Microwave dielectric properties and low-temperature sintering of Ba3Ti4Nb4O21 ceramics with B2O3 and CuO additions

The low sintering temperature and the good dielectric properties such as high dielectric constant (ɛ_r), high quality factor (Q × f) and small temperature coefficient of resonant frequency (τ_f) are required for the application of chip passive components in the wireless communication technologies. In the present study, the sintering behaviors and dielectric properties of Ba₃Ti₄Nb₄O₂₁ ceramics were investigated as a function of B₂O₃–CuO content. Ba₃Ti₄Nb₄O₂₁ ceramics with B₂O₃ or CuO addition could be sintered above 1100 °C. However, the additions of both B₂O₃ and CuO successfully reduced the sintering temperature of Ba₃Ti₄Nb₄O₂₁ ceramics from 1350 to 900 °C without detriment to the microwave dielectric properties. From the X-ray diffraction (XRD) studies, the sintering behaviors and the microwave dielectric properties of low-fired Ba₃Ti₄Nb₄O₂₁ ceramics were examined and discussed in the formation of the secondary phases. The Ba₃Ti₄Nb₄O₂₁ sample with 1 wt% B₂O₃ and 3 wt% CuO addition, sintered at 900 °C for 2 h, had the good dielectric properties: ɛ_r = 65, Q × f = 16,000 GHz and τ_f = 101 ppm/°C.     

Effect of silica sintering additive on the sintering behavior and dielectric properties of strontium barium niobate ceramics

Sr_0.5Ba_0.5Nb₂O₆ powders were prepared in the partial coprecipitation method. Using amorphous SiO₂ as the sintering additive, Sr_0.5Ba_0.5Nb₂O₆ ceramics were sintered at different temperatures and the effects of the additive on the sintering behaviors and dielectric properties were studied. The phase structure, microstructure and dielectric properties of the samples were investigated in X-ray diffraction (XRD), SEM and LCR analyzer respectively. The results indicated that the amorphous SiO₂ additive could accelerate the pore elimination, shorten the sintering time and enhance the density for Sr_0.5Ba_0.5Nb₂O₆ ceramics. The well development of microstructure promoted by the additives can result in the improvement of the dielectric constant and the weakening of the relax behavior. With the help of the additive of 1.5 wt.%, the relative density of the sample sintered at 1300 °C only for 2 h can reached 94.3% and the dielectric constant was up to 4322.     

Effect of V2O5 on sintering behaviour,microstructure and dielectric properties of textured Sr0.4Ba0.6Nb2O6 ceramics

The acicular Sr_0.39Ba_0.48K_0.32Nb₂O₆ single crystal particles were first prepared by the reaction of SrCO₃, BaCO₃ and Nb₂O₅ in molten K₂SO₄ at 1300 °C for 3 h. By using these single crystal particles as seeds and V₂O₅ as additives, textured Sr_0.4Ba_0.6Nb₂O₆ (SBN40) ceramics were obtained. The effect of V₂O₅ on sintering behaviour, microstructure and dielectric properties of textured SBN40 ceramics was investigated. The experimental results show that the addition of V₂O₅ can accelerate the densification rate of the material and encourage the texture of SBN40 ceramics, which further improves the anisotropy in dielectric properties between different directions of textured SBN40 ceramics.     

Microwave dielectric properties of (Ba1−xSrx)(Mg0.5W0.5)O3 ceramics

The densification, microstructural evolution and microwave dielectric properties of (Ba_1−xSr_x)(Mg_0.5W_0.5)O₃ ceramics with x=0, 0.25, 0.5 and 0.75 are investigated in this study. The sintering temperature of the (Ba_1−xSr_x)(Mg_0.5W_0.5)O₃ is significantly reduced from 1575 °C to 1400 °C as the x value increases from 0 to 0.25 and 0.50; this result is accompanied by the formation of the (Ba_1−ySr_y)WO₄ phase and a small quantity of second phase surrounding the grains. The grain size of the (Ba_1−xSr_x)(Mg_0.5W_0.5)O₃ ceramics is increased by raising the Sr²⁺ content, which significantly lowers the sintering temperature. The microstructure of the (Ba_0.75Sr_0.25)(Mg_0.5W_0.5)O₃ ceramic displays the smallest average grain size of approximately 0.8 μm, with a narrow grain size distribution. Without long annealing time, very high Q×f values are obtained for the (Ba_1−xSr_x)(Mg_0.5W_0.5)O₃ ceramics sintered at 1400–1575 °C for a duration of only 2 h. The (Ba_0.75Sr_0.25)(Mg_0.5W_0.5)O₃ ceramic sintered at 1400 °C results in the best microwave dielectric properties, including ε_r of 20.6, Q×f of 152,600 GHz and τ_f of +24.0 ppm/°C.     

