Low-firing and temperature stability regulation of tri-rutile MgTa_(2)O_(6)microwave dielectric ceramics

A glass frit containing Li_(2)O-MgO-ZnO-B_(2)O_(3)-SiO_(2)component was used to explore the low-temperature sintering behaviors and microwave dielectric characteristics of tri-rutile MgTa_(2)O_(6)ceramics in this study.The good low-firing effects are presented due to the high matching relevance between Li_(2)O-MgO-ZnO-B_(2)O_(3)-SiO_(2)glass and MgTa_(2)O_(6)ceramics.The pure tri-rutile MgTa_(2)O_(6)structure remains unchanged,and high sintering compactness can also be achieved at 1150℃.We found that the Li_(2)O-MgO-ZnO-B_(2)O_(3)-SiO_(2)glass not only greatly improves the low-temperature sintering characteristics of MgTa_(2)O_(6)ceramics but also maintains a high(quality factor(Q)×resonance frequency(f))value while still improving the temperature stability.Typically,great microwave dielectric characteristics when added with 2wt%Li_(2)O-MgO-ZnO-B_(2)O_(3)-SiO_(2)glass can be achieved at 1150℃:dielectric constant,ε_(r)=26.1;Q×f=34267 GHz;temperature coefficient of resonance frequency,τ_(f)=-8.7×10^(-6)/℃.

Preparation and characterization of new microwave dielectric ceramics Ba_(3-n)La_(1+n)Ti_nNb_(3-n)O_(12)

A series of new microwave dielectric ceramics Ba3-nLa1+nTinNb3-nO12 (n=0,1,2) were prepared in the BaO-La2O3-TiO2-Nb2O5 system by high temperature solid-state reaction route. The phase and structure of the ceramics were characterized by X-ray diffraction, scanning electron microscope, and microwave dielectric properties measurements. These samples were identified as single phase and adopted A4B3O12-type cation-deficient hexagonal perovskite structure, which can be described as consisting of identical perovskite-like blocks, three corner-sharing BO6 octahedra thick, separated by layers of vacant octahedral. These ceramics have high dielectric constants in the range of 48-42, high quality factors (Q×f) up to 38 000 GHz, and low temperature coefficient of resonant frequencies (τf) in the range of (-40-+6)×10-6℃-1. With increasing content of La and Ti, the dielectric constants slightly decrease butτf gradually increases.

Improved microwave dielectric properties of MgAl_(2)O_(4)spinel ceramics through(Li_(1/3)Ti_(2/3))^(3+)doping

A series of nominal compositions MgAl_(2-x)(Li_(1/3)Ti_(2/3))_(x)O_(4)(x=0,0.04,0.08,0.12,0.16,and 0.20)ceramics were successfully prepared via the conventional solid-state reaction route.The phase compositions,microstructures,and microwave dielectric properties were investigated.The results of x-ray diffraction(XRD)and scanning electron microscopy(SEM)showed that a single phase of MgAl_(2-x)(Li_(1/3)Ti_(2/3))_(x)O_(4)ceramics with a spinel structure was obtained at x≤0.12,whereas the second phase of MgTi_(2)O_(5)appeared when x>0.12.The cell parameters were obtained by XRD refinement.As the x values increased,the unit cell volume kept expanding.This phenomenon could be attributed to the partial substitution of(Li_(1/3)Ti_(2/3))^(3+)for Al^(3+).Results showed that(Li_(1/3)Ti_(2/3))^(3+)doping into MgAl_(2)O_(4)spinel ceramics effectively reduced the sintering temperature and improved the quality factor(Q_f)values.Good microwave dielectric properties were achieved for a sample at x=0.20 sintering at 1500℃in air for 4 h:dielectric constantε_(r)=8.78,temperature coefficient of resonant frequencyτ_(f)=-85 ppm/℃,and Q_(f)=62300 GHz.The Q_(f)value of the x=0.20 sample was about 2 times higher than that of pure MgAl_(2)O_(4)ceramics(31600 GHz).Thus,MgAl_(2-x)(Li_(1/3)Ti_(2/3))_(x)O_(4)ceramics with excellent microwave dielectric properties can be applied to 5G communications.

