Structural evolution,sintering behavior and microwave dielectric properties of Al(1-x)(Si0.5Zn0.5)xPO4 ceramics

Al_(1-x)(Si_0.5Zn_0.5)_xPO₄ (0 ≤x≤0.6) ceramics were prepared via solid state reaction process. Their structural evolution, sintering behavior and microwave dielectric properties were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and with a network analyzer. Phase pure AlPO₄ could not be obtained for the undoped composition. However, microscopically homogeneous single phase solid solution formed within the compositional range of 0 < x ≤ 0.05. Immiscibility with two-phase structure within apparently single phase solid solution could be observed for other doped compositions (0.1 ≤ x ≤ 0.6). Small level of doping with (Si_0.5Zn_0.5)³⁺ (x≤0.4) stabilized the orthorhombic cristobalite-like AlPO₄ (C-AlPO₄) phase; while further doping led to the transformation from orthorhombic α-C-AlPO₄ into cubic β-C-AlPO₄ phase. The doping with (Si_0.5Zn_0.5)³⁺ considerably improved the sinterability and reduced the sintering temperature to ?900 °C when x = 0.6. The dielectric permittivity slightly increases and the Q × f value decreases with the increasing doping concentration. All composition demonstrate low permittivity (?_r ?4) and negative value of τ_f. Good combined microwave dielectric properties with ?_r ?3.9, Q × f?25,000 GHz and τ_f ? -25 ppm/^oC could be obtained for the x = 0.2 composition after sintering at 1200 °C/2h.     

Enhancing the microwave dielectric performance of SrSm2Al2O7 ceramic by Sr2+ nonstoichiometry and sintering aid addition

Sr_1+xSm₂Al₂O_7+x (0 ≤ x ≤ 0.05) ceramics were prepared by a conventional solid-state reaction method. Slight Sr²⁺ nonstoichiometry dramatically enhanced the microwave dielectric performance of the ceramics. Compared with the stoichiometric material, Sr-deficient ceramics show greatly enhanced microwave dielectric properties. For x = 0.03, the ceramics exhibited good microwave dielectric properties of ε_r = 18.31, Q × f = 78,000 GHz and τ_f = 2.28 ppm/°C. ZnO and LiF sintering aids were added to the ceramic to reduce the presintering temperature and enhance the microwave dielectric properties of the ceramics. After 0.25 wt% ZnO and 0.25 wt% LiF were added, the ceramics exhibited microwave dielectric properties of ε_r = 19.40, Q × f = 81,400 GHz and τ_f = 3.27 ppm/°C.     

High-Qf value and temperature stable Zn2+-Mn4+ cooperated modified cordierite-based microwave and millimeter-wave dielectric ceramics

Cordierite-based dielectric ceramics with a lower dielectric constant would have significant application potential as dielectric resonator and filter materials for future ultra-low-latency 5G/6G millimeter-wave and terahertz communication. In this article, the phase structure, microstructure and microwave dielectric properties of Mg₂Al_4–2x(Mn_0.5Zn_0.5)_2xSi₅O₁₈ (0 ≤ x ≤ 0.3) ceramics are studied by crystal structure refinement, scanning electron microscope (SEM), the theory of complex chemical bonds and infrared reflectance spectrum. Meanwhile, complex double-ions coordinated substitution and two-phase complex methods were used to improve its Q×f value and adjust its temperature coefficient. The Q×f values of Mg₂Al_4–2x(Mn_0.5Zn_0.5)_2xSi₅O₁₈ single-phase ceramics are increased from 45,000 GHz@14.7 GHz (x = 0) to 150,500 GHz@14.5 GHz (x = 0.15) by replacing Al³⁺ with Zn²⁺-Mn⁴⁺. The positive frequency temperature coefficient additive TiO₂ is used to prepare the temperature stable Mg₂Al_3.7(Mn_0.5Zn_0.5)_0.3Si₅O₁₈-ywt%TiO₂ composite ceramic. The composite ceramic of Mg₂Al_3.7(Mn_0.5Zn_0.5)_0.3Si₅O₁₈-ywt%TiO₂ (8.7 wt% ≤ y ≤ 10.6 wt%) presents the near-zero frequency temperature coefficient at 1225 °C sintering temperature: ε_r = 5.68, Q×f = 58,040 GHz, τ_f = ?3.1 ppm/°C (y = 8.7 wt%) and ε_r = 5.82, Q×f = 47,020 GHz, τ_f = +2.4 ppm/°C (y = 10.6 wt%). These findings demonstrate promising application prospects for 5 G and future microwave and millimeter-wave wireless communication technologies.     

