Synthesis and microwave dielectric properties of pseudobrookite-type structure Mg5Nb4O15 ceramics by aqueous sol–gel technique

Pseudobrookite-type Mg₅Nb₄O₁₅ ceramics were prepared by aqueous sol–gel process and microwave dielectric properties were investigated. Highly reactive nanosized Mg₅Nb₄O₁₅ powders were successfully synthesized at 600 °C in oxygen atmosphere with particle sizes of 20–40 nm firstly and then phase evolution was detected by DTA-TG and XRD. Sintering characteristics and microwave dielectric properties of Mg₅Nb₄O₁₅ ceramics were studied at different temperatures ranging from 1200 °C to 1400 °C. With the increase of sintering temperature, density, ?_r and Q·f values increased, and then saturated at 1300 °C. Excellent microwave properties of ?_r ～11.3, Q·f ～43,300 GHz and τ_f ～?58 ppm/°C, were obtained finally. The sintering temperature of Mg₅Nb₄O₁₅ ceramics was significantly reduced by aqueous sol–gel process compared to conventional solid-state methods.     

Crystal structure and microwave dielectric properties of temperature stable (CoxZn1–x)TiNb2O8 ceramics

(Co_xZn_1–x)TiNb₂O₈ (x = 0.2–0.8) microwave dielectric ceramics were synthesized via the conventional solid-state reaction route, and the correlation of microwave dielectric properties on the crystal structure was discussed. Crystal structures of ceramic samples were systematically investigated by X-ray powder diffraction. Moreover, composition-induced phase transitions were confirmed via the following sequence: for x ≤ 0.2, single-phase orthorhombic ixiolite (ZnTiNb₂O₈) was formed, whereas for 0.3 ≤ x<0.8, ixiolite and rutile coexisted. When x ≥ 0.8, only single-phase rutile was detected. For the (Co_xZn_1–x)TiNb₂O₈ ceramics, the microwave dielectric properties were changed with the crystal structural transitions: the dielectric constant (ε_r) and the temperature coefficient of resonant frequency (τ_f) increased upon increasing the Co²⁺, but the quality factor (Q) decreased. A near-zero τ_f = +1.6 ppm/°C was obtained in the Co_0.38Zn_0.62TiNb₂O₈ ceramics with ε_r = 40.7 and high Q × f = 16 790 GHz. These research outcomes are expected to have great significance for developing microwave dielectric ceramics in practical applications.     

Temperature stability and high-Qf of low temperature firing Mg2SiO4–Li2TiO3 microwave dielectric ceramics

In this work, a series of low-temperature-firing (1−x)Mg₂SiO₄–xLi₂TiO₃–8 wt% LiF (x = 35–85 wt%) microwave dielectric ceramics was prepared through conventional solid state reaction. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses showed that the Li₂TiO₃ phase was transformed into cubic phase LiTiO₂ phase and secondary phase Li₂TiSiO₅. Partial substitution of Mg²⁺ ions for Ti³⁺ ions or Li⁺Ti³⁺ ions increased the cell volume of the LiTiO₂ phase. The dense microstructures were obtained in low Li₂TiO₃ content (x ≤ 65 wt%) samples sintered at 900 °C, whereas the small quantity of pores presented in high Li₂TiO₃ content (x ≥ 75 wt%) samples sintered at 900 °C and low Li₂TiO₃ content (x = 45 wt%) sintered at 850 and 950 °C. Samples at x = 45 wt% under sintering at 900 °C for 4 h showed excellent microwave dielectric properties of ε_r = 10.7, high Q × f = 237,400 GHz and near-zero τ_f = − 3.0 ppm/°C. The ceramic also exhibited excellent chemical compatibility with Ag. Thus, the fabricated material could be a possible candidate for low temperature co-fired ceramic (LTCC) applications.     

Phase composition,crystal structure and microwave dielectric properties of Mg2−xCuxSiO4 ceramics

In this work, the Mg_2-xCu_xSiO₄(x = 0–0.40) microwave dielectric ceramics were prepared using solid-state reaction method. Compared with the Mg₂SiO₄ sample, the Cu-substituted Mg samples could be sintered at a lower temperature. The Mg_2?xCu_xSiO₄ ceramics exhibit the composite phases of Mg₂SiO₄ and a small quantity of MgSiO₃. The Cu²⁺ ion presented a solid solution with the Mg₂SiO₄ phase and preferentially occupy Mg(1) site. The distortion of MgO₆ octahedron was modified by Cu²⁺ ions, resulting in a positive change in the temperature coefficient of resonance frequency (τ_f) values. Excellent microwave dielectric properties of ε_r = 6.35, high Qf of ～ 188,500 GHz and near zero τ_f = ?2.0 ppm/°C were achieved at x = 0.08 under sintering at 1250 °C for 4 h. Thus, the fabricated ceramics were considered as possible candidates for millimeter-wave device applications.     

