A new temperature stable microwave dielectric ceramics: ZnTiNb2O8 sintered at low temperatures

The phases, microstructure and microwave dielectric properties of ZnTiNb₂O₈-xTiO₂ composite ceramics with different weight percentages of BaCu(B₂O₅) additive prepared by solid-state reaction method have been investigated using the X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS). The results showed that the microwave dielectric properties were strongly dependent on densification, grain sizes and crystalline phases. The sintering temperature of ZnTiNb₂O₈ ceramics was reduced from 1250 °C to 950 °C by doping BaCu(B₂O₅) additive and the temperature coefficient of resonant frequency (τ_f) was adjusted from negative value of −52 ppm/°C to 0 ppm/°C by incorporating TiO₂. Addition of 2 wt% BaCu(B₂O₅) in ZnTiNb₂O₈-xTiO₂ (x = 0.8) ceramics sintered at 950 °C showed excellent dielectric properties of ?_r = 38.89, Q × f = 14,500 GHz (f = 4.715 GHz) and τ_f = 0 ppm/°C, which represented very promising candidates as LTCC dielectrics for LTCC applications.     

High-dielectric-constant and low-loss microwave dielectric in the (1 − x)La(Mg0.5Ti0.5)O3-x(Ca0.8Sr0.2)TiO3 solid solution system

The microwave dielectric properties and microstructures of (1 − x)La(Mg_0.5Ti_0.5)O₃-x(Ca_0.8Sr_0.2)TiO₃ ceramics, prepared by a mixed oxide route, have been investigated. The forming of solid solutions was confirmed by the XRD patterns and the measured lattice parameters for all compositions. A near zero τ_f was achieved for samples with x = 0.5, although the dielectric properties varied with sintering temperature. The Q × f value of 0.5La(Mg_0.5Ti_0.5)O₃-0.5(Ca_0.8Sr_0.2)TiO₃ increased up to 1475 °C, after which it decreased. The decrease in dielectric properties was coincident with the onset of rapid grain growth. The optimum combination of microwave dielectric properties was achieved at 1475 °C for samples where x = 0.5 with a dielectric constant ?_r of 47.12, a Q × f value of 35,000 GHz (measured at 6.2 GHz) and a τ_f value of −4.7 ppm/°C.     

Microwave dielectric properties and its compatibility with silver electrode of Li2MgTi3O8 ceramics

The effects of BaCu(B₂O₅) (BCB) additions on the sintering temperature and microwave dielectric properties of Li₂MgTi₃O₈ ceramic have been investigated. The pure Li₂MgTi₃O₈ ceramic shows a relative high sintering temperature (∼1000 °C) and good microwave dielectric properties as Q × f of 40,000 GHz, ?_r of 27.2, τ_f of 2.6 ppm/°C. It was found that the addition of a small amount of BCB can effectively lower the sintering temperature of Li₂MgTi₃O₈ ceramics from 1025 to 900 °C and induce no obvious degradation of the microwave dielectric properties. Typically, the 0.5 wt% BCB added Li₂MgTi₃O₈ ceramic sintered at 900 °C for 2 h exhibited good microwave dielectric properties of Q × f = 36,200 GHz (f = 7.31 GHz), ?_r = 26 and τ_f = −2 ppm/°C. Compatibility with Ag electrode indicates this material can be applied to low temperature-cofired ceramics (LTCC) devices.     

Mg-substituted ZnNb2O6-TiO2 composite ceramics for RF/microwaves ceramic capacitors

Microstructure and microwave dielectric properties of Mg-substituted ZnNb₂O₆-TiO₂ microwave ceramics were investigated. Mg acted as a grain refining reagent and columbite phase stabilization reagent. With an increasing Mg content, the amount of ixiolite (Zn, Mg) TiNb₂O₈ decreased, and the amount of (Zn_0.9Mg_0.1)_0.17Nb_0.33Ti_0.5O₂ and columbite increased. ZnO-Nb₂O₅-1.75TiO₂-5 mol.%MgO exhibited excellent dielectric properties (at 950 °C): ?_r = 35.6, Q × f = 16,000 GHz (at 5.6 GHz) and τ_f = −10 ppm/°C. The material was applied successfully to make RF/microwaves ceramic capacitor, whose self-resonance frequency was 19 GHz at low capacitance of 0.13 pF.     

