effects of Cr³⁺ substituting for Mg²⁺ on morphology, crystal structure and microwave dielectric properties of CaMg_1-xCr_2x/3Si₂O₆ ceramics were explored. XRD diffraction patterns exhibited that the CaMg_1-xCr_2x/3Si₂O₆ ceramics possessed the pure phase of CaMgSi₂O₆ when x?≤?0.06 and a small amount of secondary phase Ca₃Cr₂(SiO₄)₃ for 0.08?≤?x?≤?0.1. SEM micrographs revealed that the substitution of Mg²⁺ with Cr³⁺ could decrease the grain size. The apparent density was affected by the concentration of Mg vacancies. The correlation between crystal structure and microwave dielectric properties was investigated through the Rietveld refinement and Raman analysis. The microwave dielectric properties were mainly dependent on relative density, ionic polarizabilities, internal strain ?, disordered structure and MgO₆ octahedron distortions. Finally, CaMg_1-xCr_2x/3Si₂O₆ (x?=?0.02) ceramics sintered at 1270?°C for 3?h exhibited excellent microwave dielectric properties of ε_r?=?8.06, Q?×?f?=?89054?GHz, τ_f?=??44.92182?ppm/ºC.     

Sb-doping effects on twin-shift option and microwave dielectric properties of Ba8CoNb6O24 eight-layer hexagonal perovskite ceramics

B-site deficient eight-layer hexagonal perovskites possess in general high quality factors and large positive temperature coefficients of resonant frequency (τ_f). Recently we successfully lowered τ_f of shifted perovskite Ba₈CoNb₆O₂₄ down to near zero through one-third Ta⁵⁺ substitution but raised the cost of the materials. In this work, Ba₈CoNb₆O₂₄ was doped with cheaper elements Sb⁵⁺ on Nb⁵⁺ sites using conventional solid-state reactions, and near-zero τ_f of 0.66(2) ppm/°C, modest ε_r of 27.99(3), Q × f of 1.016(6) × 10⁴ GHz, and significantly reduced cost of the ceramics were achieved on the composition Ba₈CoNb_5.4Sb_0.6O₂₄. The lower polarizability of Sb⁵⁺ than Nb⁵⁺ results in smaller ε_r and therefore τ_f values. About 15 % Sb⁵⁺ substitution for Nb⁵⁺ in Ba₈CoNb_6-xSb_xO₂₄ dramatically transforms the shifted structure to twinned structure, in contrast with 50 % Ta⁵⁺ substitution in the Ta⁵⁺ case. This is ascribed to reduced SOJT effects and ionic size of d¹⁰ Sb⁵⁺ compared with d° Nb⁵⁺ and Ta⁵⁺.     

Cation distribution of high-performance Mn-substituted ZnGa2O4 microwave dielectric ceramics

In current study, only 5?mol% Mn²⁺ was applied to fabricate high performance microwave dielectric ZnGa₂O₄ ceramics, via a traditional solid state method. The crystal structure, cation distribution and microwave dielectric properties of as-fabricated Mn-substituted ZnGa₂O₄ ceramics were systematically investigated. Mn²⁺-substitution led to a continuous lattice expansion. Raman, EPR and crystal structure refinement analysis suggest that Mn²⁺ preferentially occupies the tetrahedral site and the compounds stay normal-spinel structure. The experimental and theoretical dielectric constant of Zn_1-xMn_xGa₂O₄ ceramics fit well. In all, this magnetic ion, Mn²⁺, could effectively adjust the τ_f value to near zero and double the quality factor from 85,824?GHz to 181,000?GHz of Zn_1-xMn_xGa₂O₄ ceramics at the meantime. Zn_1-xMn_xGa₂O₄ (x?=?0.05) ceramics sintered at 1400?°C for 2?h exhibited excellent microwave dielectric properties, with ε_r =?9.7(@9.85?GHz), Q?×?f?=?181,000?GHz, tanδ?=?5.44?×?10^?5,and τ_f =???12?ppm/°C.     

Microwave dielectric properties of the (1 − x)Mg2TiO4-xCaTiO3-y wt.% ZnNb2O6 ceramics system

Composite ceramics based on (1 − x)Mg₂TiO₄-xCaTiO₃-y wt.% ZnNb₂O₆ (x = 0.12-0.16, y = 0-8) were prepared by a conventional mixed-oxide route. Zn²⁺ partially replaced Mg²⁺ in Mg₂TiO₄ and formed the spinel-structured (Mg_1−δZn_δ)₂TiO₄ phase. Nb²⁺, is known to be solid soluble in CaTiO₃, was found to change its shape from cubic to pliable. A bi-phase system (Mg_1−δZn_δ)₂TiO₄ and CaTiO₃ exhibited in all samples, where a small amount of second phase Mg_1−δZn_δTiO₃ was also detected. The microwave dielectric properties of specimens were strongly related to ZnNb₂O₆ and CaTiO₃ content. As y increased, ?_r and τ_f decreased, however, Q × f decreased to a minimum value and started to increase thereafter. It was also found that ?_r and τ_f increased and Q × f decreased with increasing x. The optimized microwave dielectric properties with ?_r = 18.37, Q × f = 31,027 GHz (at 6 GHz), and τ_f = 0.51 ppm/°C were achieved for (1 − x)Mg₂TiO₄-xCaTiO₃-y wt.% ZnNb₂O₆ (x = 0.12, y = 4) sintered at 1360 °C for 6 h.     