Low-temperature sintering and microwave dielectric properties of Ba5Nb4O15 with ZnB2O4 glass

The Influence of ZnB₂O₄ glass addition on the sintering temperature and microwave dielectric properties of Ba₅Nb₄O₁₅ has been investigated using dilatometry, X-ray diffraction, scanning electron microscopy and network analyzer. It was found that a small amount of glass addition to Ba₅Nb₄O₁₅ lowered the sintering temperature from 1400 to 900 °C. The reduced sintering temperature was attributed to the formation of ZnB₂O₄ liquid phase and B₂O₃-rich liquid phases such as Ba₃B₂O₆. The Ba₅Nb₄O₁₅ ceramics with ZnB₂O₄ glass, sintered at a low temperature, exhibited good microwave dielectric characteristics, i.e., a quality factor (Q × f) = 12,100 GHz, a relative dielectric constant (ɛ_r) = 40, a temperature coefficient of resonant frequency (τ_f) = 48 ppm/°C. The dielectric properties were discussed in terms of the densification of specimens and the influence of glassy phases such as Ba₃B₂O₆ and ZnB₂O₄.     

Microwave dielectric properties of tungstenbronze type like (Ba1−αSrα)6−3xR8+2xTi18O54 (R = Sm,Nd) solid solutions

Tungstenbronze type like Ba_6−3xR_8+2xTi₁₈O₅₄ (R = Sm or Nd) dielectric ceramics reveal high quality factor Q·f as well as high dielectric constant ɛ_r. We have investigated the effect of Sr substitution for Ba ions on the microwave dielectric properties of the compounds. (Ba_1−αSr_α)_6−3xR_8+2xTi₁₈O₅₄ (R = Sm or Nd) ceramics were prepared in the composition ranges of x = 0–0.2 and α = 0–0.312 and the microwave dielectric properties were investigated. (Ba_1−αSr_α)_6−3xSm_8+2xTi₁₈O₅₄, where x = 0.1 and α = 0.298, and (Ba_1−αSr_α)_6−3xNd_8+2xTi₁₈O₅₄, where x = 0.2, α = 0.296 revealed remarkably higher Q·f value among the solid solutions, indicating that Q·f increased with substituting Sr ions into Ba ions at the rhombic A1-site. This fact suggests that relaxation of local distortions at the A1-sites is closely related to improvement of Q·f.     

Influence of low concentration MgCo2(VO4)2 addition on microwave dielectric properties of Ba0.6Sr0.4TiO3 ceramics

Ba_0.6Sr_0.4TiO_3?x MgCo₂(VO₄)₂ ceramics with x = 0, 0.5, 1.0, 2.0, and 5.0 wt% was fabricated via conventional solid-state reaction process. The effects of such additives on the structure, dielectric and tunability properties were systemically investigated. A small number of secondary phase identified as Ba₃(VO₄)₂ appeared in Ba_0.6Sr_0.4TiO_3?x MgCo₂(VO₄)₂ ceramics when x is more than 5.0 wt%. With increasing of MgCo₂(VO₄)₂ content, the peak values of permittivity gradually decreased and shifted to low temperature. The Ba_0.60Sr_0.40TiO₃ added with 0.5 wt% MgCo₂(VO₄)₂ possesses a dielectric constant of 2763, Q value of 267 at ～1 GHz and tunability of 35.9% under dc electric field of 30 kV/cm at 10 kHz.     

Effects of glass additions on the microstructure and dielectric properties of barium strontium titanate (BST) ceramics

Commercial glass frits (lead borosilicate glasses) were employed as the sintering aids to reduce the sintering temperatures of BST ceramics. The effects of the glass content and the sintering temperature on the microstructures, dielectric properties and tunabilities of BST ceramics have been investigated. Densification of BST ceramics of 5 wt% glass content becomes significant from sintering temperature of 1000 °C. The glass content shows a strong influence on the Curie temperature T_c, permittivity and the diffuse transition. X-ray results show all BST ceramics exhibit a perovskite structure and also the formation of a secondary phase, Ba₂TiSi₂O₈. The shift of BST diffraction peaks towards higher angle with increasing the glass content indicates the substitution of Pb²⁺ in Ba²⁺ site, which mainly accounts for the diffuse transition observed in these BST ceramics. BST ceramics with 10 wt% glass additives possess the highest tunability at all four sintering temperatures. A tunability of 12.2% at a bias field of 1 kV/mm was achieved for BST ceramics with 10 wt% glass content sintered at 900 °C.     