Low-firable high-K dielectric in the Zrx(Zn1/3Nb2/3)1−xTiO4 ceramic system

Composite ceramics in the solid solution of Zr_x(Zn_1/3Nb_2/3)_1−xTiO₄ (x = 0.1-0.4) have been prepared by the mixed oxide route. Formation of solid solution was confirmed by the X-ray diffraction patterns. The microwave dielectric properties, such as dielectric constant (?_r), Q × f value and temperature coefficient of resonant frequency (τ_f) have been investigated as a function of composition and sintering temperature. With x increasing from 0.1 to 0.4, the dielectric constant decreases from 70.9 to 43.2, and the τ_f decreases from 105 to 55 ppm/°C. The Q × f value, however, increases with increasing x value to a maximum 26,600 GHz (at 6 GHz) at x = 0.3, and then decreases thereafter. For low-loss microwave applications, a new microwave dielectric material Zr_0.3(Zn_1/3Nb_2/3)_0.7TiO₄, possessing a fine combination of microwave dielectric properties with a high ?_r of 51, a high Q × f of 26,600 GHz (at 6 GHz) and a τ_f of 70 ppm/°C, is suggested.     

Low temperature sintering and microwave dielectric properties of (Mg0.7Zn0.3)0.95Co0.05TiO3 ceramics with BaCu(B2O5) additions

The effects of BaCu(B₂O₅) additives on the sintering temperature and microwave dielectric properties of (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were investigated. The (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were not able to be sintered below 1000 °C. However, when BaCu(B₂O₅) were added, they were sintered below 1000 °C and had the good microwave dielectric properties. It was suggested that a liquid phase with the composition of BaCu(B₂O₅) was formed during the sintering and assisted the densification of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics at low temperature. BaCu(B₂O₅) powders were produced and used to reduce the sintering temperature of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics. Good microwave dielectric properties of Q × f = 35,000 GHz, ?_r = 18.5.0 and τ_f = −51 ppm/°C were obtained for the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics containing 7 wt.% mol% BaCu(B₂O₅) sintered at 950 °C for 4 h.     

Phase evolution and microwave dielectric properties of TiO2-modified (Mg0.95Co0.05)2TiO4 ceramics

Phase evolution and microwave dielectric properties of (1 − x)(Mg_0.95Co_0.05)₂TiO₄-xTiO₂ (x = 0-1) ceramics prepared by the conventional mixed oxide route have been investigated. Increasing the TiO₂ content would lead to a main phase transformation from (Mg_0.95Co_0.05)₂TiO₄ to (Mg_0.95Co_0.05)TiO₃, (Mg_0.95Co_0.05)Ti₂O₅ and then TiO₂. Not only did the TiO₂ addition compensate the τ_f, it also lowered the sintering temperature of specimen. A huge drop of Q × f occurs at a 40-60 mol% TiO₂ addition was attributed to the formation of (Mg_0.95Co_0.05)Ti₂O₅ phase. Specimen with x = 0.78 can possess an excellent combination of microwave dielectric properties: ?_r ∼ 24.77, Q × f ∼ 38,500 GHz and τ_f ∼ −1.3 ppm/°C.     

Characterization of sol-gel synthesised lead-free (1 − x)Na0.5Bi0.5TiO3-xBaTiO3-based ceramics

The crystal structure, microstructure, dielectric and ferroelectric properties of (1 − x)Na_0.5Bi_0.5TiO₃-xBaTiO₃ ceramics with x = 0, 0.03, 0.05, 0.07 and 0.1 are investigated. A structural variation according to the system composition was investigated by X-ray diffraction (XRD) analyses. The results revealed that the synthesis temperature for pure perovskite phase powder prepared by the present sol-gel process is much lower (800 °C), and a rhombohedral-tetragonal morphotropic phase boundary (MPB) is found for x = 0.07 composition which showing the highest remanent polarization value and the smallest coercive field. The optimum dielectric and piezoelectric properties were found with the 0.93Na_0.5Bi_0.5TiO₃-0.07BaTiO₃ composition. The piezoelectric constant d₃₃ is 120 pC/N and good polarization behaviour was observed with remanent polarization (P_r) of 12.18 pC/cm², coercive field (E_c) of 2.11 kV/mm, and enhanced dielectric properties ?_r > 1500 at room temperature. The 0.93Na_0.5Bi_0.5TiO₃-0.07BaTiO₃-based ceramic is a promising lead-free piezoelectric candidate for applications in different devices.     

