Low temperature firing of BiSbO4 microwave dielectric ceramic with B2O3–CuO addition

The influence of B₂O₃–CuO addition on the sintering behavior, phase composition, microstructure and microwave dielectric properties of BiSbO₄ ceramic have been investigated. The BiSbO₄ ceramics can be well densified to approach above 95% theoretical density in the sintering temperature range from 840 to 960 °C as the addition amount of B₂O₃–CuO increases from 0.6 to 1.2 wt.%. Sintered ceramic samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The microwave permittivity ?_r saturated at 19–20 and Qf values varied between 33,000 and 46,000 GHz while temperature coefficient of resonant frequency shifting between ?70 and ?60 ppm/°C at sintering temperature around 930 °C. Lowering sintering temperature of BiSbO₄ ceramics makes it possible for application in low temperature co-fired ceramic technology.     

Influence of Li2O–B2O3–SiO2 glass on the sintering behavior and microwave dielectric properties of BaO–0.15ZnO–4TiO2 ceramics

This paper reports the investigation of the performance of Li₂O–B₂O₃–SiO₂ (LBS) glass as a sintering aid to lower the sintering temperature of BaO–0.15ZnO–4TiO₂ (BZT) ceramics, as well as the detailed study on the sintering behavior, phase evolution, microstructure and microwave dielectric properties of the resulting BZT ceramics. The addition of LBS glass significantly lowers the sintering temperature of the BZT ceramics from 1150 °C to 875–925 °C. Small amount of LBS glass promotes the densification of BZT ceramic and improves the dielectric properties. However, excessive LBS addition leads to the precipitation of glass phase and growth of abnormal grain, deteriorating the dielectric properties of the BZT ceramic. The BZT ceramic with 5 wt% LBS addition sintered at 900 °C shows excellent microwave dielectric properties: ε_r=27.88, Q×f=14,795 GHz.     

Preparation and microwave dielectric properties of low-loss MgZrNb2O8 ceramics

A novel low-loss microwave dielectric material MgZrNb₂O₈ was reported for the first time. Single-phase MgZrNb₂O₈ was prepared by a conventional mixed-oxide route and sintered in the temperature range of 1280–1360 °C. The microstructure and microwave dielectric properties were investigated systematically. The X-ray diffraction results showed that all samples exhibit a single wolframite structure. When the sintering temperature was lower than 1340 °C, the Q×f value mainly depended on the relative density. However, when the sintering temperature was above 1340 °C, the Q×f value mainly relied on the grain morphology in addition to the density. The MgZrNb₂O₈ ceramic sintered at 1340 °C for 4 h exhibited excellent microwave dielectric of ε_r=26, Q×f=120,816 GHz (where f=6.85 GHz), and τ_f=?50.2 ppm/°C. These results demonstrate that MgZrNb₂O₈ could be a promising candidate material for the application of highly selective microwave ceramic resonators and filters.     

Preparation and microwave dielectric properties of cristobalite ceramics

Dense SiO₂ ceramics with cristobalite phase were prepared by the solid state sintering route, and the microwave dielectric properties were evaluated. The dielectric constant (?_r) and temperature coefficient of resonant frequency (τ_f) of the pure cristobalite ceramics showed little dependence on the sintering temperature. While, the Qf value increased significantly with increasing the sintering temperature, and it was due to the increasing grain size. The optimized microwave dielectric properties with very low ?_r of 3.81, high Qf value of 80,400 GHz and low τ_f of ?16.1 ppm/°C were obtained for the cristobalite ceramics sintered at 1650 °C for 3 h. It was indicated that cristobalite ceramic was a promising candidate as a low-dielectric-constant microwave material for applications in microwave substrates.     

Microwave dielectric properties of BaO–4.3TiO2–0.5ZnO ceramics with BaCu(B2O5)

Effect of BaCu(B₂O₅) (BCB) addition on microwave dielectric properties and sintering behaviors of BaO–4.3TiO₂–0.5ZnO system (BTZ) ceramics were investigated to develop middle-k dielectric composition with low sintering temperatures. When a small amount of BCB was added to BTZ system, the sintering temperature can be lowered from 1100 °C to 900 °C due to the formation of BCB liquid phase. The system added with 7 wt% BCB was sintered at 900 °C for 2 h and ?_r of 31, Q × f of 18,200 GHz and τ_f of 3.8 ppm/°C were obtained. The suitability of BTZ ceramics for tape casting and cofiring with Ag electrodes was investigated, and no evidence of chemical reaction between Ag and ceramics was observed. The dielectric properties of the stacked multilayer plate without any electrodes were also measured. The result shows that the as-prepared BTZ ceramics are suitable for low-temperature co-fired ceramics applications.     

