Effects of Mg/Si Ratio on Microwave Dielectric Characteristics of Forsterite Ceramics

Nonstoichiometric Mg₂SiO₄ forsterite dielectric ceramics with various Mg/Si ratios ( R =2.025, 2.05, and 2.2) were prepared and characterized. The appearance of a MgSiO₃ secondary phase could be effectively suppressed by adjusting the nonstoichiometry, and a single-phase forsterite structure was obtained in the present ceramics with Mg/Si ratios of 2.025 and 2.05. The microwave dielectric characteristics were significantly improved in the nonstoichiometric Mg₂SiO₄ ceramics on eliminating the MgSiO₃ secondary phase, where an enhanced Q × f value and a suppressed temperature coefficient of resonant frequency λ _f were obtained. The best microwave characteristics were achieved in the nonstoichiometric forsterite ceramics with an Mg/Si ratio of 2.05: ɛ _r =7.5, Q × f =114 730 GHz, and λ _f =−59 ppm/°C.     

Formation and Microwave Dielectric Properties of the Mg2V2O7 Ceramics

The formation process and microwave dielectric properties of the Mg₂V₂O₇ ceramics were investigated. The MgV₂O₆ phase that was formed at around 450°C interacted with remnant MgO above 590°C to form a homogeneous monoclinic Mg₂V₂O₇ phase. Finally, this monoclinic Mg₂V₂O₇ phase was changed to a triclinic Mg₂V₂O₇ phase for the specimen fired at 800°C. Sintering at 950°C for more than 5 h produced high-density triclinic Mg₂V₂O₇ ceramics. In particular, the Mg₂V₂O₇ ceramics sintered at 950°C for 10 h exhibited the good microwave dielectric properties of ɛ_r=10.5, Q × f =58 275 GHz, and τ_f=−26.9 ppm/°C.     

Effect of Zn/Si Ratio on the Microstructural and Microwave Dielectric Properties of Zn2SiO4 Ceramics

Zn₂SiO₄ ceramics synthesized by the conventional solid-state method exhibited a low Q × f value, possibly due to the formation of a ZnO second phase. However, with a small ZnO reduction from the Zn₂SiO₄ ceramics, the ZnO second phase disappeared and grain growth occurred due to the formation of a Si-rich liquid phase. Specimens with a large grain size exhibited an improved Q × f value. In particular, the ceramics with nominal composition Zn_1.8SiO_3.8 sintered at 1300°C exhibited improved microwave dielectric properties of ɛ_r=6.6, Q × f =147 000 GHz, and τ_f=−22 ppm/°C.     

Effect of Li2CO3 Addition on the Sintering Temperature and Microwave Dielectric Properties of Mg2V2O7 Ceramics

Li₂CO₃ was added to Mg₂V₂O₇ ceramics in order to reduce the sintering temperature to below 900°C. At temperatures below 900°C, a liquid phase was formed during sintering, which assisted the densification of the specimens. The addition of Li₂CO₃ changed the crystal structure of Mg₂V₂O₇ ceramics from triclinic to monoclinic. The 6.0 mol% Li₂CO₃-added Mg₂V₂O₇ ceramic was well sintered at 800°C with a high density and good microwave dielectric properties of ɛ _r=8.2, Q × f =70 621 GHz, and τ_f=−35.2 ppm/°C. Silver did not react with the 6.0 mol% Li₂CO₃-added Mg₂V₂O₇ ceramic at 800°C. Therefore, this ceramic is a good candidate material in low-temperature co-fired ceramic multilayer devices.     

