Microstructure and microwave dielectric properties of Al2O3 added Li2ZnTi3O8 ceramics

Recently, the rapid development of advanced communication systems increasingly strongly demands high-performance microwave dielectric ceramics in microwave circuits. Among them, Li₂ZnTi₃O₈ ceramics have been one of the most widely investigated species, due to its high quality factor, moderate firing conditions and low cost. However, the dielectric constants of the already reported Li₂ZnTi₃O₈ ceramics are fixed in a narrow range, limiting their wider applications. To adjust the dielectric constant of the Li₂ZnTi₃O₈ based ceramics, in this work Li₂ZnTi₃O₈ ceramics added with different amounts of Al₂O₃ (0–8?wt%) were prepared by conventional solid-state reaction. The microstructure and microwave dielectric properties of the samples were investigated. Due to the addition of Al₂O₃, the sintering temperature of the ceramics would be increased somewhat. Some Al³⁺ ions could substitute for Ti⁴⁺ ions in Li₂ZnTi₃O₈, and the added Al₂O₃ would react with ZnO to produce a ZnAl₂O₄ phase accompanying with the formation of TiO₂ phase, which would inhibit the growth of Li₂ZnTi₃O₈ grains. The dielectric constant of the finally obtained ceramics would be reduced from 26.2 to 17.9, although the quality factors of the obtained ceramics would decrease somewhat and the temperature coefficient of resonant frequency would deviate further from zero.     

Effects of Li2O-B2O3-SiO2 glass on the low-temperature sintering of Zn0.15Nb0.3Ti0.55O2 ceramics

The influences of Li₂O-B₂O₃-SiO₂ glass (LBS) on the activation energy, phase composition, the stability of the structure and microwave dielectric properties of Zn_0.15Nb_0.3Ti_0.55O₂ ceramics have been systematically investigated. LBS glass acted as flux former and contributed to the reactive liquid-phase sintering mechanism, which remarkably lowed the sintering temperature from 1150?°C to 900?°C and enhanced the shrinkage and densification of ceramic at the low sintering temperatures. The ceramics with 1.5?wt% LBS glass sintered at 900?°C for 3?h show great properties: ε_r = 73.59, Q × f = 8024?GHz, τ_f = 270.54?ppm/°C.     

Solubility limits and microwave dielectric properties of Ba6−3xSm8+2xTi18O54 solid solution

Upper and lower solubility limits in Ba_6−3xSm_8+2xTi₁₈O₅₄ tungsten bronze ceramics were determined by Rietveld refinement of XRD data combined with backscattered electron images, and the variation tendency of microwave dielectric characteristics was also investigated. The upper solubility limit was confirmed as x = 2/3, while the lower solubility limit was determined as 1/4 instead of the previously reported one x = 3/10. The dielectric constant of Ba_6−3xSm_8+2xTi₁₈O₅₄ ceramics decreases monotonically with increasing x, while the small temperature coefficient of resonant frequency with complex variation tendency is observed for the compositions 1/2 ≤ x ≤ 4/5. The Qf value increases at first, reaches the maximum around x = 2/3, and turns to decrease for x > 7/10.     

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.     

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.     

Phase composition,Raman spectra,infrared spectra and dielectric properties of Li2MgTi1-x(Mg1/3Nb2/3)xO4 ceramics at microwave frequency

The Li₂MgTi_1-x(Mg_1/3Nb_2/3)_xO₄ (0?≤x?≤?0.5) ceramics were prepared by the conventional solid-state method. The relationship among phase composition, substitution amount and microwave dielectric properties of the ceramics was symmetrically investigated. All the samples possess the rock salt structure with the space group of Fm-3m. As the x value increases from 0 to 0.5, the dielectric constant linearly decreases from 16.75 to 15.56, which can be explained by the variation of Raman spectra and infrared spectra. The Q·f value shows an upward tendency in the range of 0?≤x?≤?0.3, but it then decreases when x?>?0.3. In addition, the temperature coefficient of resonant frequency (τ_f) is shifted toward zero with the increasing (Mg_1/3Nb_2/3)⁴⁺ addition. By comparison, 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.     