Effect of La_2O_3-Dopant on Microstructure and Microwave Dielectric Properties of CaO-MgO-Nb_2O_5-TiO_2 System Ceramics

La_2O_3-doped CaO-MgO-Nb_2O_5-TiO_2 system ceramics were prepared by solid-state ceramic technique. The microstructure and microwave dielectric properties of CaO-MgO-Nb_2O_5-TiO_2-La_2O_3 ceramics can be adjusted by varying the amount of La^(3+) ions. The results show that the replacement of Ca^(2+) by La^(3+) at A-site of the ceramics can increase the quality factor Q·f value as well as the temperature coefficient of resonant frequency τ_f and decrease the dielectric constant ε_r. With increase of La^(3+) contents, the dielectric constant decreases from 57 to 35 and Q·f value increases from 33400 GHz to 35000 GHz (at 7.6 GHz). Meanwhile, the temperature coefficient of resonant frequency is improved towards near zero. The dielectric properties of these compounds are related to octahedra tilting due to deficient vacancies at A-site.

Effect of La^(3+), Sr^(2+) on Microwave Dielectric Properties of CaO-MgO-Nb_2O_5^-TiO_2 System Ceramics

The effect of La^3 ＋ , Sr^2＋ on the microstructure and microwave properties of CaO-MgO-Nb2O5-TiO2 system ceramics was investigated. The result shows that a single complex perovskite structure formed within investigated composition range in La^3＋ , Sr2-doped CaO-MgO-Nb2O5-TiO2 system ceramics. With increasing of La^3＋ , Sr^2＋ content, the structure of La^3＋ , Sr2-doped CaO-MgO-Nb2O5-TiO2 system ceramic respectively maintain orthorhombic type.

UltrahighQ Sr_(1+x)Y_(2)O_(4+x)(x=0-0.04)microwave dielectric ceramics for temperature-stable millimeter-wave dielectric resonator antennas

Microwave dielectric ceramics should be improved to advance mobile communication technologies further.In this study,we prepared Sr_(1+x)Y_(2)O_(4+x)(x=0-0.04)ceramics with nonstoichiometric Sr^(2+)ratios based on our previously reported SrY_(2)O_(4) microwave dielectric ceramic,which has a low dielectric constant and an ultrahigh quality factor(Q value).The ceramic exhibited a 33.6% higher Q-by-frequency(Q×f)value(Q≈12,500)at x=0.02 than SrY_(2)O_(4).All Sr_(1+x)Y_(2)O_(4+x)(x=0-0.04)ceramics exhibited pure phase structures,although variations in crystal-plane spacings were observed.The ceramics are mainly composed of Sr-O,Y1-O,and Y_(2)-O octahedra,with the temperature coefficient of the resonant frequency(τ_(f))of the ceramic increasing with Y_(2)-O octahedral distortion.The ceramic comprises uniform grains with a homogeneous elemental distribution,clear grain boundaries,and no obvious cavities at x=0.02.The Sr_(1+x)Y_(2)O_(4+x)(x=0-0.04)ceramics exhibited good microwave dielectric properties,with optimal performance observed at x=0.02(dielectric constant(εr)=15.41,Q×f=112,375 GHz,and τ_(f)=-17.44 ppm/℃).The τ_(f) value was reduced to meet the temperaturestability requirements of 5G/6G communication systems by adding CaTiO_(3),with Sr_(1.02)Y_(2)O_(4.02)+2wt% CaTiO_(3) exhibiting ε_(r)=16.14,Q×f=51,004 GHz,andτf=0 ppm/℃.A dielectric resonator antenna prepared using Sr_(1.02)Y_(2)O_(4.02)+2wt%CaTiO_(3) exhibited a central frequency of 26.6 GHz,with a corresponding gain and efficiency of 3.66 dBi and 83.14%,respectively.Consequently,Sr_(1.02)Y_(2)O_(4).02-based dielectric resonator antennas are suitable for use in 5G millimeter-wave band(24.5-27.5 GHz)applications.

Microwave dielectric properties and compatibility with silver of low-fired Li_2MgTi_3O_8 ceramics with Li_2O-MgO-B_2O_3 frit

The effects of Li2O-MgO-B2O3 （LMB） glass additive on the sintering characteristics, phase purity, microstructure, and microwave dielectric properties of Li2MgTi3O8 ceramics were investigated. The experimental results demonstrate that the addition of LMB glass effectively lowers the sintering temperature of Li2MgTi3O8 ceramic from 1025 ℃ to 875 ℃ and induces no obvious degradation of the microwave dielectric properties. Typically, the 1.5%LMB glass-added Li2MgTi3O8 ceramic sintered at 875 ℃ for 4 h shows excellent microwave dielectric properties of Q×f=45403 GHz, εr=25.9 and τf≈0 ℃-1. The dielectric ceramic exhibits stability against the reaction with the Ag electrode, which indicates that the ceramics could be applied in multilayer microwave devices requiring low firing temperatures.

