A new microwave dielectric ceramic for LTCC applications

A new low-sintering temperature microwave dielectric ceramic was found and investigated in the Li₂O–Nb₂O₅–TiO₂ (Li₂O:Nb₂O₅:TiO₂ = 5.7:1:14.7, by mole, abbreviated as LNT) system. This new microwave dielectric ceramic shows a relatively high permittivity (47), high Q × f values up to 17,800 GHz, and low temperature coefficients (57 ppm/°C), which were obtained via sintering at 1,125 °C. With the low-level doping of B₂O₃–CuO (BCu) (below 2 wt%), the sintering temperature of the LNT ceramic could be effectively reduced to 900 °C. The addition of BCu does not induce apparent degradation in the microwave properties but lowers the τ _f value. Typically, the 2.0 wt% BCu-doped ceramics sintered at 900 °C have better microwave dielectric properties of ε_r = 48.7, Q × f = 16,350 GHz, τ _f  = 32 ppm/°C, which suggest that the ceramics could be applied in multilayer microwave devices requiring low sintering temperatures.     

Low-temperature sintering and microwave dielectric properties of MgTiO<Subscript>3</Subscript> ceramics

The effects of CuO–Bi₂O₃–V₂O₅ additions on the sintering temperature and the microwave dielectric properties of MgTiO₃ ceramics were investigated systematically. The CuO–Bi₂O₃–V₂O₅ (CuBiV) addition significantly lowered the densification temperature of MgTiO₃ ceramics from 1400 °C to about 900 °C, which is due to the formation of the liquid-phase of BiVO₄ and Cu₃(VO₄)₂ during sintering. The saturated dielectric constant (ε_r) increased, the maximum quality factor (Qf) values decreased and the temperature coefficient of resonant frequency (τ_f) shifted to a negative value with the increasing CuBiV content, which is mainly attributed to the increase of the second phase BiVO₄. MgTiO₃ ceramics with 6 wt.% CuBiV addition sintered at 900 °C for 2 h have the excellent microwave dielectric properties: ε _r= 18.1, Qf = 20300 GHz and τ_f = −57 ppm/ °C.     

Effect of B2O3 and CuO additions on the sintering temperature and microwave dielectric properties of 3Li2O–Nb2O5–3TiO2 ceramics

The effects of B₂O₃–CuO (BCu, the weight ratio of B₂O₃ to CuO is 1:1) addition on the sintering behavior, microstructure, and the microwave dielectric properties of 3Li₂O–Nb₂O₅–3TiO₂ (LNT) ceramics have been investigated. The low-amount addition of BCu can effectively lower the sintering temperature of LNT ceramics from 1125 to 900 °C and induce no obvious degradation of the microwave dielectric properties. Typically, the 2 wt% BCu-added ceramic sintered at 900 °C has better microwave dielectric properties of ε _r  = 50.1, Q × f = 8300 GHz, τ _f  = 35 ppm/°C. Silver powders were cofired with the dielectric under air atmosphere at 900 °C. The SEM and EDS analysis showed no reaction between the dielectric ceramic and silver powders. This result shows that the LNT dielectric materials are good candidates for LTCC applications with silver electrode.     

Microwave dielectric properties and compatibility with silver of low-fired Ba2Ti3Nb4O18 ceramics with BaCu(B2O5) addition

The effects of BaCu(B₂O₅) (BCB) additions on the sintering temperature and microwave dielectric properties of Ba₂Ti₃Nb₄O₁₈ ceramic have been investigated. The addition of BCB can lower the sintering temperature of Ba₂Ti₃Nb₄O₁₈ ceramic from 1,250 to 900 °C and induce no obvious degradation of the microwave dielectric properties. Typically, the 5 wt% BCB added Ba₂Ti₃Nb₄O₁₈ ceramic sintered at 900 °C for 2 h exhibited good microwave dielectric properties of Q × f = 17,600 GHz, ε _r = 38.2 and τ _f  = 7 ppm/°C. The dielectric ceramic demonstrated stability against the reaction with the Ag electrode, which suggests that the ceramics could be applied in multilayer microwave devices requiring low sintering temperatures.     