The homogeneity range and the microwave dielectric properties of the BaZn2Ti4O11 ceramics

Ceramics with a composition close to BaZn₂Ti₄O₁₁ were synthesized according to various substitutional mechanisms in order to verify an existence of a homogeneity range in the vicinity of this composition. Structural and microstructural investigations showed that the crystal structure of BaZn₂Ti₄O₁₁ was formed in the homogeneity range corresponding to the formula BaZn_2 − xTi₄O_11 − x (0 < x < 0.1). Densely sintered BaZn_2 − xTi₄O_11 − x (0 < x < 0.1) ceramics exhibited a dielectric constant around 30, τ_f = −30 ppm/K and high Q × f values, which increased from 68,000 GHz at x = 0 to 83,000 GHz at x = 0.05. Structurally, the deficiency of Zn in BaZn_2 − xTi₄O_11 − x (0 < x < 0.1) resulted in a slight decrease in the unit-cell volume. The influence of secondary phases in the BaZn₂Ti₄O₁₁-based materials on the microwave dielectric properties was also investigated. A presence of small amounts of ZnO, BaTiO₃, hollandite-type solid solutions (Ba_xZn_xTi_8 − xO₁₆) and BaTi₄O₉ caused a decrease in Q × f values.     

Crystal structures and microwave dielectric properties of low-firing Ca5Zn4-xMgxV6O24 ceramics

Ca₅Zn_4-xMg_xV₆O₂₄ (x?=?0–3) microwave dielectric ceramics with low sintering temperature were synthesized via the conventional solid-state reaction. Effects of the substitution of Mg²⁺ for Zn²⁺ on crystal structures and microwave dielectric properties were investigated. XRD and Rietveld refinement showed the solid solution single phase formed when 0?≤?x?≤?2, but a few ZnO was observed when x?=?3. Meanwhile, the lattice parameters were found to decrease monotonously with Mg content increasing. The vibration modes of Raman were confirmed and the relationship with microwave dielectric properties was analyzed. Appropriate substitution of Mg²⁺ improved the packing fraction, the cation ordering degree, and the Y-site bond valence, contributing to high Q×f and low | τ_f |. However, the ε_r reduced with the increasing content of Mg²⁺ due to the decrease of ion polarizability. Finally, the best microwave dielectric properties were achieved at x?=?2 with ε_r =?11.0, Q?×?f?=?66,365?GHz (at 10.0?GHz), and τ_f =??80.4?ppm/°C.     

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.     

Dielectric properties of polymers at microwave frequencies: a review

A review of the dielectric loss spectra of polymers at microwave frequencies has been carried out. While the main focus of attention is the frequency range from 100 MHz to 100 GHz, loss spectra outside this region are also reviewed because variations in temperature can cause a shift of dielectric loss into or out of the microwave range. A large volume of data for low loss polymers (polyethylene, polypropylene and poly(tetrafluoroethylene)), which are used in the communications industry, was available for review. Other polymers, for which data were available and which have significant loss at microwave frequencies are: polystyrene, poly(vinylchloride), poly(vinylidene chloride), poly(vinylidene fluoride), poly(methyl-methacrylate), poly(methyl acrylate), poly(oxymethylene), poly(ethylene oxide), poly(propylene oxide), polyacetylene, and poly(sulphur nitride). Also, the microwave dielectric properties of engineering thermoplastics such as poly(phenylene oxide), polycarbonate and polysulphane have been reviewed. The origins of microwave dielectric loss in polymers are categorized as: (a) dipolar absorption dispersions in both crystalline and amorphous polymers; (b) dipolar losses due to impurities, additives or fillers in a polymer material; (c) microwave absorption in conducting polymers (polyacetylene and poly(sulphur nitride)) for which the current carriers are electrons; and (d) photon-phonon absorption spectra corresponding to the density of states in amorphous regions of a polymer material.     