Tape casting and characterization of Li2.08TiO3-LiF glass free LTCC for microwave applications

Li_2.08TiO₃-LiF Glass-free Low temperature co-fired ceramic (LTCC) green tapes were prepared by tape casing technique. The rheology of the slurry was characterized using rheometer. The slurry exhibited pseudoplastic behavior. The sintering kinetics of the green tape was investigated using heating microscope. The sintering activation energy was determined to be ∼173 kJ/mol. The green tape could be densified at 900 °C/2 h. Microwave dielectric properties of the sintered tape were characterized in a split-post dielectric resonator using a network analyzer. The ceramic sheet with thickness of 0.11 mm demonstrated good microwave dielectric properties: ε_r = 22.4 and Q × f = 35,490 GHz. The cross sectional microstructure of the cofired multilayer stack was observed by scanning electron microscopy (SEM). The green tape demonstrated good chemical and shrinkage compatibilities with Ag electrode during sintering process. The thermal expansion coefficient and thermal conductivity of the ceramic is 22.4 ppm/∘C and 4.75 W m⁻¹ K ⁻¹, respectively.     

Effect of BaCu(B2O5) on the sintering and microwave dielectric properties of Ca0.4Li0.3Sm0.05Nd0.25TiO3 ceramics

The sintering behaviors and microwave dielectric properties of the Ca_0.4Li_0.3Sm_0.05Nd_0.25TiO₃ (abbreviated CLSNT) ceramics with different amounts of BaCu(B₂O₅) addition were investigated in this paper. Adding BaCu(B₂O₅) to CLSNT lowered its sintering temperature from 1300 °C to 925 °C. No secondary phase was observed in the CLSNT ceramics and complete solid solution of the complex perovskite phase was confirmed. The CLSNT ceramics with small amounts of BaCu(B₂O₅) addition could be well sintered at 925 °C without much degradation in the microwave dielectric properties. Especially, the 1.75 wt.% BaCu(B₂O₅)-doped CLSNT ceramic sample sintered at 925 °C for 3 h had optimum microwave dielectric properties of ε_r = 93.5 ± 3.2, Q × f = 6486 ± 434 GHz, and τ_f = 5 ± 1.5 ppm/°C (at 3–4 GHz), enabling it a promising candidate material for LTCC applications. Obviously, BaCu(B₂O₅) could be a suitable sintering aid to facilitate the densification and microwave dielectric properties of the CLSNT ceramics.     

High quality microwave dielectric ceramic sintered at extreme-low temperature below 200° and co-firing with base metal

Ultra-low temperature co-fired ceramics technology (ULTCC) requires the microwave dielectric ceramics with lower intrinsic sintering temperature than the melting point of inner electrodes. In the present work, a novel HBO₂ ceramic was found to be densified at extreme-low temperature below 200 °C, with pores, residual H₃BO₃, amorphous B₂O₃ inside, with a relative permittivity ∼2.12 ± 0.02, a Qf value ∼32,700 ± 300 GHz and a temperature coefficient of resonant frequency value ∼ − 43 ± 3 ppm/°C. This material can be easily obtained by dehydration from H₃BO₃ by sintering at low temperature below 200 °C. Its extreme-low sintering temperature and water solubility also provides the possibility to achieve some novel multi-functional inorganic-organic composite in the future.     