Low-temperature sintered (Zn0.65Mg0.35)TiO3 microwave ceramics doped with CuV2O6

The influence of the CuV₂O₆ additives on the densification, microstructural evolution, and dielectric properties of (ZnMg)TiO₃ (ZMT) ceramics was investigated. The sintering agent CuV₂O₆ can significantly enhance the sinterability and lower the firing temperature of ZMT dielectrics to ≤930 °C. SEM shows that liquid phase sintering induced by CuV₂O₆ can promote the grain growth and elevate the bulk density dramatically. XRD indicates that excess CuV₂O₆ beyond the solubility ~1.5 wt% could form the secondary phase and affect the crystalline structure. The microwave results show that the dielectric constant (ε_r) increases gradually, but the quality factor (Q × f) and the temperature coefficients of resonant frequency (τ_f) decrease with increasing CuV₂O₆ content. Moreover, TiO₂ addition can effectively improve the microwave properties of CuV₂O₆-doped ZMT dielectrics and especially compensate the negative τ _f. (Zn_0.65Mg_0.35)TiO₃ ceramics codoped with 1 wt% CuV₂O₆ and 9 wt% TiO₂ sintered at 930 °C exhibited the optimum microwave dielectric properties: ε _r = 26.2, Q × f = 31,930 GHz, τ _f ≈ −0.32 × 10⁻⁶/°C.     

Microwave dielectric properties and its compatibility with silver electrode of LiNb<Subscript>0.6</Subscript>Ti<Subscript>0.5</Subscript>O<Subscript>3</Subscript> with B<Subscript>2</Subscript>O<Subscript>3</Subscript> and CuO additions

The influences of B₂O₃ and CuO (BCu, B₂O₃: CuO = 1:1) additions on the sintering behavior and microwave dielectric properties of LiNb_0.6Ti_0.5O₃ (LNT) ceramics were investigated. LNT ceramics were prepared with conventional solid-state method and sintered at temperatures about 1,100 °C. The sintering temperature of LNT ceramics with BCu addition could be effectively reduced to 900 °C due to the liquid phase effects resulting from the additives. The addition of BCu does not induce much degradation in the microwave dielectric properties. Typically, the excellent microwave dielectric properties of ε_r = 66, Q × f = 6,210 GHz, and τ _f  = 25 ppm/^oC were obtained for the 2 wt% BCu-doped sample sintered at 900 °C. Chemical compatibility of silver electrodes and low-fired samples has also been investigated.     

Microwave dielectric properties of Ca4La2Ti5O17–LaAlO3 system ceramic materials

Compositions in the (1 − x) Ca₄La₂Ti₅O₁₇–xLaAlO₃ system were prepared in order to modify the positive temperature coefficient of the resonant frequency (τ _f ) of Ca₄La₂Ti₅O₁₇. The microwave dielectric properties and phase composition of this system ceramics were investigated. X-ray powder diffraction results showed that Ca₄La₂Ti₅O₁₇ and LaAlO₃ formed a solid solution only when x ≤ 0.2. The τ _f values showed a near linear decrease with increasing additions of LaAlO₃. It was observed that near zero τ _f value can be achieved as x = 0.64. The permittivity (ε_r) and the quality factor (Q × f) values exhibited a non-linear behavior with LaAlO₃ additions. The microwave dielectric properties were strongly correlated with composition, secondary phases and grain sizes. For practical application, a permittivity (ε_r) of 42, a quality factor (Q × f value) of 12,450 GHz and a temperature coefficient of resonant frequency (τ _f ) of ~0 ppm/°C for 0.36 Ca₄La₂Ti₅O₁₇−0.64 LaAlO₃ were proposed.     

Microwave dielectric properties of BaO–TiO2–TeO2 ternary system

Besides the applications as optical functional materials, tellurium oxides also have attracted interest as microwave dielectric materials. Most TeO₂-based binary and ternary system have large negative temperature coefficient of resonant frequency (τ_f), which is not compatible for the low-temperature cofired ceramic. To compensate τ_f close to zero, two single-phase predecessors of BaTe₄O₉ and TiTe₃O₈ are synthesized in air at 530–560 and 620–680 °C, respectively. The two predecessors show exceptional dielectric properties and their τ_f are opposite. The BaO–TiO₂–TeO₂ ternary system compounds are investigated by adjusting the ratio of BaTe₄O₉ and TiTe₃O₈ and sintered at 520–580 °C to develop the microwave properties and compensate the τ_f. After sintered at 560 °C, the ceramic sample with the composition of 0.47BaTe₄O₉–0.53TiTe₃O₈ exhibits a dielectric permittivity of 28, a Q × f-value of 12,200 GHz, and a τ_f of 4.0 ppm/°C measured at 10 GHz.     

