A Novel Magnetodielectric Solid Solution Ceramic 0.4LiFe5O8–0.6Li2MgTi3O8 with Excellent Microwave Dielectric Properties

In this study, a novel spinel solid solution ceramic of 0.4LiFe₅O₈–0.6Li₂MgTi₃O₈ (0.4LFO–0.6LMT) has been developed and investigated. It is found that the 40 mol% LiFe₅O₈ and 60 mol% Li₂MgTi₃O₈ are fully soluble in each other and a disordered spinel phase is formed. The ceramic sample sintered at 1050°C/2 h exhibits both good magnetic and dielectric properties in the frequency range 1–10 MHz, with a permeability between 29.9~14.1 and magnetic loss tangent between 0.12~0.67, permittivity between 16.92~16.94 and dielectric loss tangent between 5.9 × 10^?3–2.3 × 10^?2. The sample also has good microwave dielectric properties with a relative permittivity of 16.1, a high quality factor (Q × f) ~28 500 GHz (at 7.8 GHz). Furthermore, 3 wt% H₃BO₃–CuO (BCu) addition can effectively lower the sintering temperature to 925°C and does not degrade the magnetodielectric properties. The chemical compatibility with silver electrode indicates that this kind of ceramics is a good candidate for the low‐temperature cofired ceramic (LTCC) application.     

High quality factor microwave dielectric ceramics in the (Mg1/3Nb2/3)O2–ZrO2–TiO2 ternary system

Novel high quality factor microwave dielectric ceramics (1?x)ZrTiO₄?x(Mg_1/3Nb_2/3)TiO₄ (0.325≤x≤0.4) and (ZrTi)_1?y(Mg_1/3Nb_2/3)_yO₄ (0.2≤y≤0.5) with the addition of 0.5 wt% MnCO₃ in the (Mg_1/3Nb_2/3)O₂–ZrO₂–TiO₂ ternary system were prepared, using solid‐state reaction method. The relationship between the structure and microwave dielectric properties of the ceramics was studied. The XRD patterns of the sintered samples reveal the main phase belonged to α‐PbO₂‐type structure. Raman spectroscopy and infrared reflectivity (IR) spectra were employed to evaluate phonon modes of ceramics. The 0.65ZrTiO₄?0.35(Mg_1/3Nb_2/3)TiO₄?0.5 wt% MnCO₃ ceramic can be well densified at 1240°C for 2 hours and exhibits good microwave dielectric properties with a relative permittivity (ε_r) of 42.5, a quality factor (Q×f) value of 43 520 GHz (at 5.9 Ghz) and temperature coefficient of resonant frequency (τ_f) value of ?5ppm/°C. Furthermore, the (ZrTi)_0.7(Mg_1/3Nb_2/3)_0.3O₄?0.5 wt% MnCO₃ ceramic sintered at 1260°C for 2 hours possesses a ε_r of 31.8, a Q×f value of 35 640 GHz (at 6.3 GHz) and a near zero τ_f value of ?5.9 ppm/°C. The results demonstrated that the (Mg_1/3Nb_2/3)O₂–ZrO₂–TiO₂ ternary system with excellent properties was a promising material for microwave electronic device applications.     

Effects of TiO2 additive on ultra-low-loss MgO–LiF microwave dielectric ceramics

MgO ceramics have good microwave dielectric properties, but the high sintering temperatures limit its application. The effects of TiO₂ additive on the phase composition and microwave dielectric properties of MgO ceramics with 4mol%LiF were investigated by solid state reaction method. TiO₂ and MgO form Mg₂TiO₄ in a magnesium-rich environment with 4mol%LiF at about 900 °C, which as a solid solution or second phase had a huge impact on MgO ceramic with 4mol % LiF. When the content of TiO₂ less than 2mol %, Mg₂TiO₄ as a solid solution in MgO ceramics, which made the grain of MgO larger. When the content of TiO₂ more than 2mol %, Mg₂TiO₄ as a second phase in MgO ceramics, which made the microwave dielectric properties of MgO ceramics bad. Typically, the MgO-4mol%LiF-0.5mol%TiO₂ ceramic sintered at 1075 °C for 6 h acquired the best dielectric properties: ε_r = 9.7, Qf = 617,000 GHz and τ_f = −59.49 ppm/°C.     