High-Q Microwave Dielectrics in the (Mg1−xCox)2TiO4 Ceramics

The microwave dielectric properties and the microstructures of (Mg_{1− x} Co _x )₂TiO₄ ceramics prepared by the conventional solid-state route were investigated. Lattice parameters were also measured for specimens with different x . The formation of solid solution (Mg_{1− x} Co _x )₂TiO₄ ( x =0.02–0.1) was confirmed by the X-ray diffraction patterns, energy dispersive X-ray analysis, and the lattice parameters measured. By increasing x from 0 to 0.05, the Q × f of the specimen can be tremendously boosted from 150 000 GHz to a maximum of 286 000 GHz. A fine combination of microwave dielectric properties (ɛ_r∼15.7, Q × f ∼286 000 GHz at 10.4 GHz, τ_f∼−52.5 ppm/°C) was achieved for (Mg_0.95Co_0.05)₂TiO₄ ceramics sintered at 1390°C for 4 h. Ilmenite-structured (Mg_0.95Co_0.05)TiO₃ was detected as a second phase. The presence of the second phase would cause no significant variation in the dielectric properties of the specimen because it possesses compatible properties compared with that of the main phase. In addition, only a small deviation in the dielectric properties was monitored for specimens with x =0.04–0.05 at 1360°–1420°C. It not only provides a wide process window but also ensures an extremely reliable material proposed as a very promising dielectric for low-loss microwave and millimeter wave applications.     

Effect of Bi2O3 Addition on the Sintering Temperature and Microwave Dielectric Properties of Zn2SiO4 Ceramics

Bi₂O₃ was added to a nominal composition of Zn_1.8SiO_3.8 (ZS) ceramics to decrease their sintering temperature. When the Bi₂O₃ content was <8.0 mol%, a porous microstructure with Bi₄(SiO₄)₃ and SiO₂ second phases was developed in the specimen sintered at 885°C. However, when the Bi₂O₃ content exceeded 8.0 mol%, a liquid phase, which formed during sintering at temperatures below 900°C, assisted the densification of the ZS ceramics. Good microwave dielectric properties of Q × f =12,600 GHz, ɛ_r=7.6, and τ_f=−22 ppm/°C were obtained from the specimen with 8.0 mol% Bi₂O₃ sintered at 885°C for 2 h.     

Synthesis of BaCu(B2O5) Ceramics and their Effect on the Sintering Temperature and Microwave Dielectric Properties of Ba(Zn1/3Nb2/3)O3 Ceramics

BaCu(B₂O₅) ceramics were synthesized and their microwave dielectric properties were investigated. BaCu(B₂O₅) phase was formed at 700°C and melted above 850°C. The BaCu(B₂O₅) ceramic sintered at 810°C had a dielectric constant (ɛ_r) of 7.4, a quality factor ( Q × f ) of 50 000 GHz and a temperature coefficient of resonance frequency (τ_f) of −32 ppm/°C. As the BaCu(B₂O₅) ceramic had a low melting temperature and good microwave dielectric properties, it can be used as a low-temperature sintering aid for microwave dielectric materials for low temperature co-fired ceramic application. When BaCu(B₂O₅) was added to the Ba(Zn_1/3Nb_2/3)O₃ (BZN) ceramic, BZN ceramics were well sintered even at 850°C. BaCu(B₂O₅) existed as a liquid phase during the sintering and assisted the densification of the BZN ceramic. Good microwave dielectric properties of Q × f =16 000 GHz, ɛ_r=35, and τ_f=22.1 ppm/°C were obtained for the BZN+6.0 mol% BaCu(B₂O₅) ceramic sintered at 875°C for 2 h.     

Low-Temperature Sintering and Microwave Dielectric Properties of the Zn2SiO4 Ceramics

B₂O₃ was added to nominal composition Zn_1.8SiO_3.8 (ZS) ceramics to decrease their sintering temperature for application to low-temperature cofired ceramic (LTCC) devices. B₂O₃ reacted with SiO₂ to form a liquid phase containing SiO₂ and B₂O₃. The composition and melting temperature of the liquid phase depended on the sintering temperature and the B₂O₃ content. The specimen containing 20.0 mol% of B₂O₃ sintered at 900°C exhibited high microwave dielectric properties of Q × f =53 000 GHz, ɛ _r=5.7, and τ_f=−16 ppm/°C, confirming the promising potential of the B₂O₃-added ZS ceramics as candidate materials for the LTCC devices.     