Temperature stability,low loss and defect relaxation of MgO-TiO2 microwave dielectric ceramics modified by Ca0.8Sr0.2TiO3

Temperature-stable and low-loss microwave dielectrics based on the MgO-TiO₂ system with nominal formation Mg_n+1Ti_nO_3n+1 (n = 5, MT) were prepared via the conventional solid-state reaction method. Ca_0.8Sr_0.2TiO₃ (CST) was chosen as a τ_f compensator for matrix MT to form the composite ceramics (1-x)Mg₆Ti₅O₁₆-xCa_0.8Sr_0.2TiO₃ (0.10 ≤ x ≤ 0.26, MT-CST). The effects of CST additions on the phase composition, defect relaxation behavior, and microwave dielectric properties of MT were investigated. It revealed that undoped MT was basically consisted of MgTiO₃ as a major phase and Mg₂TiO₄ as a minor phase, and such two phases coexisted well with CST additions. Interestingly, τ_f could be tuned close to zero (?1.28 ppm/°C) for the MT-CST ceramics at x = 0.22, accompanied with a high Q×f value ~ 74,200 GHz and a proper ε_r ~ 20.25 (9.90 GHz). These materials possessed a good potential for applications in microwave components and devices. Meanwhile, significant relaxation phenomena were observed in all the MT-CST samples using dielectric spectroscopy and thermally stimulated depolarization current (TSDC) techniques. The oxygen-vacancy-related defects, shown as ($T{i}_{Ti}^{\prime }$)-($V_O^{??}$) dipoles and $V_O^{??}$, were the main types of defects in MT-CST, which was responsible for the relaxation behavior; meanwhile, the defect concentrations increased with the increase of CST content, thus resulting in the increase of dielectric loss at low and high frequencies.     

Effects of Al2O3 addition on the microstructure and microwave dielectric properties of Ba4Nd9.33Ti18O54 ceramics

Ba₄Nd_9.33Ti₁₈O₅₄·x wt%Al₂O₃ (BNT-A) ceramics (x=0, 0.5, 1.0, 1.5, 2.0, 2.5) were prepared by the conventional solid state reaction. The effects of Al₂O₃ on the microstructure and microwave dielectric properties of Ba₄Nd_9.33Ti₁₈O₅₄ (BNT) ceramics were investigated. X-ray diffraction and backscatter electronic images showed that the Al₂O₃ additive gave rise to a second phase BaAl₂Ti₅O₁₄ (BAT). The formation mechanism and grain growth of the BAT phase were first discussed. Dielectric property test revealed that the Al₂O₃ additive had improved the dielectric properties of the BNT ceramics: increased the Q×f value from 8270 to 12,180 GHz and decreased the τ_f value from 53.4 to 11.2 ppm/°C. A BNT-A ceramic with excellent dielectric properties: ε_r=70.2, Q×f=12,180 GHz, τ_f=20 ppm/°C was obtained with 2.0 wt% Al₂O₃ added after sintering at 1320 °C for 4 h.     

The effects of dispersants on sinterability and microwave dielectric properties of Zr0.8Sn0.2TiO4 ceramics

This study investigated the effects of dispersants (deionised water and ethanol) on the sinterability, phase compositions and microwave dielectric properties of Zr_0.8Sn_0.2TiO₄ ceramics prepared by a solid-state reaction. Results showed the presence of impurity phases in low-density ceramics with ethanol as dispersant sintered from 1500?°C to 1550?°C. However, pure phase was detected in samples prepared with deionised water as dispersant when sintering temperature ranged from 1512?°C to 1550?°C. The microwave dielectric properties of the samples with deionised water significantly improved compared with those with ethanol. Thus, deionised water was suitable for preparing Zr_0.8Sn_0.2TiO₄ ceramics with a high density of approximately 98%, ε_r of 39.83, Q ×?f of 33,700?GHz and τ_f of +?3.5?ppm/°C.     