Low-temperature sintering and microwave dielectric properties of CaSnxSiO(3+2x)-based positive τf compensator

The sinterability, phase compositions, and microwave dielectric properties of LiF-doped nonstoichiometric CaSn_xSiO_(3+2x) ceramics prepared by the solid-state reaction were investigated. LiF addition effectively reduced the sintering temperature of CaSn_xSiO_(3+2x) ceramics and inhibited the volatilization of Sn. A pure monoclinic CaSnSiO₅ phase was achieved in the 1.0?wt% LiF-doped CaSn_0.94SiO_4.88 ceramics sintered at 1175?°C, which exhibited good microwave dielectric properties of ε_r =?11.6, Q?×?f?=?34000?GHz, and τ_f =?+73.2?ppm/°C. The positive τ_f value was an atypical and important phenomenon for low-permittivity microwave dielectric ceramics, which could be a promising τ_f compensator.     

A novel low-permittivity LiAl0.98(Zn0.5Si0.5)0.02O2-based microwave dielectric ceramics for LTCC application

Phase composition, morphology, and microwave dielectric properties of (1−x) LiAl_0.98(Zn_0.5Si_0.5)_0.02O₂ + x CaTiO₃ (0.05 ≤ x ≤ 0.20) materials synthesized via the solid state reaction method were investigated. All these densified materials were obtained at a sintering temperature of 1150°C. All compositions showed a major LiAlO₂ phase that was accompanied by a minor CaTiO₃ phase. The ε_r value increased gradually from 10.88 to 11.60, whereas the Q × f value remarkably decreased from 33 251 GHz to 13 511 GHz. The τ_f value changes from −85 ppm/°C to 212 ppm/°C, thereby indicating that CaTiO₃ could effectively adjust this value. HBO₃-doping was used to further decrease the sintering temperature to 900°C. The optimum value was obtained at 7 wt.% HBO₃ doped with microwave dielectric properties of ε_r = 9.39, Q × f = 10 224 GHz, and τ_f = −7.8 ppm/°C. This material also exhibited chemical compatibility with silver, making it a candidate for low temperature co-fired ceramics applications.     

Structure,Infrared Reflectivity and Microwave Dielectric Properties of (Na0.5La0.5)MoO4–(Na0.5Bi0.5)MoO4 Ceramics

A series of temperature‐stable microwave dielectric ceramics, (1?x)(Na_0.5La_0.5)MoO₄–x(Na_0.5Bi_0.5)MoO₄ (0.0 ≤ x ≤ 1.0) were prepared by using solid‐state reaction. All specimens can be well sintered at temperature of 580°C–680°C. Sintering behavior, phase composition, microstructures, and microwave dielectric properties of the ceramics were investigated. X‐ray diffraction results indicated that tetragonal scheelite solid solution was formed. Microwave dielectric properties showed that permittivity (ε_r) and temperature coefficient of resonant frequency (τ_f) were increased gradually, while quality factor (Q × f) values were decreased, at the x value was increased. The 0.45(Na_0.5La_0.5)MoO₄–0.55(Na_0.5Bi_0.5)MoO₄ ceramic sintered at 640°C with a relative permittivity of 23.1, a Q × f values of 17 500 GHz (at 9 GHz) and a near zero τ_f value of 0.28 ppm/°C. Far‐infrared spectra (50–1000 cm^?1) study showed that complex dielectric spectra were in good agreement with the measured microwave permittivity and dielectric losses.     

Improved sinterability and microwave dielectric properties of [Zn0.5Ti0.5]3+-doped ZnAl2O4 spinel solid solution

Low-permittivity ZnAl_2-x(Zn_0.5Ti_0.5)_xO₄ ceramics were synthesized via conventional solid-state reaction method. A pure ZnAl₂O₄ solid-state solution with an Fd-3m space group was achieved at x ≤ 0.1. Results showed that partial substitution of [Zn_0.5Ti_0.5]³⁺ for Al³⁺ effectively lowered the sintering temperature of the ZnAl₂O₄ ceramics and remarkably increased the quality factor (Q × f) values. Optimum microwave dielectric properties (ε_r = 9.1, Q × f = 115,800 GHz and τ_f = −78 ppm/°C) were obtained in the sample with x = 0.1 sintered at 1400°C in oxygen atmosphere for 10 h. The temperature used for the sample was approximately 250°C lower than the sintering temperature of conventional ZnAl₂O₄ ceramics.     