Structure and dielectric characterization of xNd(Mg1/2Ti1/2)O3-(1 − x)Ca0.6La0.8/3TiO3 in the microwave frequency range

The crystal structures, phase compositions and the microwave dielectric properties of the xLa(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.8Sr_0.2TiO₃ composites prepared by the conventional solid state route have been investigated. The formation of solid solution is confirmed by the XRD patterns. Doping with B₂O₃ (0.5 wt.%) can effectively promote the densification and the dielectric properties of xNd(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics. It is found that xNd(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics can be sintered at 1375 °C, due to the liquid phase effect of B₂O₃ addition observed by Scanning Electronic Microscopy. At 1375 °C, 0.4Nd(Mg_1/2Ti_1/2)O₃-0.6Ca_0.6La_0.8/3TiO₃ ceramics with 1 wt.% B₂O₃ addition possesses a dielectric constant (?_r) of 49, a Q × f value of 13,000 (at 8 GHz) and a temperature coefficients of resonant frequency (τ_f) of 1 ppm/°C. As the content of Nd(Mg_1/2Ti_1/2)O₃ increases, the highest Q × f value of 20,000 GHz for x = 0.9 is achieved at the sintering temperature 1400 °C.     

Elucidating the dielectric properties of Mg2SnO4 ceramics at microwave frequency

This study investigated the potential applications of microwave dielectric properties of Mg₂SnO₄ ceramics in mobile communication. Mg₂SnO₄ ceramics were prepared using a conventional solid-state method. The X-ray diffraction patterns of the Mg₂SnO₄ ceramics revealed no significant variation of phase with sintering temperature. A maximum density of 4.62 g/cm³, a dielectric constant (?_r) of 8.41, a quality factor (Q × f) of 55,100 GHz, and a temperature coefficient of resonant frequency (τ_f) of −62 ppm/ °C were obtained when Mg₂SnO₄ ceramics were sintered at 1550 °C for 4 h.     

Reaction-sintering method for ultra-low loss (Mg0.95Co0.05)TiO3 ceramics

Microwave dielectric properties and microstructures of (Mg_0.95Co_0.05)TiO₃ ceramics prepared by a new sintering method (reaction-sintering method) were investigated. A pure phase of (Mg_0.95Co_0.05)TiO₃ was obtained by the new method and excellent dielectric properties were observed due to uniformities of the microstructure and the phase. In contrast, the secondary phase (Mg_0.95Co_0.05)Ti₂O₅ was observed in samples prepared by conventional sintering method. In order to study the influence of secondary phase on the microwave dielectric properties quantitatively, the weight fraction of (Mg_0.95Co_0.05)Ti₂O₅ was calculated on the basis of Rietveld refinement. The pore-free?_r values of specimens prepared by two different methods indicated that porosity plays an important role in the ?_r values of (Mg_0.95Co_0.05)TiO₃ ceramics. Specimens sintered by reaction-sintering method at 1350 °C for 4 h possess excellent dielectric properties with an ?_r of 16.3, a Q × f value of 244,500 GHz, and a τ_f value of −53.5 ppm/°C.     

Enhancement microwave dielectric properties of La(Mg0.5Sn0.5)O3 ceramics by substituting Mg with Ni

The microwave dielectric properties of La(Mg_0.5−xNi_xSn_0.5)O₃ ceramics were examined with a view to their exploitation for mobile communication. The La(Mg_0.5−xNi_xSn_0.5)O₃ ceramics were prepared by the conventional solid-state method at various sintering temperatures. The X-ray diffraction patterns of the La(Mg_0.4Ni_0.1Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. Apparent density of 6.71 g/cm³, dielectric constant (?_r) of 20.19, quality factor (Q × f) of 74,600 GHz, and temperature coefficient of resonant frequency (τ_f) of −85 ppm/°C were obtained for La(Mg_0.4Ni_0.1Sn_0.5)O₃ ceramics that were sintered at 1550 °C for 4 h.     

