Low‐Temperature Sintering and Microwave Dielectric Properties of (Mg0.95Zn0.05)2(Ti0.8Sn0.2)O4–(Ca0.8Sr0.2)TiO3 Composite Ceramics

0.9(Mg_0.95Zn_0.05)₂(Ti_0.8Sn_0.2)O₄–0.1(Ca_0.8Sr_0.2)TiO₃ (MZTS–CST) ceramics were prepared by a conventional solid‐state route. The MZTS–CST ceramics sintered at 1325°C exhibited ε_r = 18.2, Q × f = 49 120 GHz (at 8.1 GHz), and τ_f = 15 ppm/°C. The effects of LiF–Fe₂O₃–V₂O₅ (LFV) addition on the sinterability, phase composition, microstructure, and microwave dielectric properties of MZTS–CST were investigated. Eutectic liquid phases 0.12CaF₂/0.28MgF₂/0.6LiF and MgV₂O₆ were developed, which lowered the sintering temperature of MZTS–CST ceramics from 1325°C to 950°C. X‐ray powder diffraction (XRPD) and energy dispersive spectroscopy (EDS) analysis revealed that MZTS and CST coexisted in the sintered ceramics. Secondary phase Ca₅Mg₄(VO₄)₆ as well as residual liquid phase affected the microwave dielectric properties of MZTS–CST composite ceramics. Typically, the MZTS–CST–5.3LFV composite ceramics sintered at 950°C showed excellent microwave dielectric properties: ε_r = 16.3, Q × f = 30 790 GHz (at 8.3 GHz), and τ_f = ?10 ppm/°C.     

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.     

Ultrahigh Q values and atmosphere-controlled sintering of Li2(1+x)Mg3ZrO6 microwave dielectric ceramics

Ultrahigh-Q Li_2(1+x)Mg₃ZrO₆ microwave dielectric ceramics were successfully prepared by means of atmosphere-controlled sintering through simultaneously adopting double crucibles and sacrificial powder. This technique played an effective role in suppressing the lithium volatilization and further promoting the formation of the liquid phase, as evidenced by the X-ray diffraction, microstructural observation and the density measurement. Both dense and even microstructure, and the suppression of detrimental secondary phases contributed to low-loss microwave dielectric ceramics with Q×f values of 150,000–300,000 GHz. Particularly, desirable microwave dielectric properties of ε_r=12.8, Q×f=307,319 GHz (@9.88 GHz), and τ_f=−35 ppm/°C were achieved in the x=0.06 sample as sintered at 1275 °C for 6 h.     

Microwave dielectric properties of La3Ti2TaO11 ceramics with perovskite-like layered structure

The first characterization of the microwave dielectric properties of the La₃Ti₂TaO₁₁ ceramics is presented. An ordinarily sintered ceramic at 1560 °C exhibits good microwave dielectric properties with ?_r = 46, Q × f = 7500 GHz and τ_f = ?47 ppm/°C. An alternative approach to tailor the temperature coefficient of resonate frequency of La₃Ti₂TaO₁₁ ceramics is also presented. Textured La₃Ti₂TaO₁₁ ceramics were fabricated using spark plasma sintering (SPS). By controlling the sintering temperature, orientation degree increased together with the steadily increase in ?_r and Q × f. A noteworthy change in τ_f from ?43.1 ppm/°C to ?13.6 ppm/°C with increasing orientation degree was observed. These results suggest that grain-orientation control was an effective way to tailor the microwave dielectric properties of La₃Ti₂TaO₁₁ ceramics.     

Sintering behavior and microwave dielectric properties of Ca1-xBixW1-xVxO4 ceramics

Structure, sintering behavior and microwave dielectric properties of ceramics have been investigated by x-ray powder diffraction (XRD) and scanning electron microscopy (SEM) in this paper. The microwave dielectric properties of the ceramics were studied with a network analyzer at the frequency of about 6–11 GHz. The sintering temperature and microwave dielectric properties could be successfully tuned in a wide window simultaneously by adjusting the A–O bond characteristics. The sintering temperature of CaWO₄ was successfully reduced from 1100 °C to about 950 °C by BiVO₄ addition. Approximately 95%–96% theoretical density could be obtained after sintering at 950 °C for 2 h. All samples exhibit single Scheelite structure (I4₁/a) phase. The dielectric constant increased, whereas the Q×f value decreased, with the increase of x. The τ_f value changed from negative to positive with the increases of x. Combined excellent microwave dielectric properties with ε_r=22. 1, Q×f=16,730 GHz and τ_f=2.39 ppm/°C could be obtained after sintered at the 950 °C for 2 h for x=0.3 compositions.     

