Structural, spectroscopic and dielectric investigations on Ba8Zn(Nb6−xSbx)O24 microwave ceramics

Ba₈Zn(Nb_6−xSb_x)O₂₄ (x = 0, 0.3, 0.6, 0.9, 1.2, 1.5, 1.8 and 2.4) ceramics were prepared through the conventional solid-state route. The materials were calcined at 1250 °C and sintered in the range 1400-1425 °C. The structure of the system was analyzed by X-ray diffraction, Fourier transform infrared and Raman spectroscopic methods. The theoretical and experimental densities were calculated. The microstructure of the sintered pellets was analyzed using scanning electron microscopy. The low frequency dielectric properties were studied in the frequency range 50 Hz-2 MHz. The dielectric constant (?_r), temperature coefficient of resonant frequency (τ_f) and the unloaded quality factor (Q_u) are measured in the microwave frequency region using cavity resonator method. The τ_f values of the samples reduced considerably with the increase in Sb concentration. The materials have intense emission lines in the visible region. The compositions have good microwave dielectric properties and photoluminescence and hence are suitable for dielectric resonator and ceramic laser applications.     

Composites and solid solutions of Pr–Y titanium tantalate microwave ceramics

Pr _x Y_1−x TiTaO₆ solid solutions were prepared through the solid state ceramic route. The materials were sintered in the range 1,525–1,600 °C. The structure of the system was analyzed by X-ray diffraction methods. The scanning electron microscopic images show the co-existence of two phases in the composite. The dielectric constant (ε_r), temperature coefficient of resonant frequency (τ_f) and the unloaded quality factor (Q _u) are measured in the microwave frequency region using cavity resonator method. The dielectric constant (ε_r) varies from 17.6 to 39.6 and temperature coefficient of resonant frequency (τ_f) from −52.2 to +55.9 ppm/°C. These variations are in accordance with the structural variation. Very low temperature coefficient of resonant frequency and high quality factor were obtained for x = 0.2, 0.23 and 0.24 and are useful materials for practical applications.     

Microwave dielectric properties of (Pb1−3x/2Lax)(Mg1/2W1/2)O3

La modified Pb(Mg_1/2W_1/2)O₃ were prepared by solid-state reaction process, and the sintering behavior, microstructure and microwave dielectric properties were investigated by X-ray powder diffraction (XRD), Raman scattering and HP network analyzer in this paper. A series of single phase perovskite type solid solutions with A-site vacancies (Pb_1−3x/2La_x(Mg_1/2W_1/2)O₃ (0 ≤ x ≤ 2/3)) were formed. The solid solution took cubic perovskite type structure (Fm3m) with random distribution of A-site vacancies when 0 < x < 0.5, and tetragonal or orthorhombic structure with the ordering of A-site vacancies when 0.5 ≤ x ≤ 2/3. The dielectric constant and temperature coefficient of resonant frequency decrease with increasing La content. Relatively good combination microwave dielectric properties were obtained for x = 0.56: ?_r = 28.7; Q × f = 18098; and τ_f = −5.8 ppm/°C.     

Effects of La substitution for Nd in (Nd2−xLax)BaZnO5 solid solutions on microwave dielectric properties and crystal structure

The synthesis and microwave dielectric characterization of (Nd_2−xLa_x)BaZnO₅ solid solutions were studied. The samples obtained were single phase over the whole composition range and the lattice parameters of solid solutions were linearly increased with increasing the composition. Moreover, the expansion of the volume in the RO₈ (R=Nd and La) and BaO₁₀ polyhedra and ZnO₄ tetrahedron were recognized when Nd ions were substituted by La. These variations in the lattice parameters and volumes of the polyhedra are basically attributed to the differences in ionic radii between Nd³⁺ and La³⁺ ions. From the evaluation of microwave dielectric properties, it was shown that the appropriate τ_f values ranging from 4.6 to −5.0 ppm/°C are obtained by La substitution for Nd ion, and the highest Q · f value was 17,832 GHz at x=2.     

