Low‐Temperature Sintering and Microwave Dielectric Properties of (Mg0.95Zn0.05)2(Ti0.8Sn0.2)O4–(Ca0.8Sr0.2)TiO3 Composite Ceramics

0.9(Mg_0.95Zn_0.05)₂(Ti_0.8Sn_0.2)O₄–0.1(Ca_0.8Sr_0.2)TiO₃ (MZTS–CST) ceramics were prepared by a conventional solid‐state route. The MZTS–CST ceramics sintered at 1325°C exhibited ε_r = 18.2, Q × f = 49 120 GHz (at 8.1 GHz), and τ_f = 15 ppm/°C. The effects of LiF–Fe₂O₃–V₂O₅ (LFV) addition on the sinterability, phase composition, microstructure, and microwave dielectric properties of MZTS–CST were investigated. Eutectic liquid phases 0.12CaF₂/0.28MgF₂/0.6LiF and MgV₂O₆ were developed, which lowered the sintering temperature of MZTS–CST ceramics from 1325°C to 950°C. X‐ray powder diffraction (XRPD) and energy dispersive spectroscopy (EDS) analysis revealed that MZTS and CST coexisted in the sintered ceramics. Secondary phase Ca₅Mg₄(VO₄)₆ as well as residual liquid phase affected the microwave dielectric properties of MZTS–CST composite ceramics. Typically, the MZTS–CST–5.3LFV composite ceramics sintered at 950°C showed excellent microwave dielectric properties: ε_r = 16.3, Q × f = 30 790 GHz (at 8.3 GHz), and τ_f = ?10 ppm/°C.     

Low temperature fired CaF2-based microwave dielectric ceramics with enhanced microwave properties

Low-temperature-fired microwave ceramics are key to realizing the integration and miniaturization of microwave devices. In this study, a facile wet chemical method was applied to synthesize homogenous nano-sized CaF₂ powders for simultaneously achieving low-temperature sintering and superior microwave dielectric properties. Pure CaF₂ ceramics sintered at 950 °C for 6 h with good microwave dielectric properties (ε_r = 6.22, Q×f = 36,655 GHz, and τ_f = ?102 ppm/°C) was achieved. The microwave dielectric properties of the CaF₂ ceramics were further improved by introducing LiF as a sintering aid. The sintering temperature of CaF₂-based ceramics was effectively lowered from 950 °C to 750 °C with 10 wt% LiF doping, and excellent microwave dielectric properties (ε_r = 6.37, Q×f = 65,455 GHz, and τ_f = ?71 ppm/°C) were obtained.     

Sintering behavior,structural phase transition,and microwave dielectric properties of La1‐xZnxTiNbO6‐x/2 ceramics

La_1‐xZn_xTiNbO_6‐x/2 (LZTN‐x) ceramics were prepared via a conventional solid‐state reaction route. The phase, microstructure, sintering behavior, and microwave dielectric properties have been systematically studied. The substitution of a small amount of Zn²⁺ for La³⁺ was found to effectively promote the sintering process of LTN ceramics. The corresponding sintering mechanism was believed to result from the formation of the lattice distortion and oxygen vacancies by means of comparative studies on La‐deficient LTN ceramics and 0.5 mol% ZnO added LTN ceramics (LTN+0.005ZnO). The resultant microwave dielectric properties of LTN ceramics were closely correlated with the sample density, compositions, and especially with the phase structure at room temperature which depended on the orthorhombic‐monoclinic phase transition temperature and the sintering temperature. A single orthorhombic LZTN‐0.03 ceramic sintered at 1200°C was achieved with good microwave dielectric properties of ε_r~63, Q×f~9600 GHz (@4.77 GHz) and τ_f ~105 ppm/°C. By comparison, a relatively high Q × f~80995 GHz (@7.40 GHz) together with ε_r~23, and τ_f ~?56 ppm/°C was obtained in monoclinic LTN+0.005ZnO ceramics sintered at 1350°C.     

Sintering behavior and microwave dielectric properties of 0.67CaTiO3–0.33LaAlO3 ceramics modified by B2O3–Li2O–Al2O3 and CeO2

A low temperature sintering method was used to avoid the relatively high sintering temperatures typically required to prepare 0.67CaTiO₃–0.33LaAlO₃ (CTLA) ceramics. Additionally, CeO₂ was introduced into the CTLA ceramics as an oxygen-storage material to improve their microwave dielectric properties. 0.67CaTiO₃–0.33LaAlO₃ ceramics co-doped with B₂O₃–Li₂O–Al₂O₃ and CeO₂ were prepared by a conventional two-step solid-state reaction process. The sintering behavior, crystal structure, surface morphology, and microwave dielectric proprieties of the prepared ceramic samples were studied, and the reaction mechanism of CeO₂ was elucidated. CTLA+0.05 wt% BLA+3 wt% CeO₂ ceramics sintered at 1360 °C for 4 h exhibited the optimal microwave dielectric properties: dielectric constant (ε_r)=45.02, quality factor (Q×f)=43102 GHz, and temperature coefficient of resonant frequency (τ_f)=2.1 ppm/°C. The successful preparation of high-performance microwave dielectric ceramics provides a direction for the future development and commercialization of CTLA ceramics.     

