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)/℃.

DIELECTRIC PROPERTIES OF ZNTIO_3 MICROWAVE CERAMICS CONSOLIDATED WITH MGTIO_3

Stabilized ZnTiO4 was prepared by doping magnesium oxide through traditional solid state reaction. The experimental results indicate that zinc titanate crystals doped with magnesium oxide grow well and the decomposition into Zn2TiO4 and TiO2 is restrained through traditional solid state reaction, By adjusting molar ratio of MgO, better properties can be obtained The dielectric properties of the ceramics doped with 30% MgO（ molar percentage） sintered at 1060℃ are as follows：the value of quality factor is greater than 20000（6.5 GHz ）, the temperature coefficient of resonance frequency is about 2 ± 10^-6 /℃,the dielectric constant ranges from 180 to 22.Besides,it is proved that heat treatment can optimize microstructure and the value of quality factor, which increases from 23833.93 to 47584.00 after 2h of heat treatment at 1040℃.

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.

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.

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,

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.

Characterization and properties of new dielectric ceramics Ba_5LnZnNb_9O_(30)(Ln=La, Nd and Sm)

Three novel dielectric ceramics Ba5LnZnNb9O30 (Ln= La, Nd and Sm) were synthesized and characterized in the BaO-Ln2O3-ZnO-Nb2O5 quaternary system, which formed the filled tungsten-bronze structures. The present ceramics exhibit high dielectric constant (εr) up to 310, low dielectric loss in the level of 10 3 at 1 MHz. Meanwhile, the temperature coefficients of the dielectric constant (τε) of Ba5LnZnNb9O3o varies from -1 390×10-6 to -1 220×10-6/℃as the radius of Ln3+ increases. The present ceramics are promising candidates for high dielectric constant and low loss dielectric ceramics.

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.

Influences of substituting of(Ni_(1/3)Nb(2/3))for Ti^(4+)on the phase compositions,microstructures,and dielectric properties of Li_(2)Zn[Ti_(1-x)(Ni_(1/3)Nb_(2/3))_(x)]_(3)O_(8)(0<≤x≤0.3)microwave ceramics

Complex ion substitution is gaining more attention as an appealing method of modifying the structure and performance of microwave ceramics.In this work,Li_(2)Zn[Ti_(1-x)(Ni_(1/3)Nb_(2/3))_(x)]_(3)O_(8),0≤x≤0.3ceramics were designed based on the complex ion substitution strategy,following the substitution rule of radius and valence to investigate the relationship among phase compositions(containing oxygen vacancies and Ti^(3+)ions),microstructures,and microwave dielectric characteristics of the LZTNNx ceramics.The samples maintained a single Li_(2)ZnTi_(3)O_(8)solid solution phase as x≤0.2,whereas the sample of x=0.3 produced a second phase with the LiNbO_(3)structure.The appropriate amount of(Ni_(1/3)Nb_(2/3))^(4+)substitution could slightly improve the densification of the LZTNNx ceramics due to the formation of the LiZnTi_(3)O_(8)solid solution accompanied by a decrease in the average grain size.The presence of a new Aig Raman active band at about 848 cm^(-1)indicated that local symmetry changed,affecting atomic interactions of the LZTNNx ceramics.The variation of the relative dielectric constant(εr)was closely related to the molar volume ionic polarizability(α_(D)^(T)),and the temperature coefficient of the resonant frequency(τ_(f))was related to the bond valence(V_(1))of Ti.The increase in density,the absence of the Ti3+ions and oxygen vacancies,and the reduction in damping behavior were responsible for the decreased dielectric loss.The LZTNNO.2 ceramics sintered at 1120℃exhibited favorable microwave dielectric properties:εr=22.13,quality factor(Q×f)=97,350 GHz,andτ_(f)=-18.60 ppm/C,which might be a promising candidate for wireless communication applications in highly selective electronics.

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.

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.

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.

Wet flashover voltage improvement of the ceramics with dielectric barrier discharge

Surface modification techniques with plasma are widely investigated to improve the surface insulation capability of polymers under dry conditions,while the relationship between treatment method,surface physical and chemical properties,and wet flashover voltage is still unclear for inorganic ceramics.In this work,the surface insulation properties of ceramics under wet conditions are improved using nanosecond-pulsed dielectric barrier discharge with polydimethylsiloxane(PDMS)as the precursor.The relationships between PDMS concentration and the water contact angle,dry and wet flashover voltages are obtained to acquire the optimal concentration.The surface charge dissipation test and surface physio-chemical property measurement with SEM,AFM,XPS are carried out to further explore the mechanism of surface insulation enhancement.The results show that film deposition with micron thickness and superhydrophobicity occurs at the PDMS concentration of 1.5%.The dry flashover voltage is increased by 14.6%due to the induction of deep traps,while the wet flashover voltage is increased by 66.7%.The gap between dry-wet flashover voltage is decreased by 62.3%compared with the untreated one due to the self-cleaning effect.

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.

Microstructure and microwave dielectric properties of lead borosilicate glass ceramics with Al_2O_3

The effects of Al2O3 addition on both the sintering behavior and microwave dielectric properties of PbO-B203-SiO2 glass ceramics were investigated by Fourier transform infrared spectroscope （FTIR）, differential thermal analysis （DTA）, X-ray diffraction （XRD） and scanning electron microscopy （SEM）. The results show that with the increase of Al2O3 content the bands assigned to [SiO4] nearly disappear. Aluminum replaces silicon in the glass network, which is helpful for the formation of boron-oxygen rings. The increase of the transition temperature Tg and softening temperature Tf of PbO-B2O3-SiO2 glass ceramics leads to the increase of liquid phase precipitation temperature and promotes the structure stability in the glasses, and consequently contributes to the decreasing trend of crystallization. Densification and dielectric constants increase with the increase of Al2O3 content, but the dielectric loss is worsened. By contrast, the 3% （mass fraction） Al2O3-doped glass ceramics sintered at 725℃ have better properties of density p=2.72 g/cm3, dielectric constant Er=6.78, dielectric loss tan8=2.6×10^-3 （measured at 9.8 GHz）, which suggest that the glass ceramics can be applied in multilayer microwave devices requiring low sintering temperatures.

Sintering Behavior and Microwave Dielectric Properties of BBSZL Glass-doped ZnTiO_3 Ceramics for LTCC Applications

A novel low temperature co-fired ceramic(LTCC) material was fabricated by zinc titanate(ZnTiO_3) ceramics doped with B_2O_3-BaO-SiO_2-ZnO-Li_2O(BBSZL) glass. The influences of BBSZL glass on wetting behavior, sintering activation energy, phase composition, microstructure and microwave dielectric properties were investigated. The experimental results show that the sintering temperature of ZnTiO3 ceramics can be reduced from 1 100 to 925 ℃, meanwhile the sintering activation energy is decreased from 465.32 to 390.54 kJ·mol^(-1) by BBSZL glass aid, respectively. Moreover, BBSZL glass can inhibit the high Q×f ZnTiO_3 phase decompose into the low Q×f value Zn_2TiO_4 phase, which is propitious to obtain high Q×f value LTCC material. The ZnTiO_3-BBSZL composite sintered at 925℃ displays the excellent microwave dielectric properties with ε_r of 21.8, Q×f value of 42000 GHz, and τ_f of-75 ppm·℃^(-1).