Microwave Dielectric Properties of Novel Glass‐Free Low‐Firing Li2CeO3 Ceramics

Novel glass–free low temperature firing microwave dielectric ceramics Li₂CeO₃ with high Q prepared through a conventional solid‐state reaction method had been investigated. All the specimens in this paper have sintering temperature lower than 750°C. XRD studies revealed single cubic phase. The microwave dielectric properties were correlated with the sintering conditions. At 720°C/4 h, Li₂CeO₃ ceramics possessed the excellent microwave dielectric properties of ε_r = 15.8, Q × f = 143 700 (GHz), and τ_f  = ?123 ppm/°C. Li₂CeO₃ ceramics could be excellent candidates for glass‐free low‐temperature co‐fired ceramics substrates.     

Low‐temperature sintering and thermal stability of Li2GeO3‐based microwave dielectric ceramics with low permittivity

A low‐permittivity dielectric ceramic Li₂GeO₃ was prepared by the solid‐state reaction route. Single‐phase Li₂GeO₃ crystallized in an orthorhombic structure. Dense ceramics with high relative density and homogeneous microstructure were obtained as sintered at 1000‐1100°C. The optimum microwave dielectric properties were achieved in the sample sintered at 1080°C with a high relative density ~ 96%, a relative permittivity ε_r ~ 6.36, a quality factor Q × f ~ 29 000 GHz (at 14.5 GHz), and a temperature coefficient of resonance frequency τ_f ~ ?72 ppm/^°C. The sintering temperature of Li₂GeO₃ was successfully lowered via the appropriate addition of B₂O₃. Only 2 wt.% B₂O₃ addition contributed to a 21.2% decrease in sintering temperature to 850°C without deteriorating the dielectric properties. The temperature dependence of the resonance frequency was successfully suppressed by the addition of TiO₂ to form Li₂TiO₃ with a positive τ_f value. These results demonstrate potential applications of Li₂GeO₃ in low‐temperature cofiring ceramics technology.     

Effects of (Mg1/3Ta2/3)-substitution for Ti-site on the microwave dielectric properties of Li2MgTiO4 ceramics

Novel high quality factor microwave dielectric ceramics Li₂MgTi_1?x(Mg_1/3Ta_2/3)_xO₄ (0 ≤ x ≤ 0.5) were successfully prepared via a conventional solid-state ceramic route. The effects of isovalent substitutions (Mg_1/3Ta_2/3)⁴⁺ at the Ti-site on the sintering behaviors, microstructures, and microwave dielectric properties of Li₂MgTiO₄ ceramics were investigated in this paper. The sintered samples exhibited the single phase with cubic rock-salt structure belonging to Fm-3m space group in the whole composition range. Rietveld refinement which could be performed by the Fullprof program was taken to explain the effects of (Mg_1/3Ta_2/3)⁴⁺ ion substitution on the crystal structures of Li₂MgTiO₄ ceramics. With the (Mg_1/3Ta_2/3)⁴⁺ content increasing from 0 to 0.5, the quality factor Q·f firstly increased and decreased thereafter, while the dielectric constant ε_r almost linearly decreased. In addition, the τ_f values shifted to positive value with the amount of (Mg_1/3Ta_2/3)⁴⁺ increasing. The best composition appeared to be Li₂MgTi_0.6(Mg_1/3Ta_2/3)_0.4O₄, which showed excellent microwave dielectric properties of ε_r = 15.73, Q·f = 184,000 GHz and τ_f = ? 12.54 ppm/°C. This made the Li₂MgTi_0.6(Mg_1/3Ta_2/3)_0.4O₄ ceramic a very promising candidate for use as a low-loss microwave material.     