Low-dielectric-constant LiAlO2 ceramics combined with LBSCA glass for LTCC applications

This study used Li₂O–B₂O₃–SiO₂–CaO–Al₂O₃ (LBSCA) glass to reduce the sintering temperature of LiAlO₂ ceramics and to realise the low dielectric constants (ɛ_r<5) of low-temperature co-fired ceramic (LTCC) materials. LBSCA glass remarkably enhanced the densification of LiAlO₂ ceramics. X-ray diffraction patterns indicated that only the γ-LiAlO₂ phase occurred within the doping range of 1 wt% to 3.5 wt%. Scanning electron microscopy images showed dense and uniform grains in samples with 3.0 wt% LBSCA glass. These samples also exhibited low dielectric constants and low dielectric loss when sintered at 900 °C and 950 °C (i.e., ɛ_r=4.48, Qf=35,540 GHz and τ_f=−53 ppm/°C at 900 °C; ɛ_r=4.50, Qf=38,979 GHz and τ_f=−55 ppm/°C at 950 °C, respectively). The material prepared was chemically compatible with silver and showed potential in applications of high-frequency LTCC microwave substrates.     

A novel low-temperature firable La2Zr3(MoO4)9 microwave dielectric ceramic

A novel low-temperature fired La₂Zr₃(MoO₄)₉ microwave dielectric ceramic was successfully fabricated by a conventional solid-state reaction method. The powder compact was densified in air in the temperature range of 700–800 °C for 4 h. X-ray diffraction analysis indicated that all studied samples presented a single phase structure. Rietveld refinement results further confirmed that La₂Zr₃(MoO₄)₉ belonged to a trigonal system with space group R$\overline{3}$c. Scanning electron microscopy results revealed dense and homogeneous microstructure of La₂Zr₃(MoO₄)₉ ceramics as sintered in the temperature range of 725–800 °C. The La₂Zr₃(MoO₄)₉ ceramic sintered at 775 °C for 4 h possessed excellent microwave dielectric properties of relative permittivity ε_r ～ 10.8, quality factor Qxf ～ 50,628 GHz (at 10.45 GHz), and temperature coefficient of the resonant frequency τ_f ～ ?38.8 ppm/°C, showing great potentials for applications of low temperature co-fired ceramic technology.     

Sintering behavior and microwave dielectric properties of Ca1-xBixW1-xVxO4 ceramics

Structure, sintering behavior and microwave dielectric properties of ceramics have been investigated by x-ray powder diffraction (XRD) and scanning electron microscopy (SEM) in this paper. The microwave dielectric properties of the ceramics were studied with a network analyzer at the frequency of about 6–11 GHz. The sintering temperature and microwave dielectric properties could be successfully tuned in a wide window simultaneously by adjusting the A–O bond characteristics. The sintering temperature of CaWO₄ was successfully reduced from 1100 °C to about 950 °C by BiVO₄ addition. Approximately 95%–96% theoretical density could be obtained after sintering at 950 °C for 2 h. All samples exhibit single Scheelite structure (I4₁/a) phase. The dielectric constant increased, whereas the Q×f value decreased, with the increase of x. The τ_f value changed from negative to positive with the increases of x. Combined excellent microwave dielectric properties with ε_r=22. 1, Q×f=16,730 GHz and τ_f=2.39 ppm/°C could be obtained after sintered at the 950 °C for 2 h for x=0.3 compositions.     

Synthesis,characterization, and microwave dielectric properties of ZnTiTa2O8 ceramics with ixiolite structure obtained through the aqueous sol–gel process

Nano-sized ZnTiTa₂O₈ powders with ixiolite structure, with particle sizes ranging from 10 nm to 30 nm, were synthesized by thermal decomposition at 950 °C. The precursors were obtained by aqueous sol–gel and the compacted and sintered ceramics with nearly full density were obtained through subsequent heat treatment. The microstructure and electrical performance were characterized by field emission scanning electron microscopy, x-ray diffraction, and microwave dielectric measurements. All the samples prepared in the range 950–1150 °C exhibit single ixiolite phase and relative density between ~87% and ~94%. The variation of permittivity and Q·ƒ value agreed with that of the relative density. Pure ZnTiTa₂O₈ ceramic sintered at 1050 °C for 4 h exhibited good microwave dielectric properties with a permittivity of 35.7, Q·ƒ value of 57,550 GHz, and the temperature coefficient of resonant frequency of about −24.7 ppm/°C. The relatively low sintering temperature and excellent dielectric properties in the microwave range would make these ceramics promising for applications in electronics.     