Low-Loss Microwave Dielectrics Using Mg2(Ti1−xSnx)O4 (x=0.01–0.09) Solid Solution

Low-loss ceramics having the chemical formula Mg₂(Ti_{1− x} Sn _x )O₄ for x ranging from 0.01 to 0.09 have been prepared by the conventional mixed oxide route and their microwave dielectric properties have been investigated. X-ray powder diffraction patterns indicate the corundum-structured solid solutions for the prepared compounds. In addition, lattice parameters, which linearly increase from 8.4414 to 8.4441 Å with the rise of x from 0.01 to 0.09, also confirm the forming of solid solutions. By increasing x from 0.01 to 0.05, the Q × f of the specimen can be tremendously boosted from 173 000 GHz to a maximum 318 000 GHz. A fine combination of microwave dielectric properties (ɛ_r∼15.57, Q × f ∼318 000 GHz at 10.8 GHz, τ_f∼−45.1 ppm/°C) was achieved for Mg₂(Ti_0.95Sn_0.05)O₄ ceramics sintered at 1390°C for 4 h. Ilmenite-structured Mg(Ti_0.95Sn_0.05)O₃ (ɛ_r∼16.67, Q × f ∼275 000 GHz at 10.3 GHz, τ_f∼−53.2 ppm/°C) was detected as a second phase. The presence of the second phase, however, would cause no significant variation in the dielectric properties of the specimen, because the second phase properties are very similar to the primary phase. These unique properties, in particular, low ɛ_r and high Q × f , can be utilized as a very promising dielectric material for ultra-high-frequency applications.     

A Novel Temperature-Compensated Microwave Dielectric (1−x)(Mg0.95Ni0.05)TiO3−xCa0.6La0.8/3TiO3 Ceramics System

The microstructure and microwave dielectric properties of a (1− x )(Mg_0.95Ni_0.05)TiO₃− x Ca_0.6La_0.8/3TiO₃ ceramics system have been investigated. The system was prepared using a conventional solid-state ceramic route. In order to produce a temperature-stable material, Ca_0.6La_0.8/3TiO₃ was added for a near-zero temperature coefficient (τ_f). With partial replacement of Mg²⁺ by Ni²⁺, the dielectric properties of the (1− x )(Mg_0.95Ni_0.05)TiO₃− x Ca_0.6La_0.8/3TiO₃ ceramics can be promoted. The microwave dielectric properties are strongly correlated with the sintering temperature and the composition. An excellent Q × f value of 118,000 GHz can be obtained for the system with x =0.9 at 1325°C. For practical application, a dielectric constant (ɛ_r) of 24.61, a Q × f value of 102,000 GHz, and a temperature coefficient of resonant frequency (τ_f) of −3.6 ppm/°C for 0.85(Mg_0.95Ni_0.05)TiO₃−0.15Ca_0.6La_0.8/3TiO₃ at 1325°C are proposed. A parallel-coupled line band-pass filter is designed and simulated using the proposed dielectric to study its performance.     

Microstructures and Microwave Dielectric Characteristics of Ca(Zn1/3Nb2/3)O3 Complex Perovskite Ceramics

Ca(Zn_1/3Nb_2/3)O₃ microwave dielectric ceramics were prepared using a solid-state reaction process, and their microwave dielectric properties were evaluated as functions of sintering and postdensification annealing conditions. The relationship between microwave dielectric properties and processing was interpreted through the variation of microstructures. The dielectric constant showed slight variation with sintering and annealing conditions, but the Q × f value increased at first and then decreased with increased sintering temperature, and annealing in oxygen indicated significant improvement in Q × f , especially for the specimens sintered at higher temperatures. The good microwave dielectric properties were obtained in the ceramics sintered at 1225°C in air for 3 h and annealed at 1100°C in oxygen for 8 h: ɛ= 34.1, Q × f = 15 890 GHz, τ_f=−48 ppm/°C.     

