Low temperature sintering of the Ba2Ti9O20 ceramics using B2O3/CuO and BaCu(B2O5) additives

The effects of B₂O₃/CuO and BaCu(B₂O₅) additives on the sintering temperature and microwave dielectric properties of Ba₂Ti₉O₂₀ ceramics were investigated. The B₂O₃ added Ba₂Ti₉O₂₀ ceramics were not able to be sintered below 1000 °C. However, when both CuO and B₂O₃ were added, they were sintered below 900 °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 Ba₂Ti₉O₂₀ ceramics at low temperature. BaCu(B₂O₅) powders were produced and used to reduce the sintering temperature of the Ba₂Ti₉O₂₀ ceramics. Good microwave dielectric properties of Qxf = 16,000 GHz, ɛ_r = 36.0 and τ_f = 9.11 ppm/°C were obtained for the Ba₂Ti₉O₂₀ ceramics containing 10.0 mol% BaCu(B₂O₅) sintered at 875 °C for 2 h.     

A novel low-fired,temperature-stable,and low-cost (1−x)BaCu(B2O5)−xTiO2 microwave dielectric ceramic

BaCu(B₂O₅) is a typical microwave dielectric ceramic (MDC) with a low sintering temperature, but it exhibits a large negative temperature coefficient of resonant-frequency (τ_f) which makes it difficult to use in wireless communications. We employ TiO₂ to improve its temperature-stability of resonant-frequency, and reveal the effects of TiO₂ on the densification and the microwave dielectric properties of BaCu(B₂O₅). Here we show that BaCu(B₂O₅) can be well-sintered at 825 °C with proper TiO₂ additions; we find that the TiO₂ grains homogeneously distribute in the boundaries of BaCu(B₂O₅) grains, resulting in the τ_f compensation of BaCu(B₂O₅). Enhanced temperature-stability of resonant-frequency can be achieved by increasing the content of TiO₂ properly. A novel temperature-stable (1-x)BaCu(B₂O₅)–xTiO₂ (x = 0.20) MDC (τ_f =?0.8 ± 3.0 ppm/°C, ε_r = 8.8 ± 0.36, Q×f = 28,612 ± 1170 GHz) is obtained using some low-cost raw materials. Our results provide the underlying insights needed to guide the design of temperature-stable MDCs for wireless communication applications.     

Effects of adding B2O3 on microwave dielectric properties of 0.9625MgTiO3-0.0375(Ca0.5Sr0.5)TiO3 composite ceramics

A series of 0.9625MgTiO₃-0.0375(Ca_0.5Sr_0.5)TiO₃ composite ceramics added with different amounts of B₂O₃ (1-5 wt%) were prepared via the solid state sintering method using the pre-synthesized raw MgTiO₃ and (Ca_0.5Sr_0.5)TiO₃ powders by molten-salt reaction. The sintering temperature of 0.9625MgTiO₃-0.0375(Ca_0.5Sr_0.5)TiO₃ composite ceramics can be reduced from 1275°C to 1175°C due to the liquid phase sintering effect of B₂O₃. When the adding amount of B₂O₃ was more than 2 wt%, a new phase MgTi₂O₅ could be detected by X-ray diffraction, which would substantially degrade the dielectric properties of the obtained ceramics. Resultantly, the quality factor (Q·f) and dielectric constant (ε_r) of the samples increase first and decrease later with increasing addition amount of B₂O₃. In addition, the temperature coefficient of resonant frequency (τ_f) progressively increases with increasing content of B₂O₃. By sintering at 1175°C for 4 hours, the obtained 0.9625MgTiO₃-0.0375Ca_0.5Sr_0.5TiO₃ composite ceramics with 2 wt% B₂O₃ possess the optimal microwave dielectric properties of ε_r = 18.9, Q·f = 57 000 GHz and τ_f = −1.2 ppm/°C.     

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.     

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.     