Property optimization of Ba0.4Sr0.6TiO3–BaMoO4 composite ceramics for tunable microwave applications

(1 ? x)Ba_0.4Sr_0.6TiO₃–xBaMoO₄ ceramics with x = 5, 10, 20, 30, 40 and 60 wt% were prepared by traditional solid-state reaction method. Two crystalline phases, a cubic perovskite structure Ba_0.4Sr_0.6TiO₃ (BST) and a tetragonal scheelite structure BaMoO₄ (BM) were obtained by XRD analysis. The microwave dielectric properties of Ba_0.4Sr_0.6TiO₃–BaMoO₄ composite ceramics were investigated systematically. The results show that the composite ceramics exhibited promising microwave properties. The dielectric constant can be adjusted in the range from 900 to 78, while maintaining relatively high tunability from 27.3% to 12.8% under a direct current electric field of 60 kV/cm and Q values from 619 to 67 in the gigahertz frequency region.     

Fabrication and dielectric properties of barium titanate-based glass ceramics for tunable microwave LTCC application

Low-fired ferroelectric glass ceramics were fabricated from glass powders with a basic composition of 0.65BaTiO₃·0.27SiO₂·0.08Al₂O₃. The combined addition of SnO₂ (or ZrO₂) and SrCO₃ was conducted to modify the dielectric properties of the glass ceramics. The Sr-component could be incorporated preferentially in the perovskite structure after heating at 1000 °C. The bulk and thick film samples obtained by sintering glass powder with a starting composition of 0.65(Ba_0.7Sr_0.3)(Ti_0.85Sn_0.15)O₃·0.27SiO₂·0.08Al₂O₃ at 1000 °C for 24 h showed a broadened ɛ_r–T relation with T_c ≈ 10 °C and ɛ_r(max) ≈ 280 and microwave tunability of 32% at 3 GHz, respectively.     

Silver cofirability differences between Bi1.5Zn0.92Nb1.5O6.92 and Zn3Nb2O8

We have investigated systematically the differences of silver cofirability and microwave dielectric properties between Zn₃Nb₂O₈ and Bi_1.5Zn_0.92Nb_1.5O_6.92 (BZN). Two type dopants: 0.29BaCO₃–0.71CuO (BC) and 0.81MoO₃–0.19CuO (MC) were used in Zn₃Nb₂O₈ and Bi_1.5Zn_0.92Nb_1.5O_6.92 ceramics so they can be cofired with silver. The BC-doped ceramics in general have better dielectric properties than those of MC-doped ceramics. The BC-doped Zn₃Nb₂O₈ exhibits better dielectric properties than those of BC-doped BZN (k = 14.7, Q × f = 8200 GHz versus k = 120.1, Q × f = 1050 GHz). For silver compatibility study, the interfacial behaviors between microwave dielectric materials and silver were investigated by using X-ray diffractometer, scanning electronic microscope, and electronic probe microanalyzer. No new crystalline phase and no silver migration behavior were found in the BC-doped Zn₃Nb₂O₈ ceramics cofired with silver, but slight silver migration was detected for BC-doped BZN. But slight silver migration was detected for MC-doped Zn₃Nb₂O₈ and BZN ceramics cofired with silver. Therefore, the good overall properties of BC-doped Zn₃Nb₂O₈ are suitable for microwave applications.     

Low-temperature microwave and THz dielectric response in novel microwave ceramics

Low-temperature dielectric properties of BaZn_1/3Nb_2/3O₃-based ceramics, CeO₂-based ceramics and Ruddlesden–Popper Sr_n+1Ti_nO_3n+1 (n = 1–4) ceramics has been studied in microwave, THz and infrared frequency range down to 10 K. Extrinsic dielectric losses originating probably from diffusion of charged defects are observed in two families of compounds by a minimum in the temperature dependence of microwave quality Q. The rise of microwave permittivity and dielectric losses at low temperatures in Sr_n+1Ti_nO_3n+1 (n = 2–4) ceramics was explained by softening of an optical polar mode in SrTiO₃, which is in the Sr_n+1Ti_nO_3n+1 (n = 3, 4) ceramics contained as a second phase.     