Microwave dielectric properties of barium substituted screen printed CaBi2Nb2O9 ceramic thick films

In the present study, Aurivillius-structured Ba²⁺ substituted CaBi₂Nb₂O₉ (CBNO) ceramic powder was synthesized by co-precipitation method. The CBNO thick films were delineated by screen printing method on alumina substrates using co-precipitated ceramic powder. The overlay method was adopted to measure the microwave dielectric properties of prepared thick films. Single phase layered perovskite structure of the prepared thick films was confirmed by X-ray Diffraction. The effects of Ba²⁺ substitution on the surface morphology, bonding, and microwave dielectric properties of thick films were systematically presented. The maximum value of microwave dielectric constant for the CBNO thick films at 11.8 GHz is 15.6 for Ba²⁺=0.8 substitution. The shift in the stretching vibration modes of the Nb-O bond of NbO₆ octahedron in the Raman spectra with a substitution of Ba²⁺ in CBNO was observed. The substitution of Ba²⁺ on A-site of CBNO improves the microwave dielectric properties of prepared thick films. This work may provide a new approach to enhance the microwave dielectric performance of Aurivillius-structured ceramic thick films.     

Effects of CaSiO3 addition on sintering behavior and microwave dielectric properties of Al2O3 ceramics

The effects of CaSiO₃ addition on the sintering behavior and microwave dielectric properties of Al₂O₃ ceramics have been investigated. The addition of CaSiO₃ into Al₂O₃ ceramics resulted in the emergence of Ca₂Al₂SiO₇ and CaAl₂Si₂O₈, which acting as liquid sintering aids can effectively lower the sintering temperature of Al₂O₃ ceramic. The Q × f value of Al₂O₃-CaSiO₃ ceramics decreased with the CaSiO₃ addition increasing because of the lower Q × f value of Ca₂Al₂SiO₇ and CaAl₂Si₂O₈. Compared with the pure CaSiO₃ ceramic, the Al₂O₃-CaSiO₃ ceramic with 20 wt% CaSiO₃ addition possessed good dielectric properties of ?_r = 9.36 and Q × f = 13,678 GHz at the similar sintering temperature.     

Microstructure and dielectric properties of low temperature sintered ZnNb2O6 microwave ceramics

Low sintering temperature ZnNb₂O₆ microwave ceramics were prepared by doping with mixed oxides of V₂O₅–Bi₂O₃ and V₂O₅–Bi₂O₃–CuO. The effects of additives on the microstructure and dielectric properties of the ceramics were investigated. The results show that doping with V₂O₅–Bi₂O₃ can reduce the sintering temperature of ZnNb₂O₆ from 1150 °C to 1000 °C due to the formation of V₂O₅ and Bi₂O₃ based eutectic phases. The combined influence of V₂O₅ and Bi₂O₃ resulted in rod-like grains. Co-doping CuO with 1 wt.% V₂O₅–1 wt.% Bi₂O₃ further lowered the sintering temperature to 880 °C, because eutectic phases could be formed between the CuO, V₂O₅ and Bi₂O₃. A second phase of (Cu₂Zn)Nb₂O₈ also forms when the content of CuO is greater than 2.5 wt.%. A pure ZnNb₂O₆ phase can be obtained when the amount of CuO was 1.0–2.5 wt.%. The Q × f values of ZnNb₂O₆ ceramics doped with V₂O₅–Bi₂O₃–CuO were all higher than 25,000 GHz. The dielectric constants were 22.8–23.8 at microwave frequencies. In addition, theτ_f values decreased towards negative as the content of CuO increased. The ceramic with composition of ZnNb₂O₆ + 1 wt.%V₂O₅ + 1 wt.% Bi₂O₃ + 2.5 wt.% CuO sintered at 880 °C exhibited the optimum microwave dielectric properties, is 23.4, Q × f is 46,975 GHz, and τ_f is −44.89 ppm/°C, which makes it a promising material for low-temperature co-fired ceramics (LTCCs).     

Microstructure and dielectric properties control of Ba4(Nd0.7Sm0.3)9.33Ti18O54 microwave ceramics

Microwave ceramics of Ba₄(Nd_0.7Sm_0.3)_9.33Ti₁₈O₅₄ with 0–3 wt% Ag additions were synthesized by a citrate sol–gel method. The BaO–B₂O₃–SiO₂ glass was also added into the sol–gel derived BNST ceramic powders as sintering aids. The undoped, Ag- and BaBS-doped samples can be sintered at 1250 °C, 1150 °C and 1000 °C, respectively. The microstructure and dielectric properties were then controlled by doping Ag or BaBS glass. Near isoaxial grains with about 250 nm and typical columnar grains were obtained for the silver-doped and BaBS-doped samples, respectively. For the <1 wt% silver-doped samples, the dielectric constant and Q × f retained unaltered but τ_f decreased from 9 ppm/°C to 1.4 ppm/°C. With increasing silver content from 1 wt% to 3 wt%, the dielectric constant and τ_f significantly increased but Q × f decreased. For the BaBS-doped samples, both dielectric constant and Q × f decreased but τ_f increased with increasing BaBS content.     