Relationships between Zr substitution for Ti and microwave dielectric properties in Mg(ZrxTi1−x)O3 ceramics

The influence of Zr substitution for Ti on the microwave dielectric properties and microstructures of the Mg(Zr_xTi_1−x)O₃(MZ_xT) (0.01 ≤ x ≤ 0.3) ceramics was investigated. The quality factors of Mg(Zr_xTi_1−x)O₃ ceramics with x = 0.01-0.05 were improved because the solid solution of a small amount of Zr⁴⁺ substitution in the B-site could increase density and grain size. An excess of Zr⁴⁺ resulted in the formation of a great deal of secondary phase that declined the microwave dielectric properties of MZ_xT ceramics. The temperature coefficient of resonant frequency (τ_f) of Mg(Zr_xTi_1−x)O₃ ceramics slightly increased with increasing Zr content, and the variation in τ_f was attributed to the formation of secondary phases.     

Microwave dielectric properties of temperature stable Li2ZnxCo1−xTi3O8 ceramics

The Li₂Zn_xCo_1−xTi₃O₈ (x = 0.2-0.8) solid solution system has been synthesized by the conventional solid-state ceramic route and the effect of Zn substitution for Co on microwave dielectric properties of Li₂CoTi₃O₈ ceramics has also been investigated. The microwave dielectric properties of these ceramics show a linear variation between the end members for all compositions. The optimized sintering temperatures of Li₂Zn_xCo_1−xTi₃O₈ ceramics increase with increasing content of Zn. The specimen with x = 0.4 sintered at 1050 °C/2 h exhibits an excellent combination of microwave dielectric properties with ?_r = 27.7, Q_u × f = 57,100 GHz and τ_f = −1.0 ppm/°C.     

Phase evolution, crystal structure and dielectric behavior of (1 − x)Nd(Zn0.5Ti0.5)O3 + xBi(Zn0.5Ti0.5)O3 compound ceramics

The phase evolution, crystal structure and dielectric properties of (1 − x)Nd(Zn_0.5Ti_0.5)O₃ + xBi(Zn_0.5Ti_0.5)O₃ compound ceramics (0 ≤ x ≤ 1.0, abbreviated as (1 − x)NZT-xBZT hereafter) were investigated. A pure perovskite phase was formed in the composition range of 0 ≤ x ≤ 0.05. The B-site Zn²⁺/Ti⁴⁺ 1:1 long range ordering (LRO) structure was detected by both XRD and Raman spectra in x ≤ 0.05 samples. However, this LRO structure became gradually degraded with an increase in x. The dielectric behaviors of the compound ceramic at various frequencies were investigated and correlated to its chemical composition and crystal structure. A gradually compensated τ_f value was obtained in (1 − x)NZT-xBZT microwave dielectrics at x = 0.03, which was mainly due to the dilution of dielectric constant in terms of Claussius-Mossotti differential equation.     

High-Q microwave dielectrics in the (Mg1−xZnx)Al2O4 (x = 0-0.1) system

The microwave dielectric properties and the microstructures of (Mg_1−xZn_x)Al₂O₄ (x = 0-0.1) ceramic system prepared by the conventional solid-state route were investigated. The forming of spinel-structured (Mg_1−xZn_x)Al₂O₄ (x = 0-0.1) solid solutions was confirmed by the XRD patterns and the measured lattice parameters, which linearly varied from a = b = c = 8.0815 Å for MgAl₂O₄ to a = b = c= 8.0828 Å for (Mg_0.9Zn_0.1)Al₂O₄. By increasing x, the Q × f of (Mg_1−xZn_x)Al₂O₄ can be tremendously boosted from 82,000 GHz at x = 0 to a maximum of 156,000 GHz at x = 0.05. The Zn substitution was effective in reducing the dielectric loss without detrimental effects on the ?_r and τ_f values of the ceramics.     