Dielectric Properties and Low‐Temperature Sintering of the Ba0.6Sr0.4TiO3 Ceramics with B2O3/CuO Additions

The sintering behaviors and dielectric properties of Ba_0.6Sr_0.4TiO₃ ceramics were investigated as a function of B₂O₃ and CuO content. The addition of both B₂O₃ and CuO reduced the sintering temperature of Ba_0.6Sr_0.4TiO₃ about 500°C. It was suggested that a liquid phase BaCu(B₂O₅) was formed and assisted the densification of Ba_0.6Sr_0.4TiO₃ ceramics. Ba_0.6Sr_0.4TiO₃ ceramics co‐doped with 3.0 mol% B₂O₃, and 2.0 mol% CuO, sintered at 950°C for 5 h, had a dense microstructure and showed good microwave dielectric properties of a moderate dielectric constant (ε = 1048), low dielectric loss (0.0090) and high tunability (42.2%) at dc electric field of 30 kV/cm.     

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.     

Microwave Dielectric Properties of MLi2Ti6O14 [M=Ba and Sr] Ceramics and Their Compatibility with Sliver

Microwave dielectric properties of Li‐containing orthorhombic compounds with the composition of MLi₂Ti₆O₁₄ (M = Ba and Sr) were investigated. The ceramics were synthesized by the conventional solid‐state reaction route. The optimized sintering temperatures for the BaLi₂Ti₆O₁₄ and SrLi₂Ti₆O₁₄ ceramics are 1025°C and 1000°C, respectively. Favorable microwave dielectric properties were obtained with moderate ε_r of 31.7 and 33.6, quality factor Q × f values of 23 300 (at 7.3 GHz) and 8700 GHz (at 6.8 GHz), and low‐temperature coefficient of resonant frequency (τ_f) values of ?15.4 and ?2.7 ppm/°C for BaLi₂Ti₆O₁₄ and SrLi₂Ti₆O₁₄ ceramics, respectively. The addition of BaCu(B₂O₅) can effectively reduce the sintering temperature below 930°C without degrading the microwave dielectric properties. Compatibility with Ag electrode indicates these materials could be applied to low‐temperature cofired ceramic devices.     

Enhanced dielectric properties and chemical bond characteristics of ZnNb2O6 ceramics due to zinc oxide doping

Regarding advanced 5G mobile communication, microwave dielectric ceramics are considered as the most potential materials to develop new-generation base station resonators. Herein, ZnNb₂O₆ ceramics with ε_r of approximately 24 have been prepared using the solid-state reaction method, with tailored extra ZnO of x mol% (x = 1, 2 and 3). We have for the first time applied the P-V-L chemical bond theory to investigate ZnNb₂O₆ ceramics with ZnO doping, by exploring the relationship of dielectric properties and chemical bond characteristics. Particularly, the Raman spectra demonstrates that the full width at half maximum of υ₁ (A_g) vibration mode can exhibit significant correlation with the quality factor (Q × f ). To further support the experimental study, we have also conducted the first-principle calculation of electron density difference via CASTEP package, which further confirms the change of temperature coefficient of resonance frequency (τ_f ). Our newly designed ZnNb₂O₆ ceramics doped with 1 mol% ZnO exhibit excellent dielectric properties, i.e., ε_r = 23.74, Q × f = 102,824 GHz and τ_f = ?55.38 ppm/°C, which demonstrates great potential to construct miniaturized 5G base station with advanced ceramic dielectrics.     

Effects of ZnO and B2O3 on the Microstructure and Microwave Dielectric Properties of 5Li2O‐1Nb2O5‐5TiO2 Ceramics

The effects of ZnO and B₂O₃ addition on the sintering behavior, microstructure, and the microwave dielectric properties of 5Li₂O‐1Nb₂O₅‐5TiO₂ (LNT) ceramics have been investigated. With addition of low‐level doping of ZnO and B₂O₃, the sintering temperature of the LNT ceramics can be lowered down to near 920°C due to the liquid phase effect. The Li₂TiO₃ss and the “M‐phase” are the two main phases, whereas other phase could be observed when co‐doping with ZnO and B₂O₃ in the ceramics. And the amount of the other phase increases with the ZnO content increasing. The addition of ZnO does not induce much degradation in the microwave dielectric properties but lowers the τ_f value to near zero. Typically, the good microwave dielectric properties of ε_r = 36.4, Q × f = 8835 GHz, τ_f = 4.4 ppm/°C could be obtained for the 1 wt% B₂O₃ and 4 wt% ZnO co‐doped sample sintered at 920°C, which is promising for application of the multilayer microwave devices using Ag as internal electrode.     