Influence of Li2O–B2O3–SiO2 glass on the sintering behavior and microwave dielectric properties of BaO–0.15ZnO–4TiO2 ceramics

This paper reports the investigation of the performance of Li₂O–B₂O₃–SiO₂ (LBS) glass as a sintering aid to lower the sintering temperature of BaO–0.15ZnO–4TiO₂ (BZT) ceramics, as well as the detailed study on the sintering behavior, phase evolution, microstructure and microwave dielectric properties of the resulting BZT ceramics. The addition of LBS glass significantly lowers the sintering temperature of the BZT ceramics from 1150 °C to 875–925 °C. Small amount of LBS glass promotes the densification of BZT ceramic and improves the dielectric properties. However, excessive LBS addition leads to the precipitation of glass phase and growth of abnormal grain, deteriorating the dielectric properties of the BZT ceramic. The BZT ceramic with 5 wt% LBS addition sintered at 900 °C shows excellent microwave dielectric properties: ε_r=27.88, Q×f=14,795 GHz.     

MgTiO3/TiO2/MgTiO3: An ultrahigh-Q and temperature-stable microwave dielectric ceramic through cofired trilayer architecture

A cofired trilayer ceramic architecture showing as MgTiO₃/TiO₂/MgTiO₃ was designed to realize temperature-stable and ultrahigh-Q microwave dielectrics in the typical MgTiO₃-TiO₂ system. The effects of TiO₂ content on the microwave dielectric properties of cofired trilayer ceramics were studied. Through the design of cofired trilayer architecture, the chemical reactions between MgTiO₃ and TiO₂ were limited within a narrow region of MgTiO₃/TiO₂ interfaces (~ 15?µm in width), which could be beneficial for optimizing the microwave dielectric properties. Excellent characteristics of ε_r ~ 18.38, Q×f value ~ 169,900?GHz and τ_f ~ ??1?ppm/°C were gained for the MgTiO₃/TiO₂/MgTiO₃ ceramic architectures stacked with 1.63?vol% TiO₂. The current work could serve as new strategies to develop high-performance dielectric resonators and multilayers for 5G wireless communication applications.     

Silver Co-Firable ZnTiNb2O8 Microwave Dielectric Ceramics with Li2O–ZnO–B2O3 Glass Additive

The effects of Li₂O–ZnO–B₂O₃ glass additive on the sintering behavior, phase formation, microstructure, and microwave dielectric properties of ZnTiNb₂O₈ ceramics have been investigated. The sintering temperature of ZnTiNb₂O₈ ceramics can be effectively reduced from 1200°C to 875°C by adding a small amount of Li₂O–ZnO–B₂O₃ glass, while no obvious degradation of the microwave dielectric properties was induced. Typically, the 2.0 wt% Li₂O–ZnO–B₂O₃ glass-added ceramic sintered at 875°C has better microwave dielectric properties of ɛ_r=31.8, Q×f=25,013 GHz, and τ_f=−62 ppm/°C. In addition, the ceramics can be co-fired well with an Ag electrode.     

Parallel preparation and properties investigation on Li2O-Nb2O5-TiO2 microwave dielectric ceramics

A parallel preparation method was developed using dry powders as starting materials to synthesize multi-compositional microwave dielectric ceramics. The Li₂O-Nb₂O₅-TiO₂ ternary system was investigated as a model material. The validity of the parallel ceramic preparation process was confirmed by synthesizing a group of LiNb_0.6Ti_0.5O₃ ceramics in parallel, which showed the same crystalline structure and close dielectric properties. The ceramic libraries with M-phase-rich samples and Li₂TiO₃-rich samples were prepared using the parallel process, and the microwave dielectric properties and crystal phases were investigated systematically. An excellent microwave ceramic with a composition of 0.55Li₂O-0.05Nb₂O₅-0.40TiO₂ was obtained, which has a dielectric constant of 18.4 and a high quality value (Q × f) of 79000 GHz. This parallel process can be applied extensively to explore a variety of bulk ceramic libraries for discovering new functional materials with high performances.     