Microwave Dielectric Properties of Li2TiO3 Ceramics Doped with ZnO–B2O3 Frit

A type of new low sintering temperature ceramic, Li₂TiO₃ ceramic, has been found. Although it is difficult for the Li₂TiO₃ compound to be sintered compactly at temperatures above 1000°C for the volatilization of Li₂O, dense Li₂TiO₃ ceramics were obtained by conventional solid-state reaction method at the sintering temperature of 900°C with the addition of ZnO–B₂O₃ frit. The sintering behavior and microwave dielectric properties of Li₂TiO₃ ceramics with less ZnO–B₂O₃ frit (≤3.0 wt%) doping were investigated. The addition of ZnO–B₂O₃ frit can lower the sintering temperature of the Li₂TiO₃ ceramics, but it does not apparently degrade the microwave dielectric properties of the Li₂TiO₃ ceramics. Typically, the good microwave dielectric properties of ɛ_r=23.06, Q × f =32 275 GHz, τ_f = 35.79 ppm/°C were obtained for 2.5 wt% ZnO–B₂O₃ frit-doped Li₂TiO₃ ceramics sintered at 900°C for 2 h. The porosity was 0.08%. The Li₂TiO₃ ceramic system may be a promising candidate for low-temperature cofired ceramics applications.     

Sintering Behavior and Dielectric Properties of Bi3NbO7 Ceramics Prepared by Mixed Oxides and High-Energy Ball-Milling Methods

The sintering behavior and dielectric properties of Bi₃NbO₇ ceramics prepared by the high-energy ball milling (HEM) method and conventional mixed oxides method with V₂O₅ addition were investigated. All the samples were sintered between 840° and 960°C. For the ceramics prepared by the mixed oxides method, the pure tetragonal Bi₃NbO₇ phase formed without any cubic phase. With changing sintering temperature, the dielectric constant ɛ_r lies between 79 and 92, while the Q × f values are between 300 and 640 GHz. The samples sintered at 870°C have the best microwave dielectric properties with ɛ_r=79, Q × f =640 GHz, and the temperature coefficients of resonant frequency τ_f between 0 and −20 ppm/°C. For the ceramics prepared by the HEM, a pure cubic phase was obtained. The ɛ_r changes between 78 and 80 and Q × f were between 200 and 290 GHz.     

Polymorphism of Calcium Orthosilicate

Therecentobservation of orthorhombic α'-Ca₂Si0₄ (bredigite) at all temperatures between about 850° and 1450°C. leads to a rational interpretation of the polymorphism of this substance, which is very satisfactory from the crystal-chemical point of view. The so-called β phase, of as yet unknown, complex structure, exists only meta-stably, and not above but below about 675°C, where γ is the stable phase. The monotropic β phase forms on cooling from α'near 675°C. as the result of the inhibition of the α'→γ inversion, at 850°C. The inhibition is caused by the need for a considerable atomic rearrangement and a 12% volume increase which accompanies the change of the coordinations CaO₂ and CaOlo, in α', to CaO₆, in γ. Among the solid phase equilibria with, Mg₂SiO₄ and Ca₃(PO₄)₂, unlimited solid solubility between γ-Ca₂SiO₄ and Mg₂SiO₄ is predicted, whereas the solubility of Mg₂SiO₄ is a limited one in α'and still more so in a-Ca₂SiO₄, as a result of the substitution, for calcium, of the smaller magnesium.     

Effect of Glass Additions on BaO–TiO2–WO3 Microwave Ceramics

The effect of glass addition on the properties of BaO–TiO₂-WO₃ microwave dielectric material N-35, which has Q = 5900 and K = 35 at 7.2 GHz for samples sintered at 1360°C, was investigated. Several glasses including B₂O₃, SiO₂, 5ZnO–2B₂O₃, and nine other commercial glasses were selected for this study. Among these glasses, one with a 5 wt% addition of B₂O₃ to N-35, when sintered at 1200°C, had the best dielectric properties: Q = 8300 and K = 34 at 8.5 GHz. Both Q and K increased with firing temperature as well as with density. The Q of N-35, when sintered with a ZnO–B₂O₃ glass system, showed a sudden drop in the sintering temperature to about 1000°C. The results of XRD, thermal analysis, and scanning electron microscopy indicated that the chemical reaction between the dielectric ceramics and glass had a greater effect on Q than on the density. The effects of the glass content and the mixing process on the densification and microwave dielectric properties are also presented. Ball milling improved the densification and dielectric properties of the N-35 sintered with ZnO–B₂O₃.     