Sintering behavior,phase structure and microwave dielectric properties of CeO2 added CaTiO3-SmAlO3 ceramics prepared by reaction sintering method

Novel 0.695CaTiO₃-0.305SmAlO₃+xwt% CeO₂ (x = 0, 0.5, 1.0, 1.5) ceramics were fabricated using a reaction-sintering (RS) approach. The crystal structure, morphology, and microwave dielectric properties of ceramics were systematically studied. The addition of CeO₂ could effectively improve the sintering behavior of 0.695CaTiO₃-0.305SmAlO₃ (CTSA) ceramics. When x = 0.5 wt%, the ceramics exhibited optimal microwave dielectric properties, with ε_r = 43.9, Q×f = 48 779 GHz, and τ_? = ?0.24 ppm/°C, thereby indicating that the samples prepared via the RS route possess superior dielectric properties compared to those prepared by the conventional solid phase reaction. The results demonstrate that CaTiO₃-SmAlO₃ ceramics can be prepared simply and efficiently through a reaction-sintering process.     

A Novel Low‐Firing and Low Loss Microwave Dielectric Ceramic Li2Mg2W2O9 with Corundum Structure

The crystal structure and microwave dielectric properties of a novel low‐firing compound Li₂Mg₂W₂O₉ were investigated in this study. The phase purity and crystal structure were investigated using X‐ray diffraction analyses and Rietveld refinement. The best microwave dielectric properties of the ceramic with a low permittivity (ε_r) ~11.5, a quality factor (Q × f) ~31 900 GHz (at 10.76 GHz) and a temperature coefficient of the resonant frequency (τ_f) ~ ?66.0 ppm/°C were obtained at the optimum sintering temperature (920°C). CaTiO₃ was added into the Li₂Mg₂W₂O₉ ceramic to obtain a near zero τ_f, and 0.93Li₂Mg₂W₂O₉–0.07CaTiO₃ ceramic exhibited improved microwave dielectric properties with a near‐zero τ_f ~ ?1.3 ppm/°C, a ε_r ~21.6, a high Q_u × f value ~20 657 GHz. The low sintering temperature and favorable microwave dielectric properties make it a promising candidate for LTCC applications.     

Novel Low‐Firing Microwave Dielectric Ceramic LiCa3MgV3O12 with Low Dielectric Loss

Novel low temperature firing microwave dielectric ceramic LiCa₃MgV₃O₁₂ (LCMV) with garnet structure was fabricated by the conventional solid‐state reaction method. The phase purity, microstructure, and microwave dielectric properties were investigated. The densification temperature for the LCMV ceramic is 900°C. LCMV ceramic possessed ε_r = 10.5, Q_u × f = 74 700 GHz, and τ_f = ?61 ppm/°C. Furthermore, 0.90LiCa₃MgV₃O₁₂–0.10CaTiO₃ ceramic sintered at 925°C for 4 h exhibited good properties of ε_r = 12.4, Q_u × f = 57 600 GHz, and τ_f = 2.7 ppm/°C. The LCMV ceramic could be compatible with Ag electrode, which makes it a promising ceramic for LTCC technology application.     

Structural ordering and dielectric properties of Ba3CaNb2O9-based microwave ceramics

Ba₃CaNb₂O₉ is a 1:2 ordered perovskite which presents a trigonal cell within the D_3d³ space group. Dense ceramics of Ba₃CaNb₂O₉ were prepared by the solid-state reaction route, and their microwave dielectric features were evaluated as a function of the sintering time. From Raman spectroscopy, by using group-theory calculations, we were able to recognize the coexistence of the 1:1 and 1:2 ordering types in all samples, in which increasing the sintering time tends to reduce the 1:1 domain, leading to an enhancement of the unloaded quality factor. We concluded that this domain acts as a lattice vibration damping, consequently raising the dielectric loss at microwave frequencies. The best microwave dielectric parameters were determined in ceramics sintered at 1500 °C for 32h: ε′ ~ 43; Q_u×f_r = 15,752 GHz; τ_f ~ 278 ppm °C⁻¹.     