Effect of BaCu(B2O5) on the sintering and microwave dielectric properties of Ca0.4Li0.3Sm0.05Nd0.25TiO3 ceramics

The sintering behaviors and microwave dielectric properties of the Ca_0.4Li_0.3Sm_0.05Nd_0.25TiO₃ (abbreviated CLSNT) ceramics with different amounts of BaCu(B₂O₅) addition were investigated in this paper. Adding BaCu(B₂O₅) to CLSNT lowered its sintering temperature from 1300 °C to 925 °C. No secondary phase was observed in the CLSNT ceramics and complete solid solution of the complex perovskite phase was confirmed. The CLSNT ceramics with small amounts of BaCu(B₂O₅) addition could be well sintered at 925 °C without much degradation in the microwave dielectric properties. Especially, the 1.75 wt.% BaCu(B₂O₅)-doped CLSNT ceramic sample sintered at 925 °C for 3 h had optimum microwave dielectric properties of ε_r = 93.5 ± 3.2, Q × f = 6486 ± 434 GHz, and τ_f = 5 ± 1.5 ppm/°C (at 3–4 GHz), enabling it a promising candidate material for LTCC applications. Obviously, BaCu(B₂O₅) could be a suitable sintering aid to facilitate the densification and microwave dielectric properties of the CLSNT ceramics.     

Two novel ultralow temperature firing microwave dielectric ceramics LiMVO6 (M = Mo,W) and their chemical compatibility with metal electrodes

Low temperature cofired ceramics technology (LTCC) has been widely studied and used in wireless communication because of their outstanding capability for device miniaturization and integration. However, many commercial microwave dielectric materials have high sintering temperatures that pose challenge for cofiring with inner electrodes. Herein, two brannerite vanadate LiMVO₆ (M = Mo, W) ceramics with intrinsically low sintering temperatures were prepared. Dense and stable LiMVO₆ (M = Mo, W) ceramics could obtained at 640 °C for LiMoVO₆ and 700 °C for LiWVO₆. Favorable microwave dielectric properties were also obtained with ε_r = 13.3, Q × f = 12,460 GHz, and τ_f = +101.0 ppm/°C for LiMoVO₆ and ε_r = 11.5, Q × f = 13,260 GHz, and τ_f = +163.8 ppm/°C for LiWVO₆. Moreover, the relationship between crystal structure and microwave dielectric properties was studied by means of packing fraction, bond valence, and octahedral distortion. Their chemical compatibility with the metal electrodes were confirmed.     

Structure and properties of low temperature sintered ZnTa2O6 microwave dielectric ceramics

ZnTa₂O₆ microwave dielectric ceramics have been prepared using ZnTa₂O₆ nano-powders synthesized by sol–gel processing in this study. The crystal structure and microstructure of the ZnTa₂O₆ powders and ceramics were characterized by XRD and SEM techniques. ZnTa₂O₆ ceramics can be densified at a lower sintering temperature of 1200 °C. Microwave dielectric properties show that both of Q × f and ?_r values are lower than those of ceramics prepared by solid state route, and the τ_f values do not show different from that of solid state route. ZnTa₂O₆ ceramics sintered at 1200 °C exhibit good microwave dielectric properties: Q × f = 50,600 GHz, ?_r = 35.12 and τ_f = 9.69 ppm/°C.     

Effects of sintering parameters and Nd doping on the microwave dielectric properties of Y2O3 ceramics

Y₂O₃ ceramics with good dielectric properties were prepared via co-precipitation reaction and subsequent sintering in a muffle furnace. The effects of Nd doping and sintering temperature on microwave dielectric properties were studied. With the increase in sintering temperature, the density, quality factor (Q×f), and dielectric constant (ε_r) values of pure Y₂O₃ ceramics increased to the maximum and then gradually decreased. The Y₂O₃ ceramics sintered at 1500 °C for 4 h showed optimal dielectric properties: ε_r=10.76, Q×f=82, 188 GHz, and τ_f=−54.4 ppm/°C. With the addition of Nd dopant, the Q×f values, ε_r, and τ_f of the Nd: Y₂O₃ ceramics apparently increased, but excessive amount degraded the quality factor. The Y₂O₃ ceramics with 2 at% Nd₂O₃ sintered at 1460 °C displayed good microwave dielectric properties: ε_r=10.4, Q×f=94, 149 GHz and τ_f=−46.2 ppm/°C.     