Effects of Gd doping on the sintering and microwave dielectric properties of BiNbO<Subscript>4</Subscript> ceramics

Gd³⁺ was chosen as a substitute for Bi³⁺ in BiNbO₄ ceramics, and the substitution effects on the sintering performance and microwave dielectric properties were studied in this paper. The high temperature triclinic phase was observed only in the Bi_0.98Gd_0.02NbO₄ ceramics when sintered at 920 °C. Both bulk densities and dielectric constant (ε_r) increased with the sintering temperature, while decreased with the Gd content. The quality factor (Q) exhibited a correlation to the Gd content and the microstructures of Bi_1−x Gd _x NbO₄ ceramics. At the sintering temperature of 900 °C, Bi_0.992Gd_0.008NbO₄ ceramics exhibited microwave dielectric properties of ε_r ∼ 43.87, Q × f ∼ 16,852 GHz (at 4.3 GHz), and its temperature coefficient of resonant frequency (τ_f) was found to be near-to-zero.     

Phase formation, sintering behavior and microwave dielectric properties of bismuth and manganese co-doped [(Pb, Ca) La](Fe, Nb)O3+δ solid solution

The phase formation, sintering behavior and microwave dielectric properties of Bi₂O₃ and MnO₂ co-doped [(Pb, Ca) La](Fe, Nb)O_3+δ (PCLFN) ceramics were investigated. The Bi₂O₃ and MnO₂ binary dopants formed stable and low melting temperature solubilities at grain boundary which resulted in an effectively lowered sintering temperature by about 140 °C a more rapid sintering process and enhanced bulk densities. Sintering procedure has significant effect on grain size and porosities in ceramics. With high sintering temperature and time, the evaporation of PbO scaled up from surface toward the bulk and resulted in a Pb²⁺ deficient layer up to 0.25 mm depth under ceramic surface. Investigation of sintering dynamic revealed that either volume diffusion or second-order interface mechanism controlled the grain growth in present system. An optimal microwave dielectric properties of ε_r = 91.1, Q _f = 4,870 GHz and τ _f = 18.5 ppm/°C could be obtained in Bi₂O₃ and MnO₂ co-doped [(Pb, Ca) La](Fe, Nb)O_3+δ ceramics sintered at 1,050 °C for 4 h when the quality ratio of Bi₂O₃/MnO₂ was 1 and the doping content w = 1 wt%.     

Dielectric properties of a ceramic oxide: Li(Ni<Subscript>7/10</Subscript>Fe<Subscript>3/10</Subscript>)VO<Subscript>4</Subscript>

The Li(Ni_7/10Fe_3/10)VO₄ compound has been synthesized by solution-based chemical route. Its dielectric response is investigated using complex impedance spectroscopy technique. Frequency dependence of dielectric constant (ε_r) at different temperatures shows low-frequency dispersion due to polarized structure of the material and mobile charge carriers. Temperature dependence of ε_r at different frequencies exhibits the dielectric anomalies in ε_r at different temperatures. Dielectric relaxation process in the material is signified by the variation of tangent loss with frequency at different temperatures. The variation of relaxation time with temperature obeys the Vogel–Fulcher law.     

Effect of preparation methods on microstructures and microwave dielectric properties of Ba(Mg1/3Nb2/3)O3 ceramics

Effect of preparation methods on microstructures and microwave dielectric properties of Ba(Mg_1/3Nb_2/3)O₃ ceramics was investigated. Ba(Mg_1/3Nb_2/3)O₃(BMN) ceramics were prepared by the conventional mixed oxides method and the molten salt synthesis method. It was shown that the single-phase of BMN was obtained at 900 °C in the molten salt synthesis method. No single-phase BMN was obtained in the conventional mixed oxides method, although the calcining temperature was increased up to 1400 °C. BMN powders prepared by the molten salt synthesis method had better sinterability than that prepared by the conventional mixed oxides method. Because of the very different nature of the powders, different microstructures were observed. The molten salt synthesis method ceramics have a higher B-site ordering parameter (S) and larger grain size than that of the conventional mixed oxides ceramics at same sintering temperature. The variation of Qf, ε _r and τ _f were also explained based on the difference in microstructures.     