Two novel low permittivity microwave dielectric ceramics Li2TiMO5 (M = Ge,Si) with abnormally positive τf

Two tetragonal natisite structured Li₂TiMO₅ (M = Ge, Si) ceramics fabricated using the conventional solid-state reaction method were investigated in terms of the thermal stability, sintering behavior and dielectric properties at radio (RF) and microwave frequency region. At the optimum sintering temperature of 1140 °C, Li₂TiGeO₅ (LTG) has ε_r ˜ 9.43, Q × f ˜ 65,300 GHz (at 14.7 GHz), and τ_f ˜ +24.1 ppm/°C, while Li₂TiSiO₅ (LTS) sintered at 1180 °C exhibits ε_r ˜ 9.89, Q × f ˜ 38,100 GHz (at 14.2 GHz), and τ_f ˜ +50.1 ppm/°C. The positive τ_f values of the present LTG and LTS are abnormal and extremely important for low-ε_r microwave dielectric ceramics, which could behave as a promising τ_f compensator. Moreover, the dielectric spectra of both ceramics revealed a phase transition at low-temperature, exhibiting a dielectric peak, which could account for the negative τ_ε and positive τ_f in operating temperature ranges.     

Degree of inversion of A/B lattice sites and microwave/millimeter wave/terahertz dielectric properties of MgAl2-x(Zn0.5Mn0.5)xO4 ceramics

In this work, spinel-structured MgAl_2-x(Zn_0.5Mn_0.5)_xO₄ (0 ≤ x ≤ 0.08) single-phase ceramics were prepared through a solid-state reaction route. The substitution of (Zn_0.5Mn_0.5)³⁺ for Al³⁺ at the octahedral site affected the degree of inversion of A/B lattice sites, bond length/strength/valence, and covalency of metal-oxygen bond in the tetrahedron and hence microwave dielectric properties of MgAl₂O₄. The variation in ε_r and tanδ of ceramics is investigated in the millimeter wave-terahertz frequency band by combining infrared reflection spectrum and terahertz time-domain spectroscopy. A high Q×f value of 111,010 GHz @ 12.01 GHz, low ε_r = 8.3, and slightly lower τ_f = −60 ppm/°C is obtained for MgAl_1.98Zn_0.01Mn_0.01O₄ ceramics, which is tuned by adding a small amount of SrTiO₃. The composite ceramics exhibited a near-zero τ_f (2.8 ppm/°C), high Q×f (55,400 GHz @ 11.15 GHz), and low ε_r (= 8.5), showing a great potential application prospect for 5G/6G wireless communication.     

Crystal structure,microwave dielectric properties and low temperature sintering of (Al0.5Nb0.5)4+ co-substitution for Ti4+ of LiNb0.6Ti0.5O3 ceramics

The phase composition, microstructure, microwave dielectric properties of (Al_0.5Nb_0.5)⁴⁺ co-substitution for Ti site in LiNb_0.6Ti_0.5O₃ ceramics and the low temperature sintering behaviors of Li₂O-B₂O₃-SiO₂ (LBS) glass were systematically discussed. XRD patterns and EDS analysis result confirmed that single phase of Li_1.075Nb_0.625Ti_0.45O₃ solid solution was formed in all component. The increase of dielectric constant (ε_r) is ascribed to the improvement of bulk density. The restricted growth of grain has a negative influence on quality factor (Q×f) value. The τ_f value could be continuously shifted to near zero as the doping content increases. Great microwave dielectric properties were obtained in LiNb_0.6Ti_(0.5-x)(Al_0.5Nb_0.5)_xO₃ ceramics (x?=?0.10) when sintered at 1100?℃ for 2?h: ε_r =?70.34, Q×f =?5144?GHz, τ_f =?4.8?ppm/℃. The sintering aid, LBS glass, can effectively reduce the temperature and remain satisfied microwave performance. Excellent microwave dielectric properties for x?=?0.10 were obtained with 1.0?wt% glass: ε_r =?70.16, Q×f =?4153?GHz (at 4?GHz), τ_f =?-0.65?ppm/℃ when sintered at 925?℃ for 2?h.     