Low-temperature sintering and microwave dielectric properties of Li_2MgTi_3O_8 ceramics doped with BaCu(B_2O_5)

The influences of BaCu（B2O5） （BCB） addition on sintering, microstructure and microwave dielectric properties of Li2MgTi308 ceramics were investigated using X-ray diffractometry, scanning electron microscopy and microwave dielectric measurements. The experimental results show that a small amount of BaCu（B2O5） addition can effectively reduce the sintering temperature to 900℃, and induce only a limited degradation of the microwave dielectric properties. Typically, the best microwave dielectric properties of er24.5, Q×f =24 622 GHz, rf=4.2×10-6℃ -1 are obtained for 1.0% BCB-doped Li2MgTi3O8 ceramics sintered at 900℃ for 3 h. The BCB-doped Li2MgTi3O8 ceramics can be compatible with Ag electrode, which may be a strong candidate for low temperature co-fired ceramics applications.

Microstructure and microwave dielectric properties of ZnO-B_2O_3 added (Ca_(0.254)Li_(0.19)Sm_(0.14))TiO_3 ceramics

The effects of ZnO-B2O3 （ZB2） on the sintering behavior and microwave dielectric properties of （Ca0.254Li0.19Sm0.14）TiO3 ceramics were investigated. The densities of the specimens reached the maximum value by adding 3 wt.% ZB2 and then decreased. The sintering temperature of the specimens was lowered from 1300 to 1100℃ without degradation of the microwave dielectric properties. The （Ca0.254Li0.19Sm0.14）TiO3＋ 3 wt.% ZB2 sintered at 1100℃ for 3 h showed good microwave dielectric properties, εr= 108.2, Qf= 6545 GHz, and rf= 6.5 ppm/℃, respectively, indicating that ZB2 was an effective sintering aid to improve the densification and microwave dielectric properties of （Ca0.254Li0.19Sm0.14）TiO3 ceramics.

Structure and Dielectric Properties of ZnO and Nb_2O_5 Doped BaO-TiO_2 System Microwave Ceramics

The microwave dielectric properties and microstructure of BaTi4.3ZnyO9.6＋y ＋0.02 mol% SnO2＋0.01 mol% MnCO3＋x mol% Nb2O5（x=0-0.05, y=0-0.08） system ceramics were studied as a function of the amount of ZnO and Nb2O5 doped. Addition of （y=0-0.05） ZnO and （x=0-0.025） Nb2O5 enhanced the reactivity and decreased the sintering temperature effectively. It also increased the dielectric constant ε r and quality factor Q（=1/tan 8） of the system due to the substitution of Ti^4＋ ions with incorporating Zn^2＋and Nb^5＋ ions, which was analyzed by the reaction ZnO＋Nb2O5＋ 3 TiTxTi →ZnTi＋ 2NbTi＋3TiO2. When the system doped with （y=0.05） ZnO and （x=0.025） Nb205 were sintered at 1 160 ℃ for 6 h, the εr. Qf0 value and rfwere 36.5, 42 000 GHz, and＋1.8 ppm/℃, respectively, at 5 GHz.

Effect of Rare Earth Oxides on the Microstructure and Microwave Dielectric Properties of CaO-MgO-Nb_2O_5-TiO_2 System Ceramics

La2O3 and SrO-doped CaO-MgO-Nb2O3-TiO2 system ceramics were prepared by solid-state ceramic technique.The microstructure and microwave dielectric properties of CaO-MgO-Nb2O5-TiO2-La2O3 cermics can be adjusted by varying the amount of La^3＋ or Sr^2＋ ions respectively.The replacement of Ca^2＋ by La^3＋ at A-site of the ceramics increases the quality factor Q value（ at 7.6GHz）as well as the temperature coefficient of resonant frequency τf and decreases the dielectric constant εr and the substitution of Sr^2＋ at A-site in this ceramics system exhibits opposite characteristics.The microwave properties of La^3＋,Sr^2＋-doped CaO-MgO-Nb2O5-TiO2 system ceramics depend on the degree of octahedral distortion inside materials.

Low-Temperature Sintering and Microwave DielectricProperties of Ba_2Ti_3Nb_4O_(18) Ceramics

The effects of CuO and H3BO3 additions on the low-temperature sintering,microstructure,and microwave dielectric properties of Ba2Ti3Nb4O18 ceramics were investigated.The addition of less amount of CuO （ 〈1 wt%） considerably facilitated the densification of Ba2Ti3Nb4O18 ceramics.Appropriate addition of H3BO3 （ 〈3.5 wt%） remarkably improved the microwave dielectric properties of ceramics.The addition of H3BO3 and CuO successfully reduced the sintering temperature of Ba2Ti3Nb4O18 ceramics from 1300 to 1050 ℃.Ba2Ti3Nb4O18 ceramics sintered at 1 050 ℃ for 4 h with the addition of 1.0 wt% CuO and 3.5 wt% H3BO3 exhibited good microwave dielectric properties：er=33.74,Q？f=13 812 GHz,and tf=-5.35 ppm/°C at about 5.0 GHz.