Low loss Sr1−xCaxLa4Ti5O17 microwave dielectric ceramics

Microwave dielectric ceramics in the Sr_1−xCa_xLa₄Ti₅O₁₇ (0 ≤ x ≤ 1) composition series were prepared through a solid state mixed oxide route. All the compositions formed single phase ceramics within the detection limit of in-house X-ray diffraction when sintered in the temperature range 1450-1580 °C. Theoretical density and molar volume decreased due to the substitution of Ca²⁺ for Sr²⁺ which was associated with a decrease in the dielectric constant (?_r) and temperature coefficient of resonant frequency (τ_f) but an increase in quality factor, Qf_o. Optimum properties were achieved for Sr_0.4Ca_0.6La₄Ti₅O₁₇ which exhibited, ?_r ∼ 53.7, Qf_o ∼ 11,532 GHz and τ_f ∼ −1.4 ppm/°C.     

Crystal structure and microwave dielectric properties of (1 − x)NdAlO3-xCaTiO3 ceramics

Crystal structure and microwave dielectric properties of (1−x)NdAlO₃-xCaTiO₃ ceramics have been investigated. Crystal structure of the specimens changed with the composition. Rhombohedral structure was found for the specimens with x≤0.1. When 0.3≤x≤0.7, the specimens had the tetragonal structure and it changed to the orthorhombic structure as x exceeded 0.7. Two types of the second phases were observed in (1−x)NdAlO₃-xCaTiO₃ ceramics. For the specimens with x≤0.5, Nd₄Al₂O₉ phase was observed and Al-rich phase was found in the specimens with x≥0.7. The dielectric constant (ε_r) and the temperature coefficient of the resonant frequency (τ_f) increased with the increase of x. The Q×f value of the specimen increased with x and exhibited the maximum value when x=0.5. The microwave dielectric properties of Q×f=45,000 GHz, ε_r=45 and τ_f=−1.5 ppm/°C were obtained for 0.3NdAlO₃-0.7CaTiO₃ ceramics.     

Dielectric properties of (1−x)(Mg0.95Co0.05)TiO3-xCaTiO3 ceramic system at microwave frequency

The microwave dielectric properties and the microstructures of the (1−x)MgTiO₃-xCaTiO₃ ceramic system were investigated. With partial replacement of Mg by Co, dielectric properties of the (1−x)(Mg_0.95Co_0.05)TiO₃-xCaTiO₃ ceramics can be promoted. The microwave dielectric properties are strongly correlated with the sintering temperature. At 1275°C, the 0.95(Mg_0.95Co_0.05)TiO₃-0.05CaTiO₃ ceramics possesses excellent microwave dielectric properties: a dielectric constant ε_r of 20.3, a Q×f value of 107 000 ( at 7 GHz) and a τ_f value of −22.8 ppm/°C. By appropriately adjusting the x value in the (1−x)(Mg_0.95Co_0.05)TiO₃-xCaTiO₃ ceramic system, zero τ_f value can be achieved. With x=0.07, a dielectric constant ε_γ of 21.6, a Q×f value of 92 000 (at 7 GHz) and a τ_f value of −1.8 ppm/°C was obtained for 0.93(Mg_0.95Co_0.05)TiO₃-0.07CaTiO₃ ceramics sintered at 1275°C for 4 h.     

Improved high-Q microwave dielectric resonator using CuO-doped MgNb2O6 ceramics

The microwave dielectric properties and the microstructures of MgNb₂O₆ ceramics with CuO additions (1-4 wt.%) prepared with conventional solid-state route have been investigated. The sintered samples exhibit excellent microwave dielectric properties, which depend upon the liquid phase and the sintering temperature. It is found that MgNb₂O₆ ceramics can be sintered at 1140 °C due to the liquid phase effect of CuO addition. At 1170 °C, MgNb₂O₆ ceramics with 2 wt.% CuO addition possesses a dielectric constant (ε_r) of 19.9, a Q×f value of 110,000 (at 10 GHz) and a temperature coefficient of resonant frequency (τ_f) of −44 ppm/°C. The CuO-doped MgNb₂O₆ ceramics can find applications in microwave devices requiring low sintering temperature.     