Crystal structure and dielectric properties of germanate melilites Ba2MGe2O7 (M = Mg and Zn) with low permittivity

Two melilite-structured ceramics, Ba₂MgGe₂O₇ and Ba₂ZnGe₂O₇, were fabricated using the simple solid-state sintering route and their microwave dielectric properties were reported for the first time. Rietveld refinements revealed that both ceramics crystallized in a tetragonal system with a space group P-42₁m. In contrast to Ba₂MgGe₂O₇ that was single phase in the whole sintering range, Ba₂ZnGe₂O₇ exhibited a second phase BaZnGeO₄ which was confirmed by SEM and Raman analysis. The sintering temperature could optimize the relative density and dielectric properties. Dense Ba₂MgGe₂O₇ and Ba₂ZnGe₂O₇ ceramics could be obtained at 1280?°C and 1180?°C with low relative permittivity(ε_r) of 7.76 and 9.0, high quality factor (Q?×?f) of 20,700 and 13,950?GHz, and negative temperature coe?cient of resonant frequency (τ_f) of ?55 and ?75?ppm/°C, respectively. Their differences in microwave dielectric properties were analyzed based on ionic polarizability and packing fraction. The thermal stability of Ba₂MgGe₂O₇ was tuned through the solid solution formation with TiO₂ and the τ_f value was adjusted successfully.     

Grain boundary segregation and microwave dielectric properties of low loss Mg1·5Zn0·5SiO4 ceramics containing Bi2O3

Abstract

Abstract

Uncommon low loss Mg_1·5Zn_0·5SiO₄ ceramics containing Bi₂O₃ were investigated by focusing on the roles of Bi₂O₃ on phase evolution and resultant microwave dielectric properties. While the primary goal of lowering sintering temperature can be easily assumed, some unexpected behaviours of the Bi₂O₃ containing materials are highlighted with experimental evidences concerning selective dissolution of Zn₂SiO₄ and grain boundary segregation of gradual Bi richer phases. These evidences are strongly dependent on the content of Bi₂O₃ and sintering temperature. As an optimal composition, Mg_1·5Zn_0·5SiO₄ with 0·5?mol.-%Bi₂O₃ exhibited promising dielectric properties of a k value ～6·8 and a Q×f value ～23?300 at a sintering temperature of 1150°C, which is much lower than typical sintering temperature of 1450°C.     

Crystal structure and microwave dielectric properties of La2(Zr1−xTix)3(MoO4)9 (0 ≤ x ≤ 0.1) ceramics

La₂(Zr_1−xTi_x)₃(MoO₄)₉ (0 ≤ x ≤ 0.1) ceramics were prepared by the traditional solid-state reaction method. XRD analysis showed that La₂(Zr_1−xTi_x)₃(MoO₄)₉ (0 ≤ x ≤ 0.1) ceramics belonged to a trigonal system. Based on the chemical bond theory, the consequences of bond energy, bond ionicity, lattice energy, and thermal expansion coefficient of ceramics on microwave dielectric properties were discussed. As Ti⁴⁺ addition was increased, the reduction in dielectric constant was ascribed to the fact that the polarizability of Ti⁴⁺ is smaller than Zr⁴⁺, and the downward trend was related to the bond ionicity. Besides, the tendency of Q·f value depended on the packing fraction and the lattice energy. The improvement in τ_f value, the increase in bond energy, and the decrease in the coefficient of thermal expansion were all correlated. The far-infrared spectra implied that the absorptions of structural phonon oscillation were the main reason for the maximum polarization contribution. La₂(Zr_0.92Ti_0.08)₃(MoO₄)₉ ceramics sintered at 750°C for 4 hours exhibited the best dielectric properties (ε_r = 10.33, Q·f = 80 658 GHz, and τ_f = 3.48 ppm/°C).     