Polarization-dependent multichannel transmission of 5G signals based on Zn0.91(Li0.5Bi0.5)0.09MoO4 low-temperature co-fired ceramics

Microwave communication for 5 G signals is the preferred solution in modern communication networks where fiber optic cables are difficult to deploy or base stations operate incorrectly. Here, a novel Zn_1-x(Li_0.5Bi_0.5)_xMoO₄ (ZLBMO∼xLB, x = 0.09) ceramic with excellent microwave dielectric properties (ε_r = 10.5, Q×f = 43,001 GHz, τ_f = −21.5 ppm/°C) is developed using solid-state reaction method. The sintering temperature is successfully reduced from 850 °C to 725 °C. For the first time, an all-ceramic device for multichannel transmission of 5 G signals is designed using this ceramic material. This device exhibits transverse dual-channel, longitudinal dual-channel, and four-channel transmission under x-, y- and 45°-polarized waves incidence, respectively. The number of channels can be changed by switching the polarization state of the incident wave. This functionality is verified by simulation results of the electric field and phase. This work provides new ideas for the combination of dielectric ceramics and communication devices.     

Co2O3 substitution effects on the structure and microwave dielectric properties of low-firing (Zn0.9Mg0.1)TiO3 ceramics

Low-firing (Zn_0.9Mg_0.1)_1?xCo_xTiO₃ (x = 0.02–0.10) (ZMC_xT) microwave dielectric ceramics with high temperature stability were synthesized via conventional solid-state reaction. The influences of Co₂O₃ substitution on the phase composition, microstructure and microwave dielectric properties of ZMC_xT ceramics were discussed. Rietveld refinement results show the coexistence of ZnTiO₃ and ZnB₂O₄ phases at x = 0.02–0.10. (Zn_0.9Mg_0.1)_1?xCo_xTiO₃ ceramic with x = 0.06 (ZMC_0.06T) obtains the best combination microwave dielectric properties of: ε_r = 21.58, Q × f = 53,948 GHz, τ_f = ? 54.38 ppm/°C. For expanding its application in LTCC field, 3 wt% ZnO-B₂O₃-SiO₂ (ZBS) and 9 wt% TiO₂ was added into ZMC_0.06T ceramic, great microwave dielectric properties were achieved at 900 °C for 4 h: ε_r = 26.03, Q × f = 34,830 GHz, τ_f = ? 4 ppm/°C, making the composite ceramic a promising candidate for LTCC industry.     

Effects of Ni2+ substitution on the crystal structure,bond valence,and microwave dielectric properties of BaAl2–2xNi2xSi2O8–x ceramics

BaAl_2?2xNi_2xSi₂O_8?x (x = 0, 0.005, 0.01, 0.02, 0.03) ceramics were prepared using traditional solid phase reaction method. The microwave dielectric properties, including permittivity (ε_r), quality factor (Q × f), and temperature coefficient of resonant frequency (τ_f), were discussed based on the bond valence theory. The first-principle calculation was adopted to determine the site (Ba, Al, and Si) where doping element (Ni²⁺) would be inclined to occupy. The substitution of Ni²⁺ for Al³⁺ contributed to the breaking of Al-O and Si-O bonds and then facilitated the BaAl₂Si₂O₈ (BAS) hexacelsian-celsian transformation. Moreover, this substitution could change the bond strength between cation and oxygen anion due to the variation of the bond valence, which reasonably explained the variation of ε_r, Q × f, and τ_f values. Well-sintered and completely transformed celsian ceramics can be obtained after doping with Ni²⁺. When x = 0.01, compact BaAl_1.98Ni_0.02Si₂O_7.99 ceramic exhibited highly promising microwave dielectric properties: ε_r = 6.89, Q × f = 53, 287 GHz and τ_f = -25.31 × 10^?6 /°C.     