Crystal structure and performance modification of a novel triclinic CaMgP2O7 microwave dielectric ceramic with low sintering temperature

In this study, crystal structure and microwave dielectric properties of phosphate CaMgP₂O₇ were comprehensively investigated. As a novel microwave dielectric ceramic, CaMgP₂O₇ consists of highly dense structure with optimal microwave dielectric properties (ε_r = 7.8 ± 0.124, Q×f = 13,165 ± 836 GHz, and τ_f = −85.04 ± 1.205 ppm/℃) at a low sintering temperature (950 ℃). The Rietveld refinement of XRD patterns revealed that CaMgP₂O₇ belongs to a triclinic system with P-1 symmetry type. Moreover, the substitution of Zn²⁺ for Mg²⁺ in CaMgP₂O₇ can further reduce the sintering temperature, effectively promote the densification process, and improve the Q×f value. The effects of porosity (or density) and chemical bond characteristics on the performance of CaMg_1-xZn_xP₂O₇ ceramics were carefully analyzed as well. Outstanding performance (ε_r = 8.05 ± 0.12, Q×f = 20,670 ± 923 GHz, and τ_f = −87.59 ± 3.24 ppm/℃) can be achieved for the CaMg_0.84Zn_0.16P₂O₇ ceramic sintered at 875 ℃ for 3 h.     

Correlation between crystal structure and modified microwave dielectric characteristics of Cu2+ substituted Li3Mg2NbO6 ceramics

Structural characteristics exert significant influences on microwave dielectric properties, and ion substitution is widely adopted to modify material performances by adjusting the crystal structure. In this work, low loss Li₃Mg_2-xCu_xNbO₆ (x?=?0–0.04) ceramics were prepared by Cu²⁺ substitution. The impacts of Cu²⁺ substitution for Mg²⁺ sites on the microwave dielectric characteristics and crystal structure were discussed in detail. Rietveld refinement results implied that a single Li₃Mg₂NbO₆ phase was formed. Additionally, a dense and homogeneous microstructure with grain sizes of 7–9?μm could be achieved, and moderate Cu²⁺ substitution could significantly promote the grain growth. The correlation between microwave dielectric characteristics and crystal structure was discussed by calculating some structural parameters. The ε_r was determined by the polarizability. The Q?×?f was influenced by the packing fraction. The τ_f value was dependent on the NbO₆ octahedron distortion, and the τ_f value could be adjusted to near zero for x?=?0.02. Typically, the Li₃Mg_2-xCu_xNbO₆ (x?=?0.02) composition exhibited remarkable microwave dielectric performances: ε_r?=?15.75, Q?×?f?=?92,134?GHz (9.86?GHz) and τ_f?=??2?ppm/°C, making it a promising candidate for temperature-stable millimeter-wave applications.     

Effect of Mn2+ doping on the lattice and the microwave dielectric properties of MgTa2O6 ceramics

A series of Mn²⁺-doped Mg_1-xMn_xTa₂O₆ (x = 0.02, 0.04, 0.06, 0.08, 0.10, 0.12) ceramics were synthesized by solid-state reaction method. The influence of introducing Mn–O bonds as a partial replacement for Mg–O bonds on the lattice and microwave dielectric properties was systematically investigated. XRD and Rietveld refinement confirm that Mn²⁺ occupies the 2a Wyckoff position and forms a pure trirutile phase. Moreover, based on the chemical bond theory, the dielectric constant is mainly affected by the ionicity of the Ta–O bond. The lattice and dielectric properties remain relatively stable with Mn²⁺ doping below 0.1, but excessive Mn²⁺ doping leads to pronounced distortion of the lattice, which is not beneficial for lattice stability and microwave dielectric properties. Introducing an appropriate amount of Mn–O bonds with high bond dissociation energy facilitates MgO6 octahedron stability, which improves the thermal stability of the lattice. Accordingly, the microwave dielectric properties for 0.06 Mn²⁺-doped MgTa₂O₆ ceramics were determined: ε_r = 28, Q × f = 105,000 GHz (at 7.5 GHz), τ_f = 19.5 ppm/^°C.     

Structure evolution of wolframite-type ZnZrC2O8 (C = Nb,Ta) ceramics in relation to microwave dielectric properties

The relationship among the sintering behavior, crystal structure, chemical bonding properties, and dielectric properties of wolframite-type ZnZr(Nb_1−xTa_x)₂O₈ (0.0 ≤ x ≤ 1.0) ceramics was investigated with the progressive replacement of Nb⁵⁺ by Ta⁵⁺. The optimum sintering temperature increases from 1225 to 1375°C with increasing Ta⁵⁺ content. The ε_r value falls from 27.34 to 22.34 due to a gradual decrease in bond ionicity and a shift in the Raman vibration modes toward higher wave numbers. The Q × f increases from 63 604 GHz (@6.71 GHz) to 115 631 GHz (@7.89 GHz), which is since the increase in the total lattice of chemical bonds. Moreover, the reduction in grain boundary area and the gradual lowering of the full width at half maximum of the Raman vibration modes contribute to the reduction in dielectric losses. First-principles calculations illustrate that the growth in bandgap and electron cloud density in the internal space of the [Zn/ZrO₆] octahedron leads to a reduction in dielectric loss. Furthermore, the reduced degree of oxygen octahedral distortion causes a change in τ_f from −46.56 to −37.40 ppm/°C.