Crystal structure and microwave dielectric properties of Zn0.9Ti0.8−xSnxNb2.2O8 ceramics

The crystal structure and microwave dielectric properties of Zn_0.9Ti_0.8?xSn_xNb_2.2O₈ (x = 0.00, 0.05, 0.10, 0.15) ceramics sintered at temperatures ranging from 1100 °C to 1140 °C for 6 h were investigated. A single phase with ixiolite structure was obtained. With the increase of Sn content, the dielectric constant decreased attributed to the decrease of dielectric polarizability. The Qf value decreased with the decrease of packing fraction and grain size. The temperature coefficient of resonant frequency (τ_f) increased due to the increase of the bond valence of Zn_0.9Ti_0.8?xSn_xNb_2.2O₈ ceramics. The excellent microwave dielectric properties of ? = 35.05, Qf = 49,100 GHz, τ_f = ?27.6 × 10^?6/°C were obtained for Zn_0.9Ti_0.8?xSn_xNb_2.2O₈ (x = 0.05) specimens sintered at 1120 °C for 6 h.     

Large dielectric constants and good thermal stability of Nb2O5-doped BaTiO3–Bi(Mg1/2Ti1/2)O3 ceramics with core–shell structure

0.96BaTiO₃-0.04Bi(Mg_1/2Ti_1/2)O₃ (0.96BT-0.04BMT) + y wt.% Nb₂O₅ ceramics (0.0 ≤ y ≤ 2.0) were sintered at 1275 °C to fabricate a ceramic with a large ε_r for an X8R multilayer ceramic capacitor (MLCC). Addition of Nb₂O₅ afforded a core–shell structure, and the compositions of the core and shell regions were similar to those of BT and BT-BMT, respectively. The sample (y = 1.25) exhibited a large ε_r of 2285 with a good temperature stability satisfying the X8R specification because of a broad shell-region phase-transition peak at −17 °C and a decreased ε_r of the core-region phase-transition peak. The 0.1 wt% BaO–CaO–SiO₂ (BCS) was used to reduce the sintering temperature, and the 9-layered MLCC produced using a BCS-doped 0.96BT-0.04BMT + 1.25 wt% Nb₂O₅ ceramic at 1200 °C showed a large capacitance of 67 nF with a good temperature stability thus complying with EIA-X8R regulations.     

Crystal structure and phase formation of MgO–MoO3-based ceramics with ultralow dielectric loss: A comprehensive study

The MgO-MoO₃ system shows significant potential for applications in microwave dielectric ceramics. However, the formation mechanism, crystal structures, and microwave dielectric properties of this system have not been systematically investigated. This work aims to comprehensively study the crystal structures, phase transitions, and microwave dielectric properties of compounds in the MgO-MoO₃ system. In particular, the research delves into the unexplored transformation mechanism from β-MgMo₂O₇ to α-MgMo₂O₇ and MgMoO₄. As a result, the three compounds exhibiting favorable microwave dielectric properties have been successfully fabricated. These compounds can be effectively sintered at temperatures ranging from 685 to 900°C and exhibited dielectric constants (ε_r) ranging from 5.41 to 6.89, as well as Qf values ranging from 100 000 to 130 000 GHz. Additionally, prototype microstrip antennas are designed and fabricated using β-MgMo₂O₇ and MgMoO₄ ceramics as substrates. The obtained antenna's performance is excellent, with S₁₁ values below −30 dB and a gain exceeding 6 dB at 5.8 GHz, highlighting the potential of the developed ceramics for practical applications in microwave devices.     

Broad sintering temperature range and stable microwave dielectric properties of Mg2TiO4–CeO2 composite ceramics

There has been extensive research on microwave dielectric materials considering their application in 5G and 6G communication technologies. In this study, the sintering temperature range of Mg₂TiO₄–CeO₂ (MT-C) ceramics was broadened using a composite of CeO₂ and Mg₂TiO₄ ceramics, and their microwave dielectric performance was stabilized. Low-loss MT-C composite ceramics were prepared using the solid-phase reaction method, and their microwave dielectric properties, microscopic morphologies, and phase structures were investigated. The proposed MT-C ceramics contained Mg₂TiO₄ and CeO₂ phases; their average grain size was maintained at 2–4 μm in the sintering temperature range of 1275–1425 °C, and the samples were uniformly dense without porosity. The cross-distribution of Mg₂TiO₄ and CeO₂ grains in the samples inhibited the growth of ceramic grains, providing uniform and dense surfaces. The dielectric loss of MT-C ceramics remained constant in the temperature range of 1300–1425 °C at 9 × 10^?4 (8.45 ≤ f ≤ 8.75 GHz). As opposed to the base material, MT-C ceramics are advantageous owing to their wide sintering temperature range and the stable microwave dielectric properties, and there are suitable substrate materials for further industrial applications.     