Dielectric and microwave properties of ZrO2 doped CaO-SiO2-B2O3 ceramic matrix composites

The behavior of dielectric and microwave properties against sintering temperature has been carried out on CaO-SiO₂-B₂O₃ ceramic matrix composites with ZrO₂ addition. The results indicated that ZrO₂ addition was advantageous to improve the dielectric and microwave properties. X-ray diffraction (XRD) patterns show that the major crystalline β-CaSiO₃ and a little SiO₂ phase existed at the temperature ranging from 950 °C to 1050 °C. At 0.5 wt% ZrO₂, CaO-SiO₂-B₂O₃ ceramic matrix composites sintered at 1000 °C possess good dielectric properties: ?_r = 5.85, tan δ = 1.59 × 10⁻⁴ (1 MHz) and excellent microwave properties: ?_r = 5.52, Q · f = 28,487 GHz (11.11 GHz). The permittivity of Zr-doped CaO-SiO₂-B₂O₃ ceramic matrix composites exhibited very little temperature dependence, which was less than ±2% over the temperature range of −50 to 150 °C. Moreover, the ZrO₂-doped CaO-SiO₂-B₂O₃ ceramic matrix composites have low permittivity below 5.5 over a wide frequency range from 20 Hz to 1 MHz.     

Crystal structure and dielectric properties of La(Mg0.5Ti0.5)O3-Ca0.8Sm0.4/3TiO3 solid solution system at microwave frequencies

The crystal structure and the dielectric properties of (1 − x)La(Mg_0.5Ti_0.5)O₃-xCa_0.8Sm_0.4/3TiO₃ ceramics have been investigated. Ca_0.8Sm_0.4/3TiO₃ was employed as a τ_f compensator and was added to La(Mg_0.5Ti_0.5)O₃ to achieve a temperature-stable material. The formation of (1 − x)La(Mg_0.5Ti_0.5)O₃-xCa_0.8Sm_0.4/3TiO₃ solid solutions were confirmed by the XRD results and the measured lattice parameters for all compositions. The dielectric properties are strongly correlated to the sintering temperature and the compositional ratio of the specimens. Although the ?_r of the specimen could be boosted by increasing the amount of Ca_0.8Sm_0.4/3TiO₃, it would instead render a decrease in the Q × f. The τ_f value is strongly correlated to the compositions and can be controlled by the existing phases. A new microwave dielectric material 0.45La(Mg_0.5Ti_0.5)O₃-0.55Ca_0.8Sm_0.4/3TiO₃, possessing a fine combination of microwave dielectric properties with an ?_r of 47.83, a Q × f of 26,500 GHz (at 6.2 GHz) and a τ_f of −1.7 ppm/°C, is proposed as a very promising candidate material for today's 3G applications.     

Synthesis, structural and microwave dielectric properties of Al2W3−xMoxO12 (x = 0-3) ceramics

Low dielectric ceramics in the Al₂W_3−xMo_xO₁₂ (x = 0-3) system have been prepared through solid state ceramic route. The phase purity of the ceramic compositions has been studied using powder X-ray diffraction (XRD) studies. The microstructure of the sintered ceramics was evaluated by Scanning Electron Microscopy (SEM). The crystal structure of the ceramic compositions as a result of Mo substitution has been studied using Laser Raman spectroscopy. The microwave dielectric properties of the ceramics were studied by Hakki and Coleman post resonator and cavity perturbation techniques. Al₂Mo_xW_3−xO₁₂ (x = 0-3) ceramics exhibited low dielectric constant and relatively high unloaded quality factor. The temperature coefficient of resonant frequency of the compositions is found to be in the range −41 to −72 ppm/°C.     

Low-loss microwave dielectrics using rock salt oxide Li2MgTiO4

Rock-salt-structured Li₂MgTiO₄ ceramic was prepared by the conventional mixed oxide route and its microwave dielectric properties were investigated. The microstructures of the ceramics were characterized by SEM. The dielectric properties of the ceramics exhibited a significant dependence on the sintering condition and crystal structure. A new microwave dielectric material, Li₂MgTiO₄ sintered at 1360 °C has a dielectric constant (?_r) of ∼17.25, a Q × f of ∼97,300 GHz (where f = 9.86 GHz, is the resonant frequency) and a τ_f of ∼-27.2 ppm/°C. The microwave dielectric properties of the ceramic are reported for the first time.