Li4Mg3Ti2O9: A novel low-loss microwave dielectric ceramic for LTCC applications

Low-loss novel Li₄Mg₃Ti₂O₉ dielectric ceramics with rock-salt structure were prepared by a conventional solid-state route. The crystalline structure, chemical bond properties, infrared spectroscopy and microwave dielectric properties of the abovementioned system were initially investigated. It could be concluded from this work that the extrinsic factors such as sintering temperatures and grain sizes significantly affected the dielectric properties of Li₄Mg₃Ti₂O₉ at lower sintering temperatures, while the intrinsic factors like bond ionicity and lattice energy played a dominant role when the ceramics were densified at 1450 °C. In order to explore the origin of intrinsic characteristics, complex dielectric constants (ε^’ and ε^’’) were calculated by the infrared spectra, which indicated that the absorptions of phonon oscillation predominantly effected the polarization of the ceramics. The Li₄Mg₃Ti₂O₉ ceramics sintered at 1450 °C exhibited excellent properties of ε_r=15.97, Q·f=135,800 GHz and τ_f=−7.06 ppm/°C. In addition, certain amounts of lithium fluoride (LiF) were added to lower the sintering temperatures of matrix. The Li₄Mg₃Ti₂O₉−3 wt% LiF ceramics sintered at 900 °C possessed suitable dielectric properties of ε_r=15.17, Q·f =42,800 GHz and τ_f=−11.30 ppm/°C, which made such materials promising for low temperature co-fired ceramic applications (LTCC).     

Preparation and microwave dielectric properties of cristobalite ceramics

Dense SiO₂ ceramics with cristobalite phase were prepared by the solid state sintering route, and the microwave dielectric properties were evaluated. The dielectric constant (?_r) and temperature coefficient of resonant frequency (τ_f) of the pure cristobalite ceramics showed little dependence on the sintering temperature. While, the Qf value increased significantly with increasing the sintering temperature, and it was due to the increasing grain size. The optimized microwave dielectric properties with very low ?_r of 3.81, high Qf value of 80,400 GHz and low τ_f of ?16.1 ppm/°C were obtained for the cristobalite ceramics sintered at 1650 °C for 3 h. It was indicated that cristobalite ceramic was a promising candidate as a low-dielectric-constant microwave material for applications in microwave substrates.     

Low-temperature sintered MgWO4–CaTiO3 ceramics with near-zero temperature coefficient of resonant frequency

The phases, microstructure, composition analysis and microwave dielectric properties of (1 ? x)MgWO₄–xCaTiO₃ ceramics with Li₂CO₃–4H₃BO₃ additions prepared by solid-state reaction method have been investigated by using X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy and advantest network analyzer. The τ_f of (1 ? x)MgWO₄–xCaTiO₃ were dependent on phase constitutions. The microwave dielectric properties of 0.91MgWO₄–0.09CaTiO₃ ceramics with Li₂CO₃–4H₃BO₃ were characterized, the results indicated that the ?_r and Q × f were associated with the sintering temperature and amount of Li₂CO₃–4H₃BO₃. The sintering temperature of ceramics was reduced to 950 °C from 1150 °C and τ_f was modified to 0 ppm/°C with good Q × f. Addition of 5.0 wt% Li₂CO₃–4H₃BO₃ in 0.91MgWO₄–0.09 CaTiO₃ ceramics sintered at 950 °C showed excellent dielectric properties of ?_r = 15.5, Q × f = 20,780 GHz (f = 7.1 GHz) and τ_f ～ 0 ppm/°C. The material has a chemical compatibility with silver, making it a very promising candidate materials for LTCC applications.     

Structure and dielectric properties of novel low temperature co-fired Bi2O3-RE2O3-MoO3 (RE=Pr,Nd, Sm,and Yb) based microwave ceramics

Novel monoclinic Bi₂O₃-xRE₂O₃-yMoO₃ (RE=Pr, Nd, Sm, and Yb) based low temperature co-fired ceramics (LTCC) systems with high sintering density and low microwave dielectric loss are synthesized by conventional solid state reaction technique. The structure and dielectric properties of Bi₂O₃-xRE₂O₃-yMoO₃ ceramics are investigated. Dense BiNdMoO₆ ceramics sintered at 900 °C for 8 h in air have a low dielectric constant ε_r=~7.5, a high quality factor Q×f=~ 24, 800 GHz at 7.0 GHz, and τ_f=~−16 ppm/̊C. Especially, good chemical compatibility of BiNdMoO₆ with Ag electrodes is represented as well. In contrast, BiSmMoO₆ ceramics sintered at 1000 °C for 8 h show enhanced Q×f=~43, 700 GHz at 7.8 GHz with ε_r=~8.5 and τ_f=~−27 ppm/°C. Bi₂O₃-xRE₂O₃-yMoO₃ (RE=Pr, Nd, Sm, and Yb) based ceramics could be considered as promising microwave ceramics for LTCC applications.     