Structure and Dielectric Properties of Sb_2O_5-Doped ZrO_2-SnO_2-TiO_2 Microwave Ceramics

The microwave dielectric properties of ZrO2-SnO2-TiO2 （ZST） system ceramics were studied as a function of the amount of Sb2O5 dopant. With the addition of 0-0.5% Sb2O5（molar ratio）, the substitution of Ti4^＋ ions with Sb^5＋ ions decreased the sintering temperature and increased the quality factor Q due to the reduction of oxygen vacancies, When the amount of Sb^5＋ increased further （above 0.5%）, Q was decreased by increasing the electron concentration. When the system doped with 0.5% Sb2O5 was sintered at 1 150℃ for 6 h, the relative dielectric constant ε, Qf0, and the temperature coefficient of resonant frequency （TCF） were 38.46, 44 500 GHz, 20.0×10^-6/℃, respectively, at 6 GHz,

Effects of V₂O₅Addition on Microwave Dielectric Properties of Li₂ZnTi₃O₈Ceramics for LTCC Applications

The sintering temperature of Li2ZnTi3O8 ceramics is still high for LTCC-based applications. In this work, V2O5 was doped as the sintering aid. The sintered density, phase composition, grain size, as well as microwave dielectric properties of Li2ZnTi3O8 ceramics with the addition of V2O5 were investigated. Based on our research, V2O5 doping effectively promoted the densification of Li2ZnTi3O8 ceramics at about 900°C, without affecting the main crystal phase of the ceramics. Li2ZnTi3O8 ceramics with 0.5 wt% V2O5 doping (sintered at 900°C) exhibited the best microwave dielectric properties (Qf =?22,400 GHz at about 6 GHz, εr = 25.5, and τf = -10.8 ppm/°C). The V2O5-doped Li2ZnTi3O8 ceramics were well cofired with Ag inner paste without cracks and diffusion, indicating its significant potential for LTCC applications.

The latest process and challenges of microwave dielectric ceramics based on pseudo phase diagrams

The explosive process of 5G communication evokes the urgent demand of miniaturized and integrated dielectric ceramics filter It is a pressing need to advance the development of dielectric ceramics utilization of emerging technology to design new materials and understand the polarization mechanism.This review provides the summary of the study of microwave dielectric ceramics(MWDCs)sintered higher than 1000℃ from 2010 up to now,with the purpose of taking a broad and historical view of these ceramics and illustrating research directions.To date,researchers endeavor to explain the structure-property relationship of ceramics with multitude of approaches and design a new formula or strategy to obtain excellent microwave dielectric properties.There are variety of factors that impact the permittivity,dielectric loss,and temperature stability of dielectric materials,covering intrinsic and extrinsic factors.Many of these factors are often intertwined,which can complicate new dielectric material discovery and the mechanism investigation.Because of the various ceramics systems,pseudo phase diagram was used to classify the dielectric materials based on the composition.In this review,the ceramics were firstly divided into ternary systems,and then brief description of the experimental probes and complementary theoretical methods that have been used to discern the intrinsic polarization mechanisms and the origin of intrinsic loss was mentioned.Finally,some perspectives on the future outlook for high-temperature MWDCs were offered based on the synthesis method,characterization techniques,and significant theory developments.

Machine learning approaches for permittivity prediction and rational design of microwave dielectric ceramics

Low permittivity microwave dielectric ceramics(MWDCs)are attracting great interest because of their promising applications in the new era of 5G and IoT.Although theoretical rules and computational methods are of practical use for permittivity prediction,unsatisfactory predictability and universality impede rational design of new high-performance materials.In this work,based on a dataset of 254 single-phase microwave dielectric ceramics(MWDCs),machine learning(ML)methods established a high accuracy model for permittivity prediction and gave insights of quantitative chemistry/structureproperty relationships.We employed five commonly-used algorithms,and introduced 32 intrinsic chemical,structural and thermodynamic features which have correlations with permittivity for modeling.Machine learning results help identify the permittivity decisive factors,including polarizability per unit volume,average bond length,and average cell volume per atom.The feature-property relationships were discussed.The optimal model constructed by support vector regression with radial basis function kernel was validated its superior predictability and generalization by verification dataset.Low permittivity material systems were screened from a dataset of~3300 materials without reported microwave permittivity by high-throughput prediction using optimal model.Several predicted low permittivity ceramics were synthesized,and the experimental results agree well with ML prediction,which confirmed the reliability of the prediction model.