Low temperature sintering and microwave dielectric properties of Ba3Ti5Nb6O28 with ZnO–B2O3 glass additions for LTCC applications

The effects of ZnB₂O₄ glass additions on the sintering temperature and microwave dielectric properties of Ba₃Ti₅Nb₆O₂₈ have been investigated using dilatometer, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and a network analyzer. The pure Ba₃Ti₅Nb₆O₂₈ system showed a high sintering temperature (1250 °C) and had the good microwave dielectric properties: Q × f of 10,600 GHz, ɛ_r of 37.0, τ_f of −12 ppm/°C. It was found that the addition of ZnB₂O₄ glass to Ba₃Ti₅Nb₆O₂₈ lowered the sintering temperature from 1250 to 925 °C. The reduced sintering temperature was attributed to the formation of ZnB₂O₄ liquid phase and B₂O₃-rich liquid phases. Also the addition of ZnB₂O₄ glass enhanced the microwave dielectric properties: Q × f of 19,100 GHz, ɛ_r of 36.6, τ_f of 5 ppm/°C. From XPS and XRD studies, these phenomena were explained in terms of the reduction of oxygen vacancies and the formation of secondary phases having the good microwave dielectric properties.     

A novel low-firing microwave dielectric ceramic Li2ZnGe3O8 with cubic spinel structure

A Li₂ZnGe₃O₈ ceramic was investigated as a promising microwave dielectric material for low-temperature co-fired ceramics applications. Li₂ZnGe₃O₈ ceramic was prepared via the conventional solid-state method. X-ray diffraction data shows that Li₂ZnGe₃O₈ ceramic crystallized into a cubic spinel structure with a space group of P4₁32. Dense ceramic with a relative densities of 96.3% were obtained when sintered at 945 °C for 4 h and exhibited the optimum microwave properties with a relative permittivity (ε_r) of 10.3, a quality factor (Q × f) of 47,400 GHz (at 13.3 GHz), and a temperature coefficient of resonance frequency (τ_f) of −63.9 ppm/°C. The large negative τ_f of Li₂ZnGe₃O₈ ceramic could be compensated by rutile TiO₂, and 0.9Li₂ZnGe₃O₈–0.1TiO₂0·1TiO₂ ceramic sintered at 950 °C for 4 h exhibited improved microwave dielectric properties with a near-zero τ_f of −1.6 ppm/°C along with ε_r of 11.3 and a Q × f of 35,800 GHz (11.6 GHz). Moreover, Li₂ZnGe₃O₈ was found to be chemically compatible with silver electrode when sintered at 945 °C.     

Broadband dielectric characterization of TiO2 ceramics sintered through microwave and conventional processes

In this work the microwave sintering (MW) of pure submicron rutile TiO₂ powder has been conducted in complete electric field using a single mode cavity of 2.45 GHz and without any susceptor. The sintering conditions were varied and similar sintering cycles were also done using a conventional furnace (CV), in carefully measuring the temperature in both processes. The dielectric properties, from kHz to GHz were determined and a comparison analysis was made between microwaved and conventional sintered specimens. It is shown that microwave sintering allows to obtain dense material (>95%) in a very short time (10–15 min) at a sintering temperature ranging from 1000 °C to 1300 °C. Some samples are fully dense (>99% theoretical density) after being microwave heated for ～10 min at ～1300 °C. Using the microwave heating, the processing temperature to get high dense material (i.e. >94%) is lowered by ～150–175 °C compared to conventionally sintered samples. It is also shown that an annealing in air at ～800 °C for ～4 h, leads to very low loss TiO₂ ceramic in the entire frequency range investigated. Owing to the lowest sintering temperature provided by microwaves, the low frequency dielectric losses are smaller for MW samples than for CV sintered samples. Among the highest reported microwave Q factors (～7350) have been measured on pure TiO₂ samples exhibiting the largest grain size (～1.5 μm) and density (>96%).     

