Sintering behavior,structure, and microwave properties of novel Li2xCu1-xMoO4 ceramics

In this study, we prepared a novel series of Li_2xCu_1-xMoO₄ (x = 0.02, 0.04, 0.06, 0.08, and 0.10) microwave ceramics. The dynamic sintering behavior, crystal phases, micro-morphologies, and dielectric properties of the samples were studied. The substitution of Li⁺ contributed to refining the crystal grain size, promoting the densification of microstructure, and enhancing the quality factor. Due to different valence substitutions, Cu