Effects of sintering parameters and Nd doping on the microwave dielectric properties of Y2O3 ceramics

Y₂O₃ ceramics with good dielectric properties were prepared via co-precipitation reaction and subsequent sintering in a muffle furnace. The effects of Nd doping and sintering temperature on microwave dielectric properties were studied. With the increase in sintering temperature, the density, quality factor (Q×f), and dielectric constant (ε_r) values of pure Y₂O₃ ceramics increased to the maximum and then gradually decreased. The Y₂O₃ ceramics sintered at 1500 °C for 4 h showed optimal dielectric properties: ε_r=10.76, Q×f=82, 188 GHz, and τ_f=−54.4 ppm/°C. With the addition of Nd dopant, the Q×f values, ε_r, and τ_f of the Nd: Y₂O₃ ceramics apparently increased, but excessive amount degraded the quality factor. The Y₂O₃ ceramics with 2 at% Nd₂O₃ sintered at 1460 °C displayed good microwave dielectric properties: ε_r=10.4, Q×f=94, 149 GHz and τ_f=−46.2 ppm/°C.     

Effects of Li2O-B2O3-SiO2 glass on the low-temperature sintering of Zn0.15Nb0.3Ti0.55O2 ceramics

The influences of Li₂O-B₂O₃-SiO₂ glass (LBS) on the activation energy, phase composition, the stability of the structure and microwave dielectric properties of Zn_0.15Nb_0.3Ti_0.55O₂ ceramics have been systematically investigated. LBS glass acted as flux former and contributed to the reactive liquid-phase sintering mechanism, which remarkably lowed the sintering temperature from 1150?°C to 900?°C and enhanced the shrinkage and densification of ceramic at the low sintering temperatures. The ceramics with 1.5?wt% LBS glass sintered at 900?°C for 3?h show great properties: ε_r = 73.59, Q × f = 8024?GHz, τ_f = 270.54?ppm/°C.     

Low‐Temperature‐Fired ReVO4 (Re = La,Ce) Microwave Dielectric Ceramics

We report a series of ReVO₄ (Re = La, Ce) microwave dielectric ceramics fabricated by a standard solid‐state reaction method. X‐ray diffraction and scanning electron microscopy measurements were performed to explore the phase purity, sintering behavior, and microstructure. The analysis revealed that pure and dense monoclinic LaVO₄ ceramics with a monazite structure and tetragonal CeVO₄ ceramics with a zircon structure could be obtained in their respective sintering temperature range. Furthermore, LaVO₄ and CeVO₄ ceramics sintered at 850°C and 950°C for 4 h possessed out‐bound microwave dielectric properties: ε_r = 14.2, Q × f = 48197 GHz, τ_f = ?37.9 ppm/°C, and ε_r = 12.3, Q × f = 41 460 GHz, τ_f = ?34.4 ppm/°C, respectively. The overall results suggest that the ReVO₄ ceramics could be promising materials for low‐temperature‐cofired ceramic technology.     

Novel Temperature Stable Li2MnO3 Dielectric Ceramics with High Q for LTCC Applications

Novel microwave dielectric ceramics in the Li₂MnO₃ system with high Q prepared through a conventional solid‐state route had been investigated. All the specimens exhibited single phase ceramics sintered in the temperature range 1140°C–1230°C. The microwave dielectric properties of Li₂MnO₃ ceramics were strongly correlated with sintering temperature and density. The best microwave dielectric properties of ε_r = 13.6, Q × f = 97 000 (GHz), and τ_f = ?5.2 ppm/°C could be obtained as sintered at 1200°C for 4 h. BaCu(B₂O₅) (BCB) could effectively lower the sintering temperature from 1200°C to 930°C and slightly induced degradation of the microwave dielectric properties. The Li₂MnO₃ ceramics doped with 2 wt% BaCu(B₂O₅) had excellent dielectric properties of ε_r = 11.9, Q × f = 80 600 (GHz), and τ_f = 0 ppm/°C. With low sintering temperature and good dielectric properties, the BCB added Li₂MnO₃ ceramics are suitable candidates for LTCC applications in wireless communication system.     