Microwave and photoluminesent characterizations of (Ca<Subscript>2</Subscript>Mg<Subscript>3</Subscript>)(X<Subscript>1.75</Subscript>Sb<Subscript>0.25</Subscript>)TiO<Subscript>12</Subscript> [X = Nb and Ta] ceramics

(Ca₂Mg₃)(X_1.75Sb_0.25)TiO₁₂ [X = Nb and Ta] ceramics are prepared through the conventional solid-state route. The samples are calcined at 1,100 and 1,180 °C, and are sintered at 1,250 and 1,375 °C. The substitution of Sb decreases the calcination and sintering temperatures of pure (Ca₂Mg₃)(Nb/Ta)₂TiO₁₂. The structure of the samples is analyzed using X-ray diffraction method. The microstructure of the sintered pellet is studied using scanning electron microscopy. The dielectric properties such as dielectric constant (ε_r), quality factor (Q_uxf) and temperature coefficient of resonant frequency (τ_f) are measured in the microwave frequency region. By Sb substitution, thermal stability is achieved, with the increase in dielectric constant, without much change in the quality factor. The materials have intense emission lines in the wavelength region 500–700 nm. The compositions have good microwave dielectric properties and photoluminescence and hence are suitable for dielectric resonator and ceramic laser applications.     

On the compound- LiNi3/5Fe2/5VO4 for dielectric response

The LiNi_3/5Fe_2/5VO₄ has been prepared by solution-based chemical method. An orthorhombic unit cell structure with lattice parameters a = 3.7778 ?, b = 15.8244 ? and c = 5.5629 ? is confirmed by X-ray diffraction. Frequency dependence of dielectric constant (ε_r) at room temperature indicates the features of dielectric material. Temperature dependence of tangent loss at some selected frequencies shows the presence of dielectric relaxation phenomena in the material. Dielectric anomalies in ε_r at different temperatures are studied by temperature dependence of ε_r at some selected frequencies. The variant of relaxation time with temperature follows the Vogel-Fulcher relation.     

Effect of B2O3 addition on the microstructure and microwave dielectric properties of Li2CoTi3O8 ceramics

The effects of B₂O₃ addition on the sintering behavior, microstructure and microwave dielectric properties of the Li₂CoTi₃O₈ ceramics were investigated. The variations of microstructure and composition of Li₂CoTi₃O₈ ceramics were observed by the X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) analysis. The small amount of B₂O₃ addition could not only effectively lower the sintering temperatures, but also reduce the temperature coefficient of resonant frequency (τ _f ) of Li₂CoTi₃O₈ ceramics. The Li₂CoTi₃O₈ ceramic with 2.0 wt% B₂O₃ addition sintered at 900 °C exhibits good microwave dielectric properties with a ε _r of 26.6, a Q × f value of 21,300 GHz and a small τ _f of 1.78 ppm/°C. Moreover, B₂O₃-added Li₂CoTi₃O₈ ceramic has a chemical compatibility with silver, which makes it a promising ceramic for LTCC technology application.     

Low-firing Li<Subscript>2</Subscript>ZnTi<Subscript>3</Subscript>O<Subscript>8</Subscript> microwave dielectric ceramics with BaCu(B<Subscript>2</Subscript>O<Subscript>5</Subscript>) additive

Phase purity, microstructure, sinterability and microwave dielectric properties of BaCu(B₂O₅)-added Li₂ZnTi₃O₈ ceramics and their cofireability with Ag electrode were investigated. A small amount of BaCu (B₂O₅) can effectively reduce the sintering temperature from 1075°C to 925°C, and it does not induce much degradation of the microwave dielectric properties. Microwave dielectric properties of ε _r = 23·1, Q × f = 22,732 GHz and τ _f = − 17·6 ppm/°C were obtained for Li₂ZnTi₃O₈ ceramic with 1·5 wt% BaCu(B₂O₅) sintered at 925°C for 4 h. The Li₂ZnTi₃O₈ +BCB ceramics can be compatible with Ag electrode, which makes it a promising microwave dielectric material for low-temperature co-fired ceramic technology application.     