Synthesis and microwave dielectric properties of Sr3Zn1−xMgxNb2O9 phases

Oxides of the type, Sr₃Zn_1−xMg_xNb₂O₉ (0≤x≤1) have been obtained by the ceramic method. These oxides crystallize in the hexagonal cell corresponding to ordered triple perovskites. Sintered disks show nearly frequency-independent dielectric constant for all the compositions. Compositions sintered at 1425°C yield dielectric constant of 20-22 at ∼6 GHz, with quality factor ranging from 1300 to 1500. Sr₃Zn_0.5Mg_0.5Nb₂O₉ shows a very low temperature coefficient of resonant frequency (τ_f) of +4 ppm/°C.     

Low-temperature sintering of temperature-stable LaNbO4 microwave dielectric ceramics

We demonstrate the correlation between sintering behavior and microstructural observations in low-temperature sintered, LaNbO₄ microwave ceramics. Small CuO additions to LaNbO₄ significantly lowered the sintering temperature from 1250 to 950 °C. To elucidate the sintering mechanism, the internal microstructure of the sample manipulated by a focused ion beam (FIB) was investigated using transmission electron microscopy (TEM) and energy-dispersive spectroscopy (EDS). LaNbO₄ with 3 wt% CuO sintered at 950 °C for 2 h possessed the following excellent microwave dielectric properties: a quality factor (Qxf) of 49,000 GHz, relative dielectric constant (?_r) of 19.5, and temperature coefficient of resonant frequency (τ_f) of 1 ppm/°C. The ferroelastic phase transformation was also investigated using in situ X-ray diffraction (XRD) to explain the variation of τ_f in low-temperature sintered LaNbO₄ as a function of CuO content.     

Dielectric properties of B2O3-doped (1 − x)LaAlO3-xSrTiO3 ceramic system at microwave frequency

The effects of B₂O₃ addition on the microwave dielectric properties and the microstructures of (1−x)LaAlO₃-xSrTiO₃ ceramics prepared by conventional solid-state routes have been investigated. Doping with 0.25 wt.% B₂O₃ can effectively promote the densification and the microwave dielectric properties of (1−x)LaAlO₃-xSrTiO₃ ceramics. It is found that LaAlO₃-SrTiO₃ ceramics can be sintered at 1400°C due to the liquid phase effect of a B₂O₃ addition observed by scanning electronic microscopy (SEM). The dielectric constant as well as the Q×f value decreases with increasing B₂O₃ content. At 1460°C, 0.46LaAlO₃-0.54SrTiO₃ ceramics with 0.25 wt.% B₂O₃ addition possesses a dielectric constant (ε_r) of 35, a Q×f value of 38,000 (at 7 GHz) and a temperature coefficients of resonant frequency (τ_f) of −1 ppm/°C.     

Dielectric properties of a new ceramic system (1 − x)Mg4Nb2O9-xCaTiO3 at microwave frequency

The microstructures and the microwave dielectric properties of the (1 − x)Mg₄Nb₂O₉-xCaTiO₃ ceramic system were investigated. In order to achieve a temperature-stable material, CaTiO₃ (τ_f ∼ 800 ppm/°C) was chosen as a τ_f compensator and added to Mg₄Nb₂O₉ (τ_f ∼ −70 ppm/°C) to form a two phase system. It was confirmed by the XRD and EDX analysis. By appropriately adjusting the x-value in the (1 − x)Mg₄Nb₂O₉-xCaTiO₃ ceramic system, near-zero τ_f value can be achieved. A new microwave dielectric material, 0.5Mg₄Nb₂O₉-0.5CaTiO₃ applicable in microwave devices is suggested and possesses the dielectric properties of a dielectric constant ?_r ∼ 24.8, a Q × f value ∼82,000 GHz (measured at 9.1 GHz) and a τ_f value ∼−0.3 ppm/°C.     

Microwave dielectric properties of LaMgAl11O19

The suitable choice of a substrate material is one of the aims to be fulfilled in high speed microwave technology. LaMgAl₁₁O₁₉ oxide ceramic material, which belongs to the magnetoplumbite family, has been reported earlier as a potential candidate for such applications. This material has been prepared by conventional solid-state ceramic route. The structure has been studied by X-ray diffraction and characterized at microwave frequencies. The effect of dopant and glass addition on the microwave dielectric properties of this material has also been investigated. LaMgAl₁₁O₁₉ has relatively low dielectric constant (ε_r=14), low dielectric loss or high quality factor (Q_u×f>28,000 GHz at 7 GHz) and small temperature variation of resonant frequency (τ_f=−12 ppm/°C) at room temperature (300 K). These properties make LaMgAl₁₁O₁₉ as a good substrate material and as a dielectric resonator to be used in microwave devices operating at relatively high frequencies.     