Low temperature synthesis and characterization of nano‐crystalline Mg(Zr0.05Ti0.95)O3 ceramics

Mg(Zr_0.05Ti_0.95)O₃ (MZrT) ceramics nanoparticles have been synthesized by polyol method for the first time. The phase evaluation of the MZrT nanoparticles was confirmed using thermo gravimetric analysis and the phase purity of the samples were analyzed using X‐ray diffraction and Raman spectroscopy. The transmission electron microscopy (TEM) images revealed the average particle size between 30 and 40 nm. The optical bandgap is in the range of 3.66‐3.82 eV and is attributed to the quantum confinement effect. Interestingly, the nanopowders sintered at 950°C for 3 hours exhibit the maximum density of 97.52% of the theoretical density which is attributed to the higher sintering velocity of the smaller particles. The obtained microstructure of the ceramics reveals porous free uniform microstructure with prominent grain boundaries. A best combination of microwave dielectric properties (ε_r ~18.04, Q × f_o ~175 THz at 9.5 GHz) are obtained for MZrT ceramics sintered at 950°C for 3 hours. The non‐Debye‐like relaxation process is found to exist inside the sample confirmed by impedance spectroscopy. The AC conduction mechanism is explained on the basis of Correlated Barrier Hopping model. Thermal conductivity of the MZrT ceramics is found to be 10 W/mK. The obtained properties of MZrT ceramics are suitable for resonator, microwave integrated circuit and LTCC applications.     

Effect of Glass Addition on the Microwave Dielectric Properties of CaMgSi2O6 Ceramics

CaMgSi₂O₆ (CMS) ceramics prepared by the solid-state ceramic route have a sintering temperature of 1300°C/2 h. The sintering temperature of CMS was reduced below the melting point of Ag using low-melting LBS and LMZBS glasses. In the case of CMS+15 wt% LMZBS sintered at 900°C/2 h, the dielectric properties obtained were ɛ_r=8.2, Q_u×f=32,000 GHz (10.15 GHz), and τ_f=–48 ppm/°C. The CMS+15 wt% LBS composite, sintered at 925°C/2 h, showed ɛ_r=8, Q_u×f=15,000 GHz (10.17 GHz), and τ_f=–49 ppm/°C. The chemical compatibility of Ag with the ceramic–glass composites was also investigated for low-temperature co-fired ceramic applications.     

Microwave dielectric properties of mineral sillimanite obtained by conventional and cold sintering process

The sillimanite (Al₂SiO₅) mineral has been sintered by conventional ceramic route and by cold sintering methods. The mineral has very poor sinterability and transformed to mullite on sintering above 1525 °C. The dielectric properties of sillimanite mineral (Al₂SiO₅) are investigated at radio and microwave frequency ranges. The mineral sintered at 1525 °C has low ε_r of 4.71 and tanδ of 0.002 at 1 MHz and at microwave frequency ε_r = 4.43, Q_u × f = 41,800 GHz with τ_f = −17 ppm/°C. The sintering aid used for cold sintering Al₂SiO₅ is sodium chloride (NaCl). The Al₂SiO₅NaCl composite was cold sintered at 120 °C. XRD analysis of the composite revealed that there is no additional phase apart from Al₂SiO₅ and NaCl. The densification of the Al₂SiO₅NaCl composite was confirmed by using microstructure analysis. The Al₂SiO₅NaCl composite has ε_r of 5.37 and tanδ of 0.005 at 1 MHz whereas at microwave frequency it has ε_r = 4.52, Q_u × f = 22,350 GHz with τ_f = −24 ppm/°C. The cold sintered NaCl has ε_r = 5.2, Q_u × f = 12,000 GHz with τ_f = −36 ppm/°C.     

Improved microstructure and high quality factor of Li2Ti0.9(Zn1/3Ta2/3)0.1O3 microwave ceramics with LiF additive for LTCC applications

In this study, LiF was utilized to decrease sintering temperature, improve microstructure, enhance Q×f, and regulate τ_f of Li₂Ti_0.9(Zn_1/3Ta_2/3)_0.1O₃ (abbreviated as LTZT) ceramics. A complete solid solution together with a phase transition from monoclinic to cubic rock salt structure occurred. The cell volume of LTZT ceramics decreased as the LiF content increased. Relatively dense and uniform microstructures were observed for the ceramics as the LiF content was not less than 2 wt%. The dielectric constant of LTZT ceramics initially increased and then decreased with the increasing LiF content. The FWHM of the Raman band at about 808 cm^?1 was closely related to the Q×f value. Notably, the samples with 3 wt% LiF exhibited the highest relative density of 97.4 % and satisfactory microwave dielectric properties of ε_r = 23.14 ± 0.16, Q×f = 110,090 ± 1100 GHz, and τ_f = +3.25 ± 1.45 ppm/°C when sintered at 950 °C. Good chemical compatibility with silver indicated the ceramic is a promising candidate in LTCC applications.     