Microwave dielectric properties of low loss microwave dielectric ceramics: A0.5Ti0.5NbO4 (A = Zn,Co)

The microwave dielectric properties of low-loss A_0.5Ti_0.5NbO₄ (A = Zn, Co) ceramics prepared by the solid-state route had been investigated. The influence of various sintering conditions on microwave dielectric properties and the structure for A_0.5Ti_0.5NbO₄ (A = Zn, Co) ceramics were discussed systematically. The Zn_0.5Ti_0.5NbO₄ ceramic (hereafter referred to as ZTN) showed the excellent dielectric properties, with ɛ_r = 37.4, Q × f = 194,000 (GHz), and τ_f = −58 ppm/°C and Co_0.5Ti_0.5NbO₄ ceramic (hereafter referred to as CTN) had ɛ_r = 64, Q × f = 65,300 (GHz), and τ_f = 223.2 ppm/°C as sintered individually at 1100 and 1120 °C for 6 h. The dielectric constant was dependent on the ionic polarizability. The Q × f and τ_f are related to the packing fraction and oxygen bond valence of the compounds. Considering the extremely low dielectric loss, A_0.5Ti_0.5NbO₄ (A = Zn and Co) ceramics could be good candidates for microwave or millimeter wave device application.     

Microwave dielectric properties of Re3Ga5O12 (Re: Nd,Sm, Eu,Dy and Yb) ceramics and effect of TiO2 on the microwave dielectric properties of Sm3Ga5O12 ceramics

Re₃Ga₅O₁₂ (Re: Nd, Sm, Eu, Dy and Yb) garnet ceramics sintered at 1350–1500 °C had a high quality factor (Q × f) ranging from 40,000 to 192,173 GHz and a low dielectric constant (ɛ_r) of between 11.5 and 12.5. They also exhibited a relatively stable temperature coefficient of resonant frequency (τ_f) in the range of −33.7 to −12.4 ppm/°C. In order to tailor the τ_f value, TiO₂ was added to the Sm₃Ga₅O₁₂ ceramics, which exhibited good microwave dielectric properties. The relative density and grain size increased with addition of TiO₂, resulting in the enhancement of Q × f value. The τ_f increased with the addition of TiO₂. Excellent microwave dielectric properties of ɛ_r = 12.4, Q × f = 240,000 GHz and τ_f = −16.1 ppm/°C were obtained from the Sm₃Ga₅O₁₂ ceramics sintered at 1450 °C for 6 h with 1.0 mol% TiO₂. Therefore, Re₃Ga₅O₁₂ ceramics, especially TiO₂-added Sm₃Ga₅O₁₂ ceramics are good candidates for advanced substrate materials in microwave integrated circuits (MICs) applications.     

Effects of microwave sintering on the properties of 0.87(Mg0.7Zn0.3)TiO3–0.13(Ca0.61La0.26)TiO3 ceramics

0.87(Mg_0.7Zn_0.3)TiO₃–0.13(Ca_0.61La_0.26)TiO₃ (referred to as 87MZCLT) ceramics were prepared by microwave sintering and conventional sintering. The experimental results demonstrated that the sintering cycle of 87MZCLT ceramics was greatly shortened and the impurity phase (Mg_0.7Zn_0.3)Ti₂O₅ was eliminated by microwave sintering. Moreover, the 87MZCLT ceramics prepared by microwave sintering show more uniform, fine-grained microstructure as well as much less Zn evaporation. As a result, the quality factor was increased by 40% compared with conventional sintering. All samples were sintered at 1275 °C for 20 min with heating and cooling rate of 15 °C/min and gave excellent microwave dielectric properties: ?_r = 26.21, Q × f = 120,000 GHz, τ_f = ?3 ppm/°C.     