Microwave dielectric properties of xNd(Zn1/2Ti1/2)O3–(1 − x)CaTiO3 ceramics

The microwave dielectric properties of xNd(Zn_1/2Ti_1/2)O₃–(1 − x)CaTiO₃ have been investigated. The system has been prepared by a conventional solid state ceramic route. Nd(Zn_1/2Ti_1/2)O₃ (NZT) possesses a dielectric constant (ε_r) of 32, a high quality factor (Q × f) of 170,000 GHz and a temperature coefficient of resonant frequency (τ_f) of − 42 ppm/°C. In order to produce a temperature-stable material, the addition of CaTiO₃ leads to a near-zero temperature variation of resonant frequency. In general, the microwave quality factor (Q × f) decreased as x increased and the temperature coefficient of resonant frequency (τ_f) was approximately linearly proportional to permittivity. The dielectric constant decreases from 77 to 32 as x varies from 0.2 to 1.0. The dielectric constant (ε_r) of 45, Q × f value of 56,000 (at 6 GHz) and temperature coefficient of resonant frequency (τ_f) of 0 ppm/°C were obtained for 0.5Nd(Zn_1/2Ti_1/2)O₃–0.5CaTiO₃ ceramics sintered at 1300 °C for 4 h. As the content of x increases, the highest Q × f value of 136,200 GHz for x = 0.8 is achieved at the sintering temperature 1300 °C.     

Ba3ZnTa2−xNbxO9 and Ba3MgTa2−xNbxO9 (0≤x≤1): synthesis, structure and dielectric properties

Oxides belonging to the families Ba₃ZnTa_2−xNb_xO₉ and Ba₃MgTa_2−xNb_xO₉ were synthesized by the solid state reaction route. Sintering temperatures of 1300°C led to oxides with disordered (cubic) perovskite structure. However, on sintering at 1425°C hexagonally ordered structures were obtained for Ba₃MgTa_2−xNb_xO₉ over the entire range (0≤x≤1) of composition, while for Ba₃ZnTa_2−xNb_xO₉ the ordered structure exists in a limited range (0≤x≤0.5). The dielectric constant is close to 30 for the Ba₃ZnTa_2−xNb_xO₉ family of oxides while the Mg analogues have lower dielectric constant of ∼18 in the range 50 Hz to 500 kHz. At microwave frequencies (5-7 GHz) dielectric constant increases with increase in niobium concentration (22-26) for Ba₃ZnTa_2−xNb_xO₉; for Ba₃MgTa_2−xNb_xO₉ it varies between 12 and 14. The “Zn” compounds have much higher quality factors and lower temperature coefficient of resonant frequency compared to the “Mg” analogues.     

Preparation, structure and dielectric properties of Ba4LaMNb3O15 (M = Ti, Sn ) ceramics

Two new cation-deficient hexagonal perovskites Ba₄LaMNb₃O₁₅ (M = Ti, Sn) ceramics were prepared by high temperature solid-state reaction route. The phase and structure of the ceramics were characterized by X-ray diffraction, scanning electron microscopy (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. The Ba₄LaTiNb₃O₁₅ has high dielectric constant of 52, high quality factors (Q) 3500 (at 4.472 GHz), and temperature variation of resonant frequency (τ_f) +93 ppm °C⁻¹ at room temperature; Ba₄LaSnNb₃O₁₅ has dielectric constant of 39 with high Q value of 2510 (at 5.924 GHz), and τ_f −29 ppm °C⁻¹.     