Crystal structure,Raman spectra,and modified dielectric properties of pure-phase ZnZrNb2O8 ceramics at low temperature

Low-temperature co-fired ceramics technology (LTCC) exhibits enormous superiorities in packaging, integration, and interconnection. However, the complex compositions of low-melting point sintering aids may react with ceramic matrix, which increases the difficulties of phase control and tape casting. In this work, the Li₂CO₃–B₂O₃–Bi₂O₃–SiO₂ (LBBS) sintering aid was adopted to sinter ZnZrNb₂O₈ ceramics with single phase at low temperatures. The LBBS glass could be used to fabricate pure-phase ZnZrNb₂O₈ ceramics at a low sintering temperature, promote the grain growth, and increase the densification of ZnZrNb₂O₈ ceramics. Furthermore, the unit cell volume, NbO₆ octahedral distortion, Raman shift, and FWHM changed along with LBBS addition, thereby affecting the microwave dielectric properties. Remarkably, ZnZrNb₂O₈ ceramics doped with 0.75 wt.% LBBS at 950°C were chemically compatible with the silver electrode and exhibited excellent microwave dielectric characteristics: ε_r = 27.1, Q × f = 54 500 GHz, and τ_f = −48.7 ppm/°C, providing candidates for LTCC applications.     

Improvement of the dielectric properties of rutile-doped Al2O3 ceramics by annealing treatment

The microwave dielectric properties of alumina (Al₂O₃) ceramics were studied. The objectives were to improve the large negative temperature coefficient of the resonant frequency (τ_f) of Al₂O₃ ceramics and to obtain a relatively large quality factor (Qf) through the addition of rutile (TiO₂), which has a large positive τ_f, and an annealing treatment. A near-zero τ_f (+1.5 ppm/°C), excellent Qf (148,000 GHz) and ɛ_r (12.4) were obtained in 0.9 Al₂O₃–0.1 TiO₂ ceramics sintered at 1350 °C for 2 h, followed by annealing at 1100 °C for 12 h in air.     

High quality factor microwave dielectric ceramics in the (Mg1/3Nb2/3)O2–ZrO2–TiO2 ternary system

Novel high quality factor microwave dielectric ceramics (1?x)ZrTiO₄?x(Mg_1/3Nb_2/3)TiO₄ (0.325≤x≤0.4) and (ZrTi)_1?y(Mg_1/3Nb_2/3)_yO₄ (0.2≤y≤0.5) with the addition of 0.5 wt% MnCO₃ in the (Mg_1/3Nb_2/3)O₂–ZrO₂–TiO₂ ternary system were prepared, using solid‐state reaction method. The relationship between the structure and microwave dielectric properties of the ceramics was studied. The XRD patterns of the sintered samples reveal the main phase belonged to α‐PbO₂‐type structure. Raman spectroscopy and infrared reflectivity (IR) spectra were employed to evaluate phonon modes of ceramics. The 0.65ZrTiO₄?0.35(Mg_1/3Nb_2/3)TiO₄?0.5 wt% MnCO₃ ceramic can be well densified at 1240°C for 2 hours and exhibits good microwave dielectric properties with a relative permittivity (ε_r) of 42.5, a quality factor (Q×f) value of 43 520 GHz (at 5.9 Ghz) and temperature coefficient of resonant frequency (τ_f) value of ?5ppm/°C. Furthermore, the (ZrTi)_0.7(Mg_1/3Nb_2/3)_0.3O₄?0.5 wt% MnCO₃ ceramic sintered at 1260°C for 2 hours possesses a ε_r of 31.8, a Q×f value of 35 640 GHz (at 6.3 GHz) and a near zero τ_f value of ?5.9 ppm/°C. The results demonstrated that the (Mg_1/3Nb_2/3)O₂–ZrO₂–TiO₂ ternary system with excellent properties was a promising material for microwave electronic device applications.     