Microwave dielectric properties of ultra-low loss Li2MgTi0.7(Mg1/3Nb2/3)0.3O4 ceramics sintered at low temperature by LiF addition

In this work, ultra-low loss Li₂MgTi_0.7(Mg_1/3Nb_2/3)_0.3O₄ ceramics were successfully prepared via the conventional solid-state method. X-ray photoelectron spectroscopy (XPS), thermally stimulated depolarization current (TSDC) and bond energy were used to determine the distinction between intrinsic and extrinsic dielectric loss in (Mg_1/3Nb_2/3)⁴⁺ ions substituted ceramics. The addition of (Mg_1/3Nb_2/3)⁴⁺ ions enhances the bond energy in unit cell without changing the crystal structure of Li₂MgTiO₄, which results in high Q·f value as an intrinsic factor. The extrinsic factors such as porosity and grain size influence the dielectric loss at lower sintering temperature, while the oxygen vacancies play dominant role when the ceramics densified at 1400?°C. The Li₂MgTi_0.7(Mg_1/3Nb_2/3)_0.3O₄ ceramics sintered at 1400?°C can achieve an excellent combination of microwave dielectric properties: ε_r =?16.19, Q·f?=?160,000?GHz and τ_f =??3.14?ppm/°C. In addition, a certain amount of LiF can effectively lower the sintering temperature of the matrix, and the Li₂MgTi_0.7(Mg_1/3Nb_2/3)_0.3O₄-3?wt% LiF ceramics sintered at 1100?°C possess balanced properties with ε_r?=?16.32, Q·f?=?145,384?GHz and τ_f =??16.33?ppm/°C.     

High‐Q microwave ceramics of Li2TiO3 co‐doped with magnesium and niobium

In order to solve the problems of acceptor/donor individual doping in Li₂TiO₃ system and clarify the superiority mechanism of co‐doping for improving the Q value, Mg + Nb co‐doped Li₂TiO₃ have been designed and sintered at a medium temperature of 1260°C. The effects of each Mg/Nb ion on structure, morphology, grain‐boundary resistance and microwave dielectric properties are investigated. The substitution of (Mg_1/3Nb_2/3)⁴⁺ inhibits not only the diffusion of Li⁺ and reduction in Ti⁴⁺, but also the formation of microcracks in ceramics, which promotes the enhancement of Q value. The experiments reveal that Q × f value of Li₂TiO₃ ceramics co‐doped with magnesium and niobium is 113 774 GHz (at 8.573 GHz), which is increased by 113% compared with the pure Li₂TiO₃ ceramics. And the co‐doped ceramics have an appropriate dielectric constant of 19.01 and a near‐zero resonance frequency temperature coefficient of 13.38 ppm/°C. These results offer a scientific basis for co‐doping in Li₂TiO₃ system, and the outstanding performance of (Mg + Nb) co‐doped ceramics provides a solid foundation for widespread applications of microwave substrates, resonators, filters and patch antennas in modern wireless communication equipments.     

Sintering behavior,phase evolution and microwave dielectric properties of thermally stable Li2O-3MgO-mTiO2 ceramics (1≤m≤6)

Li₂O-3MgO-mTiO₂ (1≤m≤6) ceramics were prepared by the solid state reaction method. X-ray diffraction, energy dispersive spectrometer and scanning electron microscopy techniques were used to investigate the phase composition and crystal structure. With increasing m values, the phase structures of ceramics changed as: (Li₂Mg₃TiO₆, m=1)→(Li₂Mg₃Ti₄O₁₂ and Mg₂TiO₄, m=2,3)→(Li₂Mg₃Ti₄O₁₂, m=4)→(Li₂Mg₃Ti₄O₁₂, MgTiO₃ and Li₂MgTi₃O₈, m=5)→(Li₂Mg₃Ti₄O₁₂, MgTiO₃, Li₂MgTi₃O₈ and MgTi₂O₅, m=6). The optimized sintering temperature was lowered from 1275 °C to 1050 °C. When m=5, Li₂O-3MgO-5TiO₂ ceramics showed good microwave dielectric properties at a wide sintering temperature range of 1000–1200 °C, and the best microwave dielectric properties of Q×f=71,726 GHz, ε_r=21.9 and τ_f=−20.9 ppm/°C were obtained at a relatively low sintering temperature of 1050 °C.     