Phase compositions and crystal structure of Sn-deficient Ca2Sn2Al2O9 microwave dielectric ceramics with high Q×f values

The phase compositions and microwave dielectric properties of Sn-deficient Ca₂Sn₂Al₂O₉ ceramics in this study were explored. The CaSnO₃ and SnO₂ second phases existed at Ca₂Sn_2-xAl₂O_9-2x (x = 0) ceramic. Single-phase Ca₂Sn₂Al₂O₉ ceramics were obtained at 0.08 ≤ x ≤ 0.1, and the orthorhombic structure with the Pbcn space group of Ca₂Sn₂Al₂O₉ was verified. For multi-phase Ca₂Sn_2-xAl₂O_9-2x (0 ≤ x ≤ 0.06) ceramics, their microwave dielectric properties were mainly affected by second phase contents, and their Q × f values increased gradually with the rise in x. High Q × f (105,700 GHz at 12.99 GHz) was obtained by the Ca₂Sn_2-xAl₂O_9-2x (x = 0.08) ceramic with high intrinsic Q × f (175,000 GHz). The large deviation between measured Q × f values and fitted intrinsic Q × f values could be ascribed to the Sn⁴⁺ vacancies of the Sn-deficient Ca₂Sn₂Al₂O₉ ceramics. The Ca₂Sn_2-xAl₂O_9-2x (0 ≤ x ≤ 0.1) ceramics presented large negative τ_f values, and this τ_f was mainly affected by τ_ε. Meanwhile, the Ca₂Sn_2-xAl₂O_9-2x (x = 0.08) ceramic achieved optimal microwave dielectric properties (ε_r = 8.3, Q × f = 105,700 GHz at 12.99 GHz and τ_f = ?63.7 ppm/°C), indicating the good feature of this material for millimetre-wave applications.     

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.     

Silver cofirable (Ca0.9, Mg0.1)SiO3 microwave dielectric ceramics with Li2CO3–Bi2O3 additive

The effects of Li₂CO₃–Bi₂O₃ (LB) additive on the microstructure, phase formation, microwave dielectric properties and applicability for low-temperature co-fired ceramics (LTCC) technology of (Ca_0.9Mg_0.1)SiO₃ (CMS) ceramics were investigated. The sintering temperature of the CMS ceramics was reduced from 1290 °C to 890 °C by the addition of LB. Secondary phases SiO₂ and Bi₄(SiO₄)₃ were detected when LB content was less than 9 wt%. Low melting point liquid phases were formed when LB content was 11–14 wt%. The Q_f value initially increased with the addition of LB and attained the maximum value for the 9 wt% LB-doped CMS ceramic. When the LB content exceeded 9 wt%, the Q_f value decreased because of the presence of liquid phase and abnormal growth of grains. ?_r of 6.92, Q_f of 27,600 GHz and τ_f of ?43.6 ppm/°C were obtained for 9 wt% LB-doped CMS ceramics sintered at 890 °C for 2 h. Also the ceramics can be well co-fired with Ag electrode.     

La(Mg1/2Ti1/2)O3–La2/3TiO3 microwave dielectric ceramics

Structure and microwave dielectric properties were studied in the (1−x)La(Mg_1/2Ti_1/2)O₃–xLa_2/3TiO₃ system. Ceramics with this composition in the 0⩽x⩽0.5 range were processed from powders obtained by a citrate-based chemical route. Structure of these perovskite solid solutions changed from orthorhombic for x=0.1 and 0.3 to pseudocubic for x=0.5. Microwave and radio frequency measurements revealed increase in permittivity and temperature coefficient of the resonant frequency τ_f with increasing of La_2/3TiO₃ content. Close to zero τ_f value was found near to x=0.5 composition of (1−x)La(Mg_1/2Ti_1/2)O₃–x La_2/3TiO₃.     