Ultra-low fired fluoride composite microwave dielectric ceramics and their application for BaCuSi2O6-based LTCC

A total of 14 fluoride composite ceramics were prepared through solid-state method and their microwave dielectric properties were investigated. Among the fluoride composite ceramics, 0.36LiF–0.39MgF₂–0.25SrF₂ (LMS) had the lowest sintering temperature (600°C) and presented a dielectric constant (ε_r) of 6.24 ± 0.05, a quality factor (Q × f) of 33 274 ± 900 GHz, and a temperature coefficient resonant frequency (τ_f) of −86.74 ± 8 ppm/°C. As the LMS ceramic had a low melting point (646°C), it can be used as sintering aid for LTCC applications. The sintering temperature of BaCuSi₂O₆ decreased from 1050°C to 875°C with 2 wt% LMS doped and excellent microwave dielectric properties of ε_r = 8.16 ± 0.04, Q × f = 24 351 ± 300 GHz, and τ_f = −9.74 ± 1 ppm/°C were obtained. Moreover, BaCuSi₂O₆-2 wt% LMS can be co-fired with Ag powders, which makes it a potential new candidate for LTCC applications.     

Microwave dielectric properties of LiNb3O8 ceramics with TiO2 additions

The microwave dielectric properties of LiNb₃O₈ ceramics were investigated as a function of the sintering temperature and the amount of TiO₂ additive. LiNb₃O₈ ceramics, which were calcined at 750 °C and sintered at 1075 °C for 2 h, showed a dielectric constant (ɛ_r) of 34, a quality factor (Q × f₀) of 58,000 GHz and a temperature coefficient of resonance frequency (τ_f) of −96 ppm/°C, respectively. The density of the samples influenced the properties of these properties. As the TiO₂ content increased in the LiNb₃O₈–TiO₂ system, ɛ_r and τ_f of the material were increased due to the mixing effect of TiO₂ phase, which has higher dielectric constant and larger positive τ_f. The 0.65LiNb₃O₈–0.35TiO₂ ceramics showed a dielectric constant ɛ_r of 46.2, a quality factor (Q × f₀) of 5800 GHz and a temperature coefficient of resonance frequency τ_f of near to 0 ppm/°C.     

Ba5Li2W3O15: A New Li‐Containing Perovskite‐Type Microwave Ceramic with High Q and Low τf

A new Li‐containing microwave ceramic Ba₅Li₂W₃O₁₅ with hexagonal perovskite structure was prepared through a solid‐state ceramic route. Small amount of scheelite BaWO₄ appeared as a second phase during sintering. The Ba₅Li₂W₃O₁₅ could be well densified at 1120°C and exhibits good microwave dielectric properties with permittivity (ε_r) of 25.4, high Q × f value about 39 000 GHz, and low temperature coefficient of resonate frequency (τ_f) of 10 ppm/°C. The addition of BaCu(B₂O₅) can effectively lower the sintering temperature from 1120°C to 900°C and does not induce degradation of the microwave dielectric properties. These results indicate that the Ba₅Li₂W₃O₁₅ ceramic might be a promising candidate in microwave dielectric resonators.     

Effect of B2O3 and CuO additives on the sintering temperature and microwave dielectric properties of Ba(Zn1/3Nb2/3)O3 ceramics

The B₂O₃ added Ba(Zn_1/3Nb_2/3)O₃ (BBZN) ceramic was sintered at 900 °C. BaB₄O₇, BaB₂O₄, and BaNb₂O₆ second phases were found in the BBZN ceramic. Since BaB₄O₇ and BaB₂O₄ second phases have an eutectic temperature around 900 °C, they might exist as the liquid phase during sintering at 900 °C and assist the densification of the BZN ceramics. Microwave dielectric properties of dielectric constant (ɛ_r) = 32, Q × f = 3500 GHz, and temperature coefficient of resonance frequency (τ_f) = 20 ppm/°C were obtained for the BZN with 5.0 mol% B₂O₃ sintered at 900 °C for 2 h. The BBZN ceramics were not sintered below 900 °C and the microwave dielectric properties of the BBZN ceramics sintered at 900 °C were very low. However, when CuO was added, BBZN ceramic was well sintered even at 875 °C. The liquid phase related to the BaCu(B₂O₅) second phase could be responsible for the decrease of sintering temperature. Good microwave dielectric properties of ɛ_r = 36, Q × f = 19,000 GHz and τ_f = 21 ppm/°C can be obtained for CuO doped BBZN ceramics sintered at 875 °C for 2 h.     