Structure–property relationships of perovskite-structured Ca0.61Nd0.26Ti1-x(Cr0.5Nb0.5)xO3 ceramics

A series of Ca_0.61Nd_0.26Ti_1-x(Cr_0.5Nb_0.5)_xO₃ (CNTCNx) (0 ≤ x ≤ 0.1) ceramics were prepared via a solid state reaction method. All CNTCNx samples were crystallized into the orthorhombic perovskite structure. The SEM micrographs indicated that the average grain sizes of samples depended on (Cr_0.5Nb_0.5)⁴⁺ concentration. And as (Cr_0.5Nb_0.5)⁴⁺ concentration increased, the average grain size of samples decreased significantly. The short range order (SRO) structure and structural distortion of oxygen octahedra proved to exist in CNTCNx crystals from Raman spectra analysis results. The microwave dielectric properties highly depended on the B-site bond strength, oxygen octahedra distortion, reduction of Ti⁴⁺ to Ti³⁺ and internal strain η. At last, the CNTCN0.06 ceramic sintered at 1400 °C for 4 h exhibited good and stable comprehensive microwave dielectric properties of ε_r = 92.3, Q × f = 13,889 GHz, τ_f = + 152.8 ppm/°C.     

Microstructure and microwave dielectric properties of Li2Ti1−x(Zn1/3Nb2/3)xO3 ceramics

Li₂Ti_1?x(Zn_1/3Nb_2/3)_xO₃ (0≤x≤0.5) ceramics were prepared by a solid state ceramic route, and the phase purity, microstructure, and microwave dielectric properties were investigated. The XRD results suggest the formation of solid solutions for all studied compositions (0≤x≤5). The dielectric properties are strongly dependent on the compositions, the densifications and the microstructures of the samples. The Q×f value increases with x up to x=0.2 and then decreases with the further increase of x. The best microwave dielectric properties of ε_r=20.5, Q×f =75,257 GHz, and τ_f =15.4 ppm/°C could be obtained when x=0.2.     

Correlation between crystal structure,bond characteristics,Raman vibrations,and improved microwave dielectric properties of high-performance Zn0.5Zr0.5NbO4 ceramics: First principle calculation and experiment

The structure–performance mechanism provides new insights into performance modification and materials discovery. Herein, the electronic structure, Raman vibration, chemical bond factors and enhanced microwave dielectric properties of Zn_0.5Zr_0.5NbO₄ ceramics through oxygen-assisted reaction sintering were investigated by Raman spectroscopy, first-principle calculations, and complex P–V-L theory. Pure-phase Zn_0.5Zr_0.5NbO₄ ceramics were synthesized under oxygen-assisted reaction sintering, confirmed by XRD refinement and Raman analysis. Systematic vibration analysis was first introduced to provide complete mode assignments and Raman shift. Optimized microstructure with full density was obtained through morphology and EDS analysis. First-principle calculations indicated that the d orbit exerts the main contribution to Fermi energy with energy gap of 3.51 eV and Nb–O bonds may possess strong vibration, exhibiting a remarkable effect on dielectric loss. P–V-L results showed that Nb–O bonds have a significant influence on the dielectric constant and Q×f value while the Zn–O bonds dominate the τ_f value. In addition, high-performance Zn_0.5Zr_0.5NbO₄ ceramics were fabricated through oxygen-assisted reaction sintering at 1250 °C, with ε_r = 28.4, Q×f = 79,800 GHz, and τ_f = −47.7 ppm/^°C, exhibiting tremendous superiorities for commercial production.     

Effects of structural characteristics on microwave dielectric properties of low-loss (Zn1-xNix)ZrNbTaO8 ceramics

Low-loss (Zn_1-xNi_x)ZrNbTaO₈ (0.02?≤?x?≤?0.10) ceramics possessing single wolframite structure are initiatively synthesized by solid-state route. Based on the results of Rietveld refinement, complex chemical bond theory is used to establish the correlation between structural characteristics and microwave performance in this ceramic system. A small amount of Ni²⁺ (x?=?0.06) in A-site with the fixed substitution of Ta⁵⁺ in B-site can effectually raise the Q?×?f value of ZnZrNb₂O₈ ceramic, embodying a dense microstructure and high lattice energy. The dielectric constant and τ_f are mainly affected by bond ionicity and the average octahedral distortion. The (Zn_0.94Ni_0.06)ZrNbTaO₈ ceramic sample sintered at 1150?°C for 3?h exhibits an outstanding combination of microwave dielectric properties: ε_r =?27.88, Q?×?f?=?128,951?GHz, τ_f =?–39.9?ppm/°C. Thus, it is considered to be a candidate material for the communication device applications at high frequency.     