Preparation,structure and microwave dielectric properties of novel La2MgGeO6 ceramics with hexagonal structure and adjustment of its τf value

A novel La₂MgGeO₆ ceramic was synthesized through a solid-state reaction process within a sintering temperature range of 1450–1550 °C. By a combination of X-ray diffraction and Rietveld refinement analyses, the ceramics were found to have a pure hexagonal phase structure belonging to space group R3/146. The scanning electron microscopy images revealed that the ceramic grains were closely connected. The effects of internal (lattice energy, valence bond, and fraction packing) and external factors (density) on the microwave properties of ceramics were also studied. The ceramic exhibited excellent microwave dielectric performances, with a relative permittivity (?_r) of 21.2, a quality factor (Q × f) of 52 360 GHz, and a temperature coefficient of resonant frequency (τ_f) of ?44.2 ppm/°C, when sintered at 1500 °C for 4 h. The τ_f value of the La₂MgGeO₆ ceramic doped with CaTiO₃ could be adjusted to zero. Particularly, 0.2La₂MgGeO₆-0.8CaTiO₃ ceramics have good microwave dielectric properties with τ_f = +2.1 ppm/°C, Q × f = 15 610 GHz, and ?_r = 40.3.     

Effects of LiF addition on sintering behavior and microwave dielectric properties of (Mg0.95Zn0.05)2(Ti0.8Sn0.2)O4 ceramics

The effects of LiF addition on the sinterability and microwave dielectric properties of (Mg_0.95Zn_0.05)₂(Ti_0.8Sn_0.2)O₄ (MZTS) ceramics were investigated. A small amount of LiF addition can effectively lower the sintering temperature of MZTS from 1325 °C to 1150 °C due to the liquid phase effect and induce no apparent degradation of the microwave dielectric properties. With increasing LiF content, the apparent density and dielectric constant decreased gradually, the quality factor increased firstly and then decreased. In particular, MZTS–3.0 wt% LiF ceramics sintered at 1150 °C for 5 h exhibited good microwave dielectric properties of ?_r = 13.05, Q · f = 119,310 GHz (at 10 GHz) and τ_f = ?59.2 ppm/°C.     

A novel ultralow-loss Sr2CeO4 microwave dielectric ceramic and its property modification

A new ultralow-loss Sr₂CeO₄ microwave dielectric ceramic was prepared via a conventional solid-state method. The X-ray diffraction and Rietveld refinement results demonstrate that pure-phase Sr₂CeO₄ ceramics belong to the orthorhombic structure with a Pbam space group. Scanning electron microscopy analysis reveals dense and homogeneous microstructure. Optimum microwave dielectric properties of ε_r = 14.8, Q × f = 172,600 GHz (9.4 GHz) and τ_f = -62 ppm/°C were obtained as it was sintered at 1270 °C for 4 h. In addition, the substitution of a few amount of Ti⁴⁺ for Ce⁴⁺ was found to have significant influences on the grain morphology, sintering behavior, phase structure and microwave dielectric properties. Among them, the Sr₂Ce_0.65Ti_0.35O₄ ceramic sintered at 1350 °C for 4 h demonstrates near-zero τ_f of -1.8 ppm/°C, ε_r of 20.7 and Q×f of 115,550 GHz (8.1 GHz) because of its two-phase structure, showing large application potentials.     

Structure and dielectric properties of novel low temperature co-fired Bi2O3-RE2O3-MoO3 (RE=Pr,Nd, Sm,and Yb) based microwave ceramics

Novel monoclinic Bi₂O₃-xRE₂O₃-yMoO₃ (RE=Pr, Nd, Sm, and Yb) based low temperature co-fired ceramics (LTCC) systems with high sintering density and low microwave dielectric loss are synthesized by conventional solid state reaction technique. The structure and dielectric properties of Bi₂O₃-xRE₂O₃-yMoO₃ ceramics are investigated. Dense BiNdMoO₆ ceramics sintered at 900 °C for 8 h in air have a low dielectric constant ε_r=~7.5, a high quality factor Q×f=~ 24, 800 GHz at 7.0 GHz, and τ_f=~−16 ppm/̊C. Especially, good chemical compatibility of BiNdMoO₆ with Ag electrodes is represented as well. In contrast, BiSmMoO₆ ceramics sintered at 1000 °C for 8 h show enhanced Q×f=~43, 700 GHz at 7.8 GHz with ε_r=~8.5 and τ_f=~−27 ppm/°C. Bi₂O₃-xRE₂O₃-yMoO₃ (RE=Pr, Nd, Sm, and Yb) based ceramics could be considered as promising microwave ceramics for LTCC applications.