Microwave dielectric properties of low-temperature sinterable α-MoO3

The α-MoO₃ ceramics were prepared by uniaxial pressing and sintering of MoO₃ powder at 650 °C and their structure, microstructure, densification and sintering and microwave dielectric properties were investigated. The sintering temperature of α-MoO₃ was optimized based on the best densification and microwave dielectric properties. After sintering at 650 °C the relative permittivity was found to be 6.6 and the quality factor was 41,000 GHz at 11.3 GHz. The full-width half-maximum of the A_1g Raman mode of bulk α-MoO₃ at different sintering temperatures correlated well with the Qf values. Moreover, the sintered samples showed a temperature coefficient of the resonant frequency of ?25 ppm/°C in the temperature range from ?40 to 85 °C and they exhibited a very low coefficient of thermal expansion of ±4 ppm/°C. These microwave dielectric properties of α-MoO₃ will be of great benefit in future MoO₃ based materials and their applications.     

Microwave dielectric properties of Mg3(VO4)2–xBa3(VO4)2 ceramics for LTCC with near zero temperature coefficient of resonant frequency

The Mg₃(VO₄)₂–xBa₃(VO₄)₂ ceramics have been investigated to obtain a low-temperature co-fired ceramic (LTCC). The highest quality factor (Q_f) of approximately 114,000 GHz was obtained when the ceramic with x = 0.2 was sintered at 950 °C for 5 h in air. The temperature coefficient of resonant frequency (τ_f) of the ceramics sintered at 1025 °C varied from −90 to 60 ppm/°C as the amount of xBa₃(VO₄)₂ increased, and was a near zero value in the sample obtained at x = 0.5 where the dielectric constant (ɛ_r) and the Q_f values were approximately 12 and 55,000 GHz, respectively. In order to reduce the sintering temperatures of Mg₃(VO₄)₂–xBa₃(VO₄)₂ ceramics, the effects of Li₂CO₃ addition as a sintering aid on the microwave dielectric properties of Mg₃(VO₄)₂–0.5Ba₃(VO₄)₂ ceramics were also characterized in this study. The Li₂CO₃ addition was effective in reducing the sintering temperature without detrimental effects on the Q_f values of the ceramics. One result: the microwave dielectric properties of Mg₃(VO₄)₂–0.5Ba₃(VO₄)₂ with 0.0625 wt%-doped Li₂CO₃ ceramic, which was sintered at 950 °C for 5 h in air, has a ɛ_r value of 13, a Q_f value of 74,000 GHz, and a τ_f value of −6 ppm/°C.     

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.     

Low-temperature sintering and microwave dielectric properties of Ca5Co4(VO4)6 ceramics

A novel low temperature firing high Q microwave dielectric ceramic Ca₅Co₄(VO₄)₆ was prepared by the conventional solid-state reaction method. The phase purity, microstructure, and microwave dielectric properties were investigated. The Ca₅Co₄(VO₄)₆ ceramic sintered at 875 °C exhibited excellent microwave dielectric properties: Qxf = 95,200 GHz (at 10.6 GHz), τ_f = −63 ppm/°C, ɛ_r = 10.1, and its ɛ_r corrected for porosity was calculated as 11.1.     

Li4Mg3Ti2O9: A novel low-loss microwave dielectric ceramic for LTCC applications

Low-loss novel Li₄Mg₃Ti₂O₉ dielectric ceramics with rock-salt structure were prepared by a conventional solid-state route. The crystalline structure, chemical bond properties, infrared spectroscopy and microwave dielectric properties of the abovementioned system were initially investigated. It could be concluded from this work that the extrinsic factors such as sintering temperatures and grain sizes significantly affected the dielectric properties of Li₄Mg₃Ti₂O₉ at lower sintering temperatures, while the intrinsic factors like bond ionicity and lattice energy played a dominant role when the ceramics were densified at 1450 °C. In order to explore the origin of intrinsic characteristics, complex dielectric constants (ε^’ and ε^’’) were calculated by the infrared spectra, which indicated that the absorptions of phonon oscillation predominantly effected the polarization of the ceramics. The Li₄Mg₃Ti₂O₉ ceramics sintered at 1450 °C exhibited excellent properties of ε_r=15.97, Q·f=135,800 GHz and τ_f=−7.06 ppm/°C. In addition, certain amounts of lithium fluoride (LiF) were added to lower the sintering temperatures of matrix. The Li₄Mg₃Ti₂O₉−3 wt% LiF ceramics sintered at 900 °C possessed suitable dielectric properties of ε_r=15.17, Q·f =42,800 GHz and τ_f=−11.30 ppm/°C, which made such materials promising for low temperature co-fired ceramic applications (LTCC).