Liquid‐phase sintering,microstructural evolution,and microwave dielectric properties of Li2Mg3SnO6–LiF ceramics

The liquid‐phase sintering behavior and microstructural evolution of x wt% LiF aided Li₂Mg₃SnO₆ ceramics (x = 1‐7) were investigated for the purpose to prepare dense phase‐pure ceramic samples. The grain and pore morphology, density variation, and phase structures were especially correlated with the subsequent microwave dielectric properties. The experimental results demonstrate a typical liquid‐phase sintering in LiF–Li₂Mg₃SnO₆ ceramics, in which LiF proves to be an effective sintering aid for the Li₂Mg₃SnO₆ ceramic and obviously reduces its optimum sintering temperature from ~1200°C to ~850°C. The actual sample density and microstructure (grain and pores) strongly depended on both the amount of LiF additive and the sintering temperature. Higher sintering temperature tended to cause the formation of closed pores in Li₂Mg₃SnO₆‐x wt% LiF ceramics owing to the increase in the migration ability of grain boundary. An obvious transition of fracture modes from transgranular to intergranular ones was observed approximately at x = 4. A single‐phase dense Li₂Mg₃SnO₆ ceramic could be obtained in the temperature range of 875°C‐1100°C, beyond which the secondary phase Li₄MgSn₂O₇ (<850°C) and Mg₂SnO₄ (>1100°C) appeared. Excellent microwave dielectric properties of Q × f = 230 000‐330 000 GHz, ε_r = ~10.5 and τ_f = ~?40 ppm/°C were obtained for Li₂Mg₃SnO₆ ceramics with x = 2‐5 as sintered at ~1150°C. For LTCC applications, a desirable Q × f value of ~133 000 GHz could be achieved in samples with x = 3‐4 as sintered at 875°C.     

Effects of adding B2O3 on microwave dielectric properties of 0.9625MgTiO3-0.0375(Ca0.5Sr0.5)TiO3 composite ceramics

A series of 0.9625MgTiO₃-0.0375(Ca_0.5Sr_0.5)TiO₃ composite ceramics added with different amounts of B₂O₃ (1-5 wt%) were prepared via the solid state sintering method using the pre-synthesized raw MgTiO₃ and (Ca_0.5Sr_0.5)TiO₃ powders by molten-salt reaction. The sintering temperature of 0.9625MgTiO₃-0.0375(Ca_0.5Sr_0.5)TiO₃ composite ceramics can be reduced from 1275°C to 1175°C due to the liquid phase sintering effect of B₂O₃. When the adding amount of B₂O₃ was more than 2 wt%, a new phase MgTi₂O₅ could be detected by X-ray diffraction, which would substantially degrade the dielectric properties of the obtained ceramics. Resultantly, the quality factor (Q·f) and dielectric constant (ε_r) of the samples increase first and decrease later with increasing addition amount of B₂O₃. In addition, the temperature coefficient of resonant frequency (τ_f) progressively increases with increasing content of B₂O₃. By sintering at 1175°C for 4 hours, the obtained 0.9625MgTiO₃-0.0375Ca_0.5Sr_0.5TiO₃ composite ceramics with 2 wt% B₂O₃ possess the optimal microwave dielectric properties of ε_r = 18.9, Q·f = 57 000 GHz and τ_f = −1.2 ppm/°C.     

Novel ultra-low loss and low-fired Li8MgxTi3O9+xF2 microwave dielectric ceramics for resonator antenna applications

Low temperature sintered Li₈Mg_xTi₃O_9+xF₂ microwave dielectric ceramics with x = 2−7 were developed based on a newly designed pseudo ternary phase diagram of the Li₂TiO₃–MgO–LiF system. Dense solid solution ceramics (of relative density >96 %) with cubic rock-salt structure, accompanied by a small amount of secondary phase MgO, were obtained in the temperature range of 800−925 °C. With increasing Mg²⁺ content, the value of ε_r decreased, whereas that of τ_f remained nearly constant, and the Q × f increased to a maximum at x = 5. The Li₈Mg₅Ti₃O₁₄F₂ ceramic sintered at 875 °C exhibited superior microwave dielectric properties with ε_r = 16.8, Q × f = 119,700 GHz, and τ_f = −41.6 ppm/°C. The good compatibility with Ag electrodes highlights the promising prospects of this ceramic in low-temperature co-fired ceramic technology. Furthermore, a dielectric resonator antenna fabricated based on a Li₈Mg₅Ti₃O₁₄F₂ ceramic exhibited an outstanding S₁₁ of −34.7 dB and a broad bandwidth of 360 MHz at the desired resonant frequency of 5.98 GHz.     