Microwave dielectric properties of Re3Ga5O12 (Re: Nd,Sm, Eu,Dy and Yb) ceramics and effect of TiO2 on the microwave dielectric properties of Sm3Ga5O12 ceramics

Re₃Ga₅O₁₂ (Re: Nd, Sm, Eu, Dy and Yb) garnet ceramics sintered at 1350–1500 °C had a high quality factor (Q × f) ranging from 40,000 to 192,173 GHz and a low dielectric constant (ɛ_r) of between 11.5 and 12.5. They also exhibited a relatively stable temperature coefficient of resonant frequency (τ_f) in the range of −33.7 to −12.4 ppm/°C. In order to tailor the τ_f value, TiO₂ was added to the Sm₃Ga₅O₁₂ ceramics, which exhibited good microwave dielectric properties. The relative density and grain size increased with addition of TiO₂, resulting in the enhancement of Q × f value. The τ_f increased with the addition of TiO₂. Excellent microwave dielectric properties of ɛ_r = 12.4, Q × f = 240,000 GHz and τ_f = −16.1 ppm/°C were obtained from the Sm₃Ga₅O₁₂ ceramics sintered at 1450 °C for 6 h with 1.0 mol% TiO₂. Therefore, Re₃Ga₅O₁₂ ceramics, especially TiO₂-added Sm₃Ga₅O₁₂ ceramics are good candidates for advanced substrate materials in microwave integrated circuits (MICs) applications.     

Low‐Temperature Sintering Microwave Characteristics of B2O3‐doped CaLa4Ti4O15 Dielectric Ceramics

Preparation and microwave dielectric properties of B₂O₃‐doped CaLa₄Ti₄O₁₅ ceramics have been investigated. X‐ray diffraction data show that CaLa₄Ti₄O₁₅ ceramic has a trigonal structure coupled with a second phase of CaLa₄Ti₅O₁₇. The CaLa₄Ti₄O₁₅ ceramic with addition of 0.5 wt% B₂O₃, sintered at 1220°C for 4 h, exhibits microwave dielectric properties with a dielectric constant of 45.8, Q × f value of 24,000 GHz, and temperature coefficient of resonant frequency (τ_f) of ?19 ppm/^°C. B₂O₃‐doped CaLa₄Ti₄O₁₅ ceramics, which have better sintering behavior (decrease in sintering temperature ~ 330°C) and dielectric properties than pure CaLa₄Ti₄O₁₅ ceramics, are candidates for applications in microwave devices.     

Enhanced temperature stability of Mg2TiO4-based ceramics by LCB additive

The Mg₂TiO₄-xwt% LiF–2CaF₂–2B₂O₃ (LCB, 3.0 ≤ x ≤ 10.0) ceramics were fabricated to study the relationship among LCB additive and the sintering behavior, phase composition, micro-structure and dielectric performance of ceramics in this study. The sintered ceramics are mainly Mg₂TiO₄ phase, accompanied by small amount of second phase CaTiO₃ and Mg₃B₂O₆. They are generated from the chemical reaction of CaF₂ and B₂O₃ with the matrix material, respectively. Appropriate LCB additive significantly enhanced sintering ability and dielectric performance of Mg₂TiO₄-based ceramics. Sintered at 1175 °C, Mg₂TiO₄-7.5 wt% LCB ceramics exhibited a dielectric performance: ε_r of 15.3, Q × f of 32 950 GHz and τ_f of +1.96 ppm/°C, which is expected to be an alternative material for communication component.