Effect of Li2O–V2O5 on the low temperature sintering and microwave dielectric properties of Li1.0Nb0.6Ti0.5O3 ceramics

Li₂O–Nb₂O₅–TiO₂ based ceramic systems have been the candidate materials for LTCC application, due to their high dielectric constant and Q × f value and controllable temperature coefficient in the microwave region. However, the sintering temperature was relatively higher (above 1100 °C) for practical application. In this study, dielectric properties of Li_(1+x−y)Nb_(1−x−3y)Ti_(x+4y)O₃ solid solution were studied with different x and y contents and among them, the Li_1.0Nb_0.6Ti_0.5O₃ composition (x = 0.1, y = 0.1) was selected, due to its reasonable dielectric properties to determine the possibility of low temperature sintering. The effects of 0.17Li₂O–0.83V₂O₅, as a sintering agent, on sinterability and microwave dielectric properties of Li_1.0Nb_0.6Ti_0.5O₃ ceramics were investigated as a function of the sintering agent content and sintering temperature. With addition of 0.17Li₂O–0.83V₂O₅ above 0.5 wt%, the specimens were well densified at a relatively lower temperature of 850 °C. Only slight decrease in apparent density was observed with increasing 0.17Li₂O–0.83V₂O₅ content above 0.75 wt%. In the case of 0.5 wt% 0.17Li₂O–0.83V₂O₅ addition, the values of dielectric constant and Q × f reached maximum. Further addition caused inferior microstructure, resulting in degraded dielectric properties. For the specimens with 0.5 wt% 0.17Li₂O–0.83V₂O₅ sintered at 850 °C, dielectric constant, Q × f and TCF values were 64.7, 5933 GHz and 9.4 ppm per °C, respectively.     

Dielectric tunable properties of high dielectric breakdown Ba0.5Sr0.5TiO3–Zn2P2O7 composite ceramics

Dielectric properties of Ba_0.5Sr_0.5TiO₃–xZn₂P₂O₇ (x = 1, 3, 5, 10, 15 wt%) composite ceramics, which were prepared by solid-state reaction process, were intensively investigated. The results showed that the Curie temperature (T_c) of composites gradually shifted to lower temperature (?140 °C) with increasing the content of Zn₂P₂O₇, and the dielectric constant were tuned effectively from 2020 to 107, while maintaining a relatively high tunability. Zn₂P₂O₇ additions remarkably inhibited the grain growth of Ba_0.5Sr_0.5TiO₃ phases, and improved the breakdown strength of samples up to 385 kV/cm. The sample with x = 10 wt% exhibited good dielectric properties (?_r = 290, tg δ = 0.0006, T = 20.5%, BDS = 297 kV/cm). Meanwhile Zn₂P₂O₇ addition also made the T_c far away from the room temperature, which reduced the sensitivity of the dielectric constant to temperature change and simultaneously improved the stability of materials.     

Effect of nonstoichiometry on the structure and microwave dielectric properties of Ba(Co1/3Nb2/3)O3 ceramics

The effect of B-site cation deficiency on the structure and microwave dielectric properties of Ba(Co_1/3Nb_2/3)O₃ (BCN) was investigated. Stoichiometric and co-deficient compositions based on Ba(Co_1/3−xNb_2/3)O₃ [x = 0.0, 0.01, 0.02, 0.03 and 0.04] were prepared using the conventional mixed oxide route. Small amounts of V₂O₅ (0.1 wt%) were added to promote densification. The dielectric loss is very sensitive to the composition; it was found that co-deficiency degraded the microwave dielectric properties. The stoichiometric formulation (x = 0) exhibited the best microwave properties. The improvements in the microwave dielectric properties were achieved by increasing the degree of 1:2 cation ordering. The highly ordered, stoichiometric BCN ceramics showed a relative permittivity (ɛ_r) of 32, quality factor (Q × f) of 66,500 GHz and a negative temperature coefficient of resonant frequency (τ_f) of −10 ppm/°C at 4 GHz.     

Synthesis and microwave dielectric properties of pseudobrookite-type structure Mg5Nb4O15 ceramics by aqueous sol–gel technique

Pseudobrookite-type Mg₅Nb₄O₁₅ ceramics were prepared by aqueous sol–gel process and microwave dielectric properties were investigated. Highly reactive nanosized Mg₅Nb₄O₁₅ powders were successfully synthesized at 600 °C in oxygen atmosphere with particle sizes of 20–40 nm firstly and then phase evolution was detected by DTA-TG and XRD. Sintering characteristics and microwave dielectric properties of Mg₅Nb₄O₁₅ ceramics were studied at different temperatures ranging from 1200 °C to 1400 °C. With the increase of sintering temperature, density, ?_r and Q·f values increased, and then saturated at 1300 °C. Excellent microwave properties of ?_r ～11.3, Q·f ～43,300 GHz and τ_f ～?58 ppm/°C, were obtained finally. The sintering temperature of Mg₅Nb₄O₁₅ ceramics was significantly reduced by aqueous sol–gel process compared to conventional solid-state methods.     