Effect of sintering time on crystal structure and microwave dielectric properties in aeschynite-structured (Sm1−xYx)(Ti1.5W0.5)O6 (x = 0 and 0.5) ceramics

The crystal structure and microwave dielectric properties of the (Sm_1−xY_x)(Ti_1.5W_0.5)O₆ (x = 0 and 0.5) ceramics sintered at 1375 °C for 2-50 h were investigated in this study. No secondary phase was observed in the samples sintered for various sintering times, whereas a secondary phase was formed in the (Sm_0.5Y_0.5)(Ti_1.5W_0.5)O₆ ceramic sintered at 1400 °C for 50 h. As for the microstructure analysis, the formation of the liquid phase was observed in the both of the samples sintered for 20 and 50 h. The formation of the liquid phase is related to the compositional change of Ti and W from the stoichiometric composition of the samples caused by the instability of crystal structure. The dielectric constants were increased with increased sintering time in the both of the samples, though variations in the temperature coefficient of resonant frequency of the samples were not recognized with the variation in the sintering time. Moreover, although the quality factors of the each sample increased with increasing the sintering time from 2 to 10 h, decreases in the quality factors were recognized when the sintering time was over 10 h.     

Microwave dielectric properties of Ba2 − xSrxLa3Ti3NbO15 ceramics

High dielectric constant and low loss ceramics in the system Ba_2 − xSr_xLa₃Ti₃NbO₁₅ (x = 0-1) have been prepared by conventional solid-state ceramic route. Ba_2 − xSr_xLa₃Ti₃NbO₁₅ solid solutions adopted A₅B₄O₁₅ cation-deficient hexagonal perovskite structure for all compositions. The materials were characterized at microwave frequencies. They show a linear variation of dielectric properties with the value of x. Their dielectric constant varies from 48.34 to 43.03, quality factor Q_u × f from 20,291 to 39,088 GHz and temperature variation of resonant frequency from 8 to 1.39 ppm/°C as the value of x increases. These low loss ceramics might be used for dielectric resonator (DR) applications.     

Improved microwave dielectric properties of B2O3-doped Nd(Co1/2Ti1/2)O3 ceramics with near zero temperature coefficient of resonant frequency

The microwave dielectric properties and the microstructures of Nd(Co_1/2Ti_1/2)O₃ ceramics prepared by conventional solid-state route have been studied. The prepared Nd(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. It is found that low-level doping of B₂O₃ (up to 0.75 wt.%) can significantly improve the density and dielectric properties of Nd(Co_1/2Ti_1/2)O₃ ceramics. Nd(Co_1/2Ti_1/2)O₃ ceramics with additives could be sintered to a theoretical density higher than 98.5% at 1320 °C. Second phases were not observed at the level of 0.25-0.75 wt.% B₂O₃ addition. The temperature coefficient of resonant frequency (τ_f) was not significantly affected, while the dielectric constants (?_r) and the unloaded quality factors Q were effectively promoted by B₂O₃ addition. At 1320 °C/4 h, Nd(Co_1/2Ti_1/2)O₃ ceramics with 0.75 wt.% B₂O₃ addition possesses a dielectric constant (?_r) of 27.2, a Q × f value of 153,000 GHz (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of 0 ppm/°C. The B₂O₃-doped Nd(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.     

Effect of B2O3-Bi2O3-SiO2-ZnO glass on the sintering and microwave dielectric properties of 0.83ZnAl2O4-0.17TiO2

The 0.83ZnAl₂O₄-0.17TiO₂ (ZAT) ceramics were synthesized by solid state ceramic route. The effect of 27B₂O₃-35Bi₂O₃-6SiO₂-32ZnO (BBSZ) glass on the microwave dielectric properties of ZAT was investigated. The crystal structure and the microstructure of the ceramic-glass composites were studied by X-ray diffraction and scanning electron microscopic techniques. The low frequency dielectric loss was measured at 1 MHz. The dielectric properties of the sintered samples were measured in the microwave frequency range by the resonance method. Addition of 0.2 wt% of BBSZ improved the dielectric properties with quality factor (Q_u × f) > 120,000 GHz, temperature coefficient of resonant frequency (τ_f) = −7.3 ppm/°C and dielectric constant (?_r) = 11.7. Addition of 10 wt% of BBSZ lowered the sintering temperature to about 950 °C with Q_u × f > 10,000 GHz, ?_r = 10 and τ_f = −23 ppm/°C. The reactivity of 10 wt% BBSZ added ZAT with silver was also studied. The results show that ZAT doped with suitable amount of BBSZ glass is a possible material for low-temperature co-fired ceramic (LTCC) application.