Impedance spectroscopy,B-site cation ordering and structure–property relations of (1 − x) La[Al0.9(Mg0.5Ti0.5)0.1]O3–x CaTiO3 ceramics for 5G dielectric waveguide filters

Dense (1 ? x) La[Al_0.9(Mg_0.5Ti_0.5)_0.1]O₃–x CaTiO₃ ceramics were synthesized via solid-state reaction. The crystal structure and microwave dielectric properties of the ceramics were systematically investigated. Rietveld refinement revealed that when x ≤ 0.2, the ceramics had a rhombohedral structure with an R-3c space group. When x ≥ 0.5, the ceramics had an orthorhombic structure with a Pbnm space group. Selected area electron diffraction and Raman spectroscopy analyses proved that the microwave dielectric ceramics had a B-site order, which accounted for the great improvement in microwave dielectric properties. The content of oxygen vacancies was identified through X-ray photoelectron spectroscopy, and the change rule of Q × f was closely related to oxygen vacancy content. The perturbation of A-site cations had an important influence on dielectric constant. Specifically, with the increase in Ti⁴⁺ content, the perturbation effect of the A-site cations was enhanced and dielectric constant increased. When x = 0.65, the temperature coefficient of resonant frequency of the (1 ? x) La[Al_0.9(Mg_0.5Ti_0.5)_0.1]O₃–x CaTiO₃ microwave dielectric ceramics was near zero. The optimal microwave dielectric properties of 0.35LaAl_0.9(Mg_0.5Ti_0.5)_0.1O₃–0.65CaTiO₃ were ε_r = 44.6, Q × f = 32,057 GHz, and τ_f = +2 ppm/°C.     

Chemical bond and microwave dielectric properties of two novel low-εr AGa4O7 (A = Ca,Sr) ceramics

Two novel low-ε_r microwave dielectric ceramics AGa₄O₇ (A = Ca, Sr; called CGO and SGO, respectively) were analyzed by XRD, SEM, and Raman spectroscopy, showed the monoclinic structure with a C2/c space group. Encouraging microwave dielectric properties (CGO: ε_r = 9.1, Q × f = 40 600 GHz (f = 12.4 GHz), and τ_f = ?86.3 ppm °C^?1; SGO: ε_r = 9.2, Q × f = 62 400 GHz (f = 14.6 GHz), and τ_f = ?63.4 ppm °C^?1) are obtained. The PVL chemical bond theory indicated that GaO bonds play a role in affecting the ε_r and Q × f values. The τ_f of AGa₄O₇ (A = Ca, Sr) had adjusted close to zero (0.93CGO-0.07CaTiO₃:ε_r = 11.3, Q × f = 31,043 GHz, and τ_f = 3.97 ppm °C^?1; 0.82SGO-0.18LiCa₂Mg₂V₃O_12：ε_r = 11.8, Q × f = 55,564 GHz, and τ_f = 5.62 ppm °C^?1).     

Effect of B-site ion substitution on chemical bond characteristics and microwave dielectric properties of ZnWO4 ceramics

Herein, the influence of Mo⁶⁺ substitution on the crystal structure, microstructures, chemical bond characteristics, vibration characteristics and microwave dielectric properties of ZnMo_xW_1-xO₄(x = 0−0.12) ceramics prepared by a solid-state reaction were investigated. The results show that Mo⁶⁺ substitution does not produce secondary phase, the densification temperature decreases from 1100 to 925 ℃, and Q × f values increased from 19605 GHz (x = 0) to 61640 GHz (x = 0.06) at 925 ℃, which resulted from the packing fraction, U_tW-O and microstructures. Also, the τ_f values were optimized to −34 ppm/°C due to changes in the degree of structural order and stability of chemical bonds.Af_iW-O, molecular polarizability and porosity first led to an increase in permittivity and decrease thereafter. The ZnMo_0.06W_0.94O₄ ceramics sintered at 925℃ exhibited satisfactory properties (ε_r = 15.10, Q × f = 61,640 GHz, and τ_f = -34 ppm/°C), providing a potential candidate for microwave devices.