Synthesis and Dielectric Properties of Solution Sol-Gel-Derived 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3 Ceramics

A solution sol-gel method has been developed to prepare 0.9Pb(Mg_1/3Nb_2/3)O₃-0.1PbTiO₃ (0.9PMN-0.1PT) ceramics. During the processing the gel first converted to cubic pyrochlore phase at a calcination temperature of 600°C followed by the formation of pure perovskite phase at 775°C. The ceramics sintered at 1250°C for 4 h showed ≈98% of the theoretical density. The room-temperature dielectric constant of the pellets sintered at 1250°C showed a maximum value of 25035 at 1 kHz. Sintering studies at different temperatures revealed that the dielectric constant increased with increasing grain size in these ceramics.     

Synthesis and Microwave Dielectric Properties of Re3Ga5O12 (Re: Nd, Sm, Eu, Dy, Yb, and Y) Ceramics

Re₃Ga₅O₁₂ (Re: Nd, Sm, Eu, Dy, Yb, and Y) garnet ceramics were synthesized and their microwave dielectric properties were investigated for advanced substrate materials in microwave integrated circuits. The Re₃Ga₅O₁₂ 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 particular, the Sm₃Ga₅O₁₂ ceramics sintered at 1450°C exhibited good microwave dielectric properties of ɛ_r=12.4, Q × f =192 173 GHz, and τ_f=−19.2 ppm/°C.     

Low-Temperature Firing and Microwave Dielectric Properties of Ca[(Li1/3Nb2/3)0.84Ti0.16]O3−δ Ceramics for LTCC Applications

The effects of LiF and ZnO–B₂O₃–SiO₂ (ZBS) glass combined additives on phase composition, microstructures, and microwave dielectric properties of Ca[(Li_1/3Nb_2/3)_0.84Ti_0.16]O_3−δ (CLNT) ceramics were investigated. The LiF and ZBS glass combined additives lowered the sintering temperature of CLNT ceramics effectively from 1150° to 880°C. The main diffraction peaks of all the specimens split due to the coexistence of the non-stoichiometric phase (A) and stoichiometric phase (B), which all possess CaTiO₃-type perovskite structures. The transformation from A into B became accelerated with the increase of LiF or ZBS content. ZBS glass restrained the volatilization of lithium salt, which greatly affected the microstructures and microwave dielectric properties. CLNT ceramics with 2 wt% LiF and 3 wt% ZBS sintered at 900°C for 2 h show excellent dielectric properties: ɛ_r=34.3, Q × f =17 400 GHz, and τ_f=−4.6 ppm/°C. It is compatible with Ag electrodes, which makes it a promising ceramic for low-temperature cofired ceramics technology application.     

Microwave Dielectric Properties of 5Li2O–0.583Nb2O5–3.248TiO2 Ceramics with V2O5

The effects of V₂O₅ addition on the sintering behavior, microstructure, and the microwave dielectric properties of 5Li₂O–0.583Nb₂O₅–3.248TiO₂ (LNT) ceramics have been investigated. With addition of low-level doping of V₂O₅ (≤2 wt%), the sintering temperature of the LNT ceramics could be lowered down to around 920°C due to the liquid phase effect. A secondary phase was observed at the level of 2 wt% V₂O₅ addition. The addition of V₂O₅ does not induce much degradation in the microwave dielectric properties but lowers the τ_f value to near zero. Typically, the excellent microwave dielectric properties of ɛ_r=21.5, Q × f =32 938 GHz, and τ_f=6.1 ppm/°C could be obtained for the 1 wt% V₂O₅-doped sample sintered at 920°C, which is promising for application of the multilayer microwave devices using Ag as an internal electrode.     

A New Compound with Ultra Low Dielectric Loss at Microwave Frequencies

A new ultra low loss microwave dielectric ceramic, Mg(Sn_0.05Ti_0.95)O₃ (MSnT), was found and investigated. The compounds were prepared by the conventional solid-state route, and sintered at 1360°–1480°C for 2–6 h. The investigations show that the MgTi₂O₅ secondary phase was observed. Moreover, the dielectric properties were correlated with the formation second phase. The excellent microwave dielectric properties of Q × f =322 000 (GHz), ɛ_r=17.4, and τ_f=−54 ppm/°C were obtained from the new MSnT ceramics sintered at 1390°C for 4 h.