Room-temperature-densified H_(3)BO_(3) microwave dielectric ceramics with ultra-low permittivity and ultra-high Qf value

With the rapid development of mobile communication technology towards 5G and 6G,the microwave dielectric materials with ultra-low permittivity and ultra-high Qf value are urgently demanded.Here,the excellent microwave dielectric properties are reported in H3BO3 ceramics with the molecular crystal structure,whose permittivity(2.84)and density(1.46 g/cm^(3))are record-low among the low-loss ceramics.The ultra-high Qf value of 146,000 GHz(or the ultra-low dielectric loss of 1.03×10^(-4) at 15 GHz)is also distinguished.Besides,the H_(3)BO_(3) ceramics can be densified at room temperature by a simple cold sintering process in a short time of 10 min,and this brings many advantages for the integration with microwave circuits.The large molecule volume originating from the molecular crystal structure and the low dielectric polarizabilities of H^(+) and B^(3+) are responsible for the ultra-low permittivity of H_(3)BO_(3) ceramics,and more microwave dielectric materials with ultra-low permittivity and ultra-high Qf value are expected to be explored in the molecular crystals.

Ba_3La_2Ti_2Ta_2O_(15):A New Microwave Dielectricof A_5B_4O_(15)-type Cation-deficient Perovskites

The synthesis, structure and properties of a new A5B4O15-type cation-deficient perovskite Ba3La2Ti2Ta2O15 were discribed. The compound was prepared by the conventional solid-state reaction route. The phase and structure of the ceramics were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）. The results reveal that the compound is successfully synthesized. The compound crystallizes in the trigonal system with unit cell parameter a=5.6730（2） A, c=11.6511（2） A, V=324.93（1） A^3 and Z=1. The microwave dielectric properties of the ceramic are studied using a network analyzer, and it shows a high dielectric constant of 45.1, a high quality factors with Q×fof21 029 GHz, and a positive τf of 5.3 ppm℃^-1.

Preparation and Properties of Si2N2O Ceramics for Microwave Sintering Furnaces

Si2N2O ceramics were prepared using amorphous Si3N4 as the raw material and Li2CO3 as the sintering additive through vacuum multi-stage sintering.The influence of the Li2CO3 addition(0%,1%,2%,3%,and 5%,by mass)on the phase composition,the microstructure,the porosity,the mechanical properties,the dielectric constant and the tangent of the dielectric loss angle of the porous Si2N2O ceramics was investigated.The results reveal that a suitable addition of Li2CO3 can promote the generation of Si2N2O but excessive or inadequate Li2CO3 causes decomposition of Si2N2O ceramics.The prepared porous Si2N2O ceramics have good mechanical properties,good thermal shock resistance,and low dielectric properties,which have excellent potential for application in microwave sintering furnaces.

Effect of LiF addition on sintering behavior and dielectric breakdown mechanism of MgO-based microwave dielectric ceramics

Glass-free MgO-based microwave dielectric ceramics(1-x)wt%(0.98 MgO-0.02 Al2O3)-x wt%LiF(x=0.5,1,2,3,4)were synthesized where LiF and Al2O3 were utilized as sintering additive and reinforcement phase in MgO matrix respectively.It was found that ion substitution is apt to occur between LiF and MgO,leading to the formation of oxygen vacancies and MgF2.Nevertheless,different from ordinary liquidphase sintering,morphologies of ceramics were distinctly altered with grains changing from polyhedron to sphere-like shape and densities underwent obvious decrease when excessive amount of LiF was introduced and we call it excessive liquid-phase sintering.Grain boundary weakening caused by this circumstance would exert an adverse effect on physical properties.Moreover,LiF addition dramatically reduced dielectric breakdown strength and altered the dielectric breakdown behavior of MgO-based ceramics,which is dominated by electrical breakdown mechanism.Combination of good properties were achieved in 1 wt%LiF modified MgO-based ceramics sintered at 950℃ which exhibited superior microwave properties(εr=9.56,tanδ=9.2×10^(-5),Qf=124,600 GHz),high flexural strength(184.5 MPa),high thermal conductivity(21.3 W/(m,K)),high coefficient of thermal expansion(-12 ppm/℃)and moderate electrical properties(Eb=35.9 kV/mm,r=4.9×10^(12) U cm).