Effects of MnO2 and WO3 co-doping and sintering temperature on microstructure,microwave dielectric properties of Ba2Ti9O20 microwave ceramics

Ba₂Ti₉O₂₀ (short for B2T9) ceramics doped with 0.9 mol% MnO₂ and y mol% WO₃ were prepared by solid-state reaction. The influence of sintering temperature, content of WO₃ dopant and the molar ratio x of TiO₂: BaCO₃ on crystal structure, microstructures as well as microwave dielectric properties of B2T9 ceramics was systematically investigated. The major phase of all samples is B2T9, and the minor phase is BaWO₄, respectively. The content of impurity TiO₂ alternates with the variation of compositions and sintering temperature, which also leads to different microwave dielectric properties. With the continuous increase of the sintering temperature, the B2T9 phase grains gradually grow larger and transform from rod grains to plate-like grains. The enlargement and flattening of grains also result in the decrease of compactness and deterioration of microwave dielectric properties. It is found that B2T9 ceramics possess better performance when the sintering temperature is 1340°C, which is related to lower TiO₂ content, BaWO₄, B2T9 grain size, aspect ratio of B2T9 phase and high compactness. When x = 4 and y = 0.2, the relative dielectric constant, quality factor and the temperature coefficient of resonant frequency are 38, 23758 and 7 ppm/°C, respectively.     

Microstructure and dielectric properties of Ba0.6Sr0.4TiO3-MgAl2O4 composite ceramics

(1 − x)Ba_0.6Sr_0.4TiO₃-xMgAl₂O₄(x = 25, 30, 35 and 40 wt%) composite ceramics were prepared by conventional solid-state reaction method. The microstructures, dielectric properties and tunability of the composites have been investigated. The XRD patterns analysis reveals two crystalline phases, a cubic perovskite structure Ba_0.6Sr_0.4TiO₃ (BST) and a spinel structure MgAl₂O₄ (MA). SEM observations show that the BST grains slightly dwindle and agglomerate with increasing amounts of MA. A dielectric peak with very strong frequency dispersion is observed at higher MA content, and the Curie temperature shifts to a higher temperature with increasing MA content. The ceramic sample with 30 wt% MA has the optimized properties: the dielectric constant is 1503, the dielectric loss is 0.003 at 10 kHz and 25 °C, the tunability is 23.63% under a dc electric field of 1.0 kV/mm, which is suitable for ferroelectric phase shifter.     

Structure stability,bond characteristics and microwave dielectric properties of co-substituted NdNbO4 ceramics

Structure-property relationship of co-substituted (Mg²⁺_1/4Mo⁶⁺_3/4)⁵⁺, (Al³⁺_1/3Mo⁶⁺_2/3)⁵⁺, (Si⁴⁺_1/2Mo⁶⁺_1/2)⁵⁺, (Zr⁴⁺_1/2Mo⁶⁺_1/2)⁵⁺ for Nb⁵⁺ in NdNbO₄ ceramics was investigated systematically. The remarkable differences in dielectric properties of each composition originated from their bond characteristics and structure stability. The elongated/compressed bonds have an effect on the cell volume and polarization. And the average bond covalency of Nb-O bond was responsible for the development of permittivity. Q×f values and the total lattice energy went up to maximum when (Si_0.5Mo_0.5) occupied Nb-site. Variations of lattice energy together with Nb-O bond energy suggest that a more stable structure was obtained through co-substitution. The optimal microwave dielectric properties is: ε_r =?18.97, Q×f?=?49466?GHz, τ_f =?7.34?ppm/°C for NdNb_0.97(Si_0.5Mo_0.5)_0.03O₄, sintered at 1250?°C.