Effect of B2O3 and CuO additives on the sintering temperature and microwave dielectric properties of Ba(Zn1/3Nb2/3)O3 ceramics

The B₂O₃ added Ba(Zn_1/3Nb_2/3)O₃ (BBZN) ceramic was sintered at 900 °C. BaB₄O₇, BaB₂O₄, and BaNb₂O₆ second phases were found in the BBZN ceramic. Since BaB₄O₇ and BaB₂O₄ second phases have an eutectic temperature around 900 °C, they might exist as the liquid phase during sintering at 900 °C and assist the densification of the BZN ceramics. Microwave dielectric properties of dielectric constant (ɛ_r) = 32, Q × f = 3500 GHz, and temperature coefficient of resonance frequency (τ_f) = 20 ppm/°C were obtained for the BZN with 5.0 mol% B₂O₃ sintered at 900 °C for 2 h. The BBZN ceramics were not sintered below 900 °C and the microwave dielectric properties of the BBZN ceramics sintered at 900 °C were very low. However, when CuO was added, BBZN ceramic was well sintered even at 875 °C. The liquid phase related to the BaCu(B₂O₅) second phase could be responsible for the decrease of sintering temperature. Good microwave dielectric properties of ɛ_r = 36, Q × f = 19,000 GHz and τ_f = 21 ppm/°C can be obtained for CuO doped BBZN ceramics sintered at 875 °C for 2 h.     

Microwave dielectric characteristics of SrLaGaO4 and SrNdGaO4 ceramics

SrLnGaO₄ (Ln = La and Nd) ceramics with K₂NiF₄ structure were prepared by solid-state reaction approach, and the microwave dielectric properties and microstructures were characterized. The SrLaGaO₄ and SrNdGaO₄ ceramics with minor secondary phase, Sr₃Ga₂O₆, were obtained by sintering at 1250–1350 °C for 3 h, and good microwave dielectric characteristics were achieved: the ceramics had (1) ɛ = 20.3, Q × f = 16,219 GHz, and τ_f = −33.5 ppm/°C for SrLaGaO₄; and (2) ɛ = 21.4, Q × f = 16,650 GHz, and τ_f = 7.1 ppm/°C for SrNdGaO₄.     

Microwave dielectric properties of novel temperature stable high Q Li2Mg1−xZnxTi3O8 and Li2A1−xCaxTi3O8 (A = Mg,Zn) ceramics

The Li₂Mg_1?xZn_xTi₃O₈ (x = 0–1) and Li₂A_1?xCa_xTi₃O₈ (A = Mg, Zn and x = 0–0.2) ceramics are synthesized by solid-state ceramic route and the microwave dielectric properties are investigated. The Li₂MgTi₃O₈ ceramic shows ?_r = 27.2, Q_u × f = 42,000 GHz, and τ_f = (+)3.2 ppm/°C and Li₂ZnTi₃O₈ has ?_r = 25.6, Q_u × f = 72,000 GHz, and τ_f = (?)11.2 ppm/°C respectively when sintered at 1075 °C/4 h. The Li₂Mg_0.9Zn_0.1Ti₃O₈ dielectric ceramic composition shows the best dielectric properties with ?_r = 27, Q_u × f = 62,000 GHz, and τ_f = (+)1.1 ppm/°C. The effect of Ca substitution on the structure, microstructure and microwave dielectric properties of Li₂A_1?xCa_xTi₃O₈ (A = Mg, Zn and x = 0–0.2) has also been investigated. The materials reported in this paper are excellent in terms of dielectric properties and cost of production compared to commercially available high Q dielectric resonators.     

Structure and properties analysis for low-loss (Mg1−xCox)TiO3 microwave dielectric materials prepared by reaction-sintering method

(Mg_1?xCo_x)TiO₃ (x = 0.00–0.09) ceramics were prepared by reaction sintering method. The correlations of crystal structure and the properties were analyzed on the basis of Rietveld refinement for specimens with different x. For x ≤ 0.5, solid solution phases with the ilmenite structure were obtained, which can be confirmed by the X-ray diffraction patterns and the lattice parameters measured. Whereas for x > 0.05, secondary phase was detected besides the main phase. Dielectric properties were closely related with theoretical dielectric polarizabilities, packing fraction and average octahedral distortion. By increasing x from 0.00 to 0.09, the Q × f value of the specimen decreased from a maximum of 289,400 GHz to 228,100 GHz. A fine combination of microwave dielectric properties (?_r ～ 16.1, Q × f ～ 289,400 GHz, τ_f  ～ ?54.4 × 10^?6/°C) was achieved for MgTiO₃ ceramics sintered at 1350 °C for 4 h.