Molten-salt synthesis of Ba5−xSrxNb4O15 solid solutions and their enhanced humidity sensing properties

Layered perovskite-type niobates A₅Nb₄O₁₅ (A = Ba, Sr) are thought to be good candidates for microwave dielectric and water-splitting applications, but traditional solid-state syntheses of these compounds usually require high temperatures and complicated procedures. In this work, Ba_5?xSr_xNb₄O₁₅ (x = 0 ? 5) perovskite solid solutions were obtained using a facile molten salt synthetic method. The crystal structure of Ba_5?xSr_xNb₄O₁₅ solid solutions were characterized by X-ray diffraction (XRD). Crystal structure parameters with different Sr²⁺ concentrations show that the lattice parameters and unit cell volumes of Ba_5?xSr_xNb₄O₁₅ decrease with increasing [Sr²⁺]. The humidity sensing behavior of Ba_5?xSr_xNb₄O₁₅ solid solutions was investigated over a wide relative humidity (RH) range, from 11% to 95%. Ba₂Sr₃Nb₄O₁₅ shows the highest sensitivity among the obtained samples with a humidity hysteresis of ca. 4% RH. The response-recovery times of the Ba₂Sr₃Nb₄O₁₅ sensor are only 2 s and 17 s as the humidity alternates between 11% and 95% RH, respectively, showing excellent potential as a humidity sensing material for practical applications.     

A comparative study of Sr0.7Ba0.3Nb2O6 relaxor ferroelectric ceramics prepared by conventional and microwave sintering techniques

Sr_0.7Ba_0.3Nb₂O₆ (SBN70) ceramics were prepared by conventional sintering (CS) and microwave sintering (MWS) techniques. High-density ceramics were obtained by the MWS method in 2 h of cycle time, whereas it took 14 h by the CS method. Samples prepared by both sintering techniques showed single phase formation according to XRD results. It was observed that MWS SBN70 ceramics showed better densification and more uniform grain size than those of CS samples. The dielectric characteristics of both samples showed diffuse phase transition phenomenon features, which was confirmed by linear fitting of the modified Curie–Weiss law. Besides, the relaxor ferroelectric properties of both samples followed the Vogel–Fulcher relationship well. The value of spontaneous polarization (P_s) and the P–E hysteresis loop for MWS samples were significantly higher and slimmer than those of the CS samples, respectively.     

Low temperature sintering and microwave dielectric properties of Ba3Ti5Nb6O28 with ZnO–B2O3 glass additions for LTCC applications

The effects of ZnB₂O₄ glass additions on the sintering temperature and microwave dielectric properties of Ba₃Ti₅Nb₆O₂₈ have been investigated using dilatometer, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and a network analyzer. The pure Ba₃Ti₅Nb₆O₂₈ system showed a high sintering temperature (1250 °C) and had the good microwave dielectric properties: Q × f of 10,600 GHz, ɛ_r of 37.0, τ_f of −12 ppm/°C. It was found that the addition of ZnB₂O₄ glass to Ba₃Ti₅Nb₆O₂₈ lowered the sintering temperature from 1250 to 925 °C. The reduced sintering temperature was attributed to the formation of ZnB₂O₄ liquid phase and B₂O₃-rich liquid phases. Also the addition of ZnB₂O₄ glass enhanced the microwave dielectric properties: Q × f of 19,100 GHz, ɛ_r of 36.6, τ_f of 5 ppm/°C. From XPS and XRD studies, these phenomena were explained in terms of the reduction of oxygen vacancies and the formation of secondary phases having the good microwave dielectric properties.     

Changes in ordered structure and dielectric properties with the A-site and B-site cation ratios of complex perovskites (Sr1−xBax)(Sr0·33+yTa0·67−y)O3−δ

Complex perovskites with large-sized B′-site cations, (Sr_1−xBa_x)(Sr_0·33+yTa_0·67-y)O_3−δ (0 ≦ x ≦ 1, 0 ≦ y≦ 0·17), were fabricated to examine the transformation behavior between the (1:1) and (1:2) order types and dielectric property change with A-site cation substitution. The (1:2) type order was found to appear in a limited Ba-rich composition range. Structural strain induced by size difference between the A-site and large-sized B′-site cations might be responsible for the occurrence of the (1:1) type order in perovskite compounds substituted with more than 50% Sr²⁺ on the A-site sublattice. Low ε_r and positive temperature coefficient of ε_r observed for the (1:2) ordered samples were explained by the restricted ion movement in the (1:2) type order array.