Effects of ZnO and B2O3 on the Microstructure and Microwave Dielectric Properties of 5Li2O‐1Nb2O5‐5TiO2 Ceramics

The effects of ZnO and B₂O₃ addition on the sintering behavior, microstructure, and the microwave dielectric properties of 5Li₂O‐1Nb₂O₅‐5TiO₂ (LNT) ceramics have been investigated. With addition of low‐level doping of ZnO and B₂O₃, the sintering temperature of the LNT ceramics can be lowered down to near 920°C due to the liquid phase effect. The Li₂TiO₃ss and the “M‐phase” are the two main phases, whereas other phase could be observed when co‐doping with ZnO and B₂O₃ in the ceramics. And the amount of the other phase increases with the ZnO content increasing. The addition of ZnO does not induce much degradation in the microwave dielectric properties but lowers the τ_f value to near zero. Typically, the good microwave dielectric properties of ε_r = 36.4, Q × f = 8835 GHz, τ_f = 4.4 ppm/°C could be obtained for the 1 wt% B₂O₃ and 4 wt% ZnO co‐doped sample sintered at 920°C, which is promising for application of the multilayer microwave devices using Ag as internal electrode.     

Temperature stable dielectric properties of Mg2TiO4–MgTiO3–CaTiO3 Ceramics Over a Wide Temperature range

The zero resonant frequency temperature coefficient (τ_f) of microwave dielectric ceramics (MWDCs) at high and low temperature have attracted great attention in the development of microwave communication equipment. In this work, the Mg₂TiO₄–MgTiO₃–CaTiO₃ (MMC) ceramics with meeting the application requirements of 5G communication were prepared by traditional solid-phase sintering after investigating the relationship among phase compositions of xMg₂TiO₄-(0.931-x)MgTiO₃-0.069CaTiO₃ and 0.34Mg₂TiO₄-0.591MgTiO₃-yCaTiO₃, sintering process, and dielectric properties in detail. The results show that the dielectric properties of MMC ceramics are strongly affected by the phase relative contents of MgTiO₃, Mg₂TiO₄ and CaTiO₃. For instance, MMC ceramics with approximate τ_f = 0 is contributed by mutual compensation of Mg₂TiO₄ and MgTiO₃, in which the Mg₂TiO₄ phase plays an important role in decreasing the τ_f value; and the increase of CaTiO₃ will greatly increase the ε_r value for MMC ceramics, while has a negative effect in the Q × f value. After three-phase regulation, the 0.32Mg₂TiO₄-0.611MgTiO₃-0.069CaTiO₃ microwave dielectric ceramic has a better dielectric temperature stability, associated with dielectric properties of ε_r = 19.7, Q × f = 55,400 GHz (at 8.43 GHz), τ_f- = 4.5 ppm/°C (?40 °C–25 °C), and τ_f+ = ?5.1 ppm/°C (25 °C–90 °C).     

Microwave Dielectric Properties and Thermally Stimulated Depolarization Currents of (1 − x)MgTiO3–xCa0.8Sr0.2TiO3 Ceramics

(1 ? x)MgTiO₃–xCa_0.8Sr_0.2TiO₃ (0.04 ≤ x ≤ 0.2, MT‐CST) composite ceramics were prepared by the conventional solid‐state reaction process. The phase composition, microwave dielectric properties, and microwave dielectric loss mechanisms were studied. Ca_0.8Sr_0.2TiO₃ was employed as a τ_f compensator for MgTiO₃, and they coexisted well without forming any secondary phases. Interestingly, significant dielectric relaxations associated with oxygen vacancy defects were observed in all the MT‐CST ceramics through the dielectric‐temperature spectra. Thermally simulated depolarization current was therefore conducted to obtain the defects associated with extrinsic dielectric loss mechanisms. The concentrations of both defect dipole and in‐grain oxygen vacancies increased with the increasing x, which could induce microwave dielectric loss consequently. It demonstrated that the behaviors of Q × f were basically influenced by phase composition and defects here. Temperature‐stable ceramics can be achieved at x = 0.06, where the microwave dielectric properties were ε_r = 21.19, Q × f = 110 900 GHz (f = 9.295 GHz), and τ_f = ?0.9 ppm/°C, respectively.