Phase evolution and microwave dielectric properties of SrTiO3 added ZnAl2O4–Zn2SiO4–SiO2 ceramics

Phase evolution and microwave dielectric properties of SrTiO₃ added ZnAl₂O₄–3Zn₂SiO₄–2SiO₂ ceramics system were investigated. With the addition of SrTiO₃, the sintering temperature for dense ceramic is reduced from 1320 °C to 1180–1200 °C. According to the nominal composition ZnAl₂O₄–3Zn₂SiO₄–2SiO₂-ySrTiO₃, phase evolution is revealed by XRD patterns and Back Scattering Electron images: Zn₂SiO₄, ZnAl₂O₄ and SiO₂ phases coexist at y = 0; SrTiO₃ reacts with ZnAl₂O₄ and SiO₂ to form SrAl₂Si₂O₈, TiO₂ and Zn₂SiO₄ at y = 0.2 to 0.8, and SiO₂ phase disappears at y = 0.8; new phase of Zn₂TiO₄ is obtained at y = 1. The existence of TiO₂ has important effect on the dielectric properties. The optimized microwave dielectric properties are obtained at y = 0.6 and the ceramics show low dielectric constant (7.16), high-quality factor (57, 837 GHz), and low temperature coefficient of resonant frequency (−30 ppm °C⁻¹).     

Microwave dielectric properties of high dielectric tunable - low permittivity Ba0.5Sr0.5TiO3–Mg2(Ti0.95Sn0.05)O4 composite ceramics

Ba_0.5Sr_0.5TiO₃–Mg₂(Ti_0.95Sn_0.05)O₄ composite ceramics have been synthesized by the solid-state reaction. Phase structure, microstructure and microwave dielectric properties have been systematically characterized. The permittivity is tailored to a certain extent with the addition of Mg₂(Ti_0.95Sn_0.05)O₄. Both X-ray diffraction (XRD) and back electric image (BEI) analysis show the co-existence of two-phase structures of ABO₃ perovskite and A₂BO₄ spinel structure. A high dielectric tunablity can be obtained and a high Q value can be achieved at microwave frequency. The composition 30 wt.%Ba_0.5Sr_0.5TiO₃–70 wt.%Mg₂(Ti_0.95Sn_0.05)O₄ exhibits good dielectric properties with ? of 79, Q of 152 (at 2.997 GHz) and T of 15.8% (30 kV/cm & 10 kHz) at room temperature, which make it a promising candidate for tunable microwave device applications in the wireless communication system.     

Microwave dielectric properties of BiNbO4 ceramics with CuO–V2O5 addition

BiNbO₄ ceramics were developed by using CuO–V₂O₅ as a liquid phase sintering agent. The resultant dielectric properties were analyzed in terms of the densification and the amount of CuO–V₂O₅ sintering agent. The addition of 0.8 wt.% CuO–V₂O₅ as its sintering agent was observed to perform most satisfactory. At 850 °C, uniform and enhanced microstructure was observed for the BiNbO₄ specimen with 0.8 wt.% CuO–V₂O₅ addition. Furthermore, the effect of CuO–V₂O₅ addition on the microwave dielectric properties of BiNbO₄ was also investigated. As the sintering temperature increased to 900 °C, the dielectric constant increased but nearly constant and the quality factor (QF) showed a maximum at 850 °C and then decreased for all compositions of the 900 °C sintered specimens. With an increase in CuO–V₂O₅ content, the temperature coefficient of frequency (TCF) increased in accordance with the dielectric mixing rule and microstructural behavior.     

High permittivity and low loss dielectric ceramics in the BaO–La2O3–TiO2–Ta2O5 system

Dielectric ceramics were synthesized and characterized in the BaO–La₂O₃–TiO₂–Ta₂O₅ quaternary system for the three typical compositions: Ba₃La₃Ti₅Ta₅O₃₀, Ba₄La₂Ti₄Ta₆O₃₀ and Ba₅LaTi₃Ta₇O₃₀, which formed the filled tungsten-bronze structures. The present ceramics indicated high dielectric constant ε (127.7–148.1) and low dielectric loss tanδ (in the order of 10⁻⁴–10⁻³ at 1 MHz). Meanwhile, the temperature coefficient of dielectric constant τ_ε varied from −728 to −1347 ppm/°C with increasing Ba and Ta and decreasing La and Ti concentration in the temperature range of 20–85 °C. The present ceramics are promising candidates for high-ε and low loss dielectric ceramics, and the suppression of τ_ε should be the primary issue in the future work.