The role of dopants in tailoring the microwave properties of Ba6-xR8+2/3x Ti18O54 R = (La–Gd) Ceramics

Microwave dielectric ceramics with a high dielectric constant need to satisfy very high technical demands. They should possess extremely low losses to achieve high Q-values (Quality factor) a small temperature coefficient of resonant frequency (τf), and a relative permittivity (εr) higher than 80. Industrial applications require very stringent electrical and dimensional tolerances, typically ± 0.5–1.0 ppm K-1 for a specified τf and ± 0.25% for a specified εr. To meet such requirements ceramics based on BaO–R2O3 – TiO2 (R = La–Gd) are used. The investigation of this type of ceramic was stimulated by the observation that ceramics based on compositions in the TiO2-rich region of the system exhibit highly temperature stable electrical properties. Especially interesting are compositions within the solid solubility region with the general formula Ba6-xR8+2/3x Ti18O54. As the ionic radius of the rare earth decreases the extent of the solid solubility region becomes narrower, i.e., 0<x<3 for La and x = 0.5 for Gd. Further improvements in the dielectric microwave properties can be achieved by combining different rare earth oxides, and by partial replacement of Ba2+ with other alkaline earth atoms such as Ca2+ and Sr2+. Typically such ceramics meet the requirements for Q and εr; however, τf must be additionally adjusted by the use of dopants. Most commonly bismuth and lead oxides or titanates are used. In the present contribution the role of different dopants and their influence on the resulting microwave dielectric properties of Ba6-xR8+2/3x Ti18O54 based ceramics are discussed. This revised version was published online in November 2006 with corrections to the Cover Date.     

Microwave dielectric properties of 3Li2O–Nb2O5–3TiO2 ceramics with Li2O–V2O5 additions

A new Li₂O–Nb₂O₅–TiO₂ (LNT) ceramic with the Li₂O:Nb₂O₅:TiO₂ mole ratio of 3:1:3 has been investigated. The compound is composed of two phases, the Li₂TiO₃ and “M-phase” solid solution phase. The microwave dielectric ceramic has low sintering temperature (∼1100 °C) and good microwave dielectric properties of a relatively high permittivity (∼51), high Q × f value up to 8700, and small temperature coefficient (∼37 ppm/°C). The low-amount doping of 0.83Li₂O–0.17V₂O₅ (LV) can effectively lower the sintering temperature from 1100 to 900 °C and induce no obvious degradation of the microwave dielectric properties. Typically, the 1 wt.% LV-doped ceramic sintered at 900 °C has better microwave dielectric properties of ε_r = 51.3, Q × f = 7235 GHz, τ _f  = 22 ppm/°C, which suggests that the ceramics can be applied in microwave LTCC devices.     

Dielectric and photoluminesent properties of (Ca2Mg3-xPbx)A2(Ti0.75Zr0.25)O12 [x?=?0 & 0.25; A?=?Nb & Ta] microwave ceramics

(Ca₂Mg_3−xPb_x)A₂(Ti_0.75Zr_0.25)O₁₂ [x = 0 & 0.25; A = Nb & Ta] ceramics are prepared through the conventional solid-state route. The substitution of Zr decreases the calcination and sintering temperatures of pure (Ca₂Mg₃)(Nb/Ta)₂TiO₁₂. The structure of the samples is analyzed using X-ray diffraction method. The dielectric properties such as dielectric constant (ε_r), quality factor (Q_u x f) and temperature coefficient of resonant frequency (τ_f) are measured in the microwave frequency region. By Pb substitution in (Ca₂Mg₃)(Nb/Ta)₂(Ti_0.75Zr_0.25)O₁₂, thermal stability is achieved with the increase in dielectric constant and quality factor. The dielectric behavior at low frequency range 50 Hz–5 MHz is also studied. The microstructure of the sintered pellet is studied using scanning electron microscopy. The materials have intense emission lines in the wavelength region 590 nm to 750 nm. The compositions have good microwave dielectric properties and photoluminescence and hence are suitable for dielectric resonator and ceramic laser applications.     

Compound-LiCo<Subscript>3/5</Subscript>Fe<Subscript>1/5</Subscript>Mn<Subscript>1/5</Subscript>VO<Subscript>4</Subscript> and dielectric characteristics

The LiCo_3/5Fe_1/5Mn_1/5VO₄ compound was successfully synthesized by solution-based chemical method. The variation of dielectric constant (ε_r) with frequency at different temperatures shows a dispersive behavior at low frequencies. Temperature dependence of ε_r at different frequencies indicates dielectric anomalies in ε_r at temperature (T_max) = 220, 235, 245, 260 and 275 °C with (ε_r)_max ~ 6,830, 2,312, 1,224, 649 and 305 for 10, 50, 100, 200 and 500 kHz, respectively. The variation of tangent loss with frequency at different temperatures shows the presence of dielectric relaxation in the material. The variation of relaxation time as a function of temperature follows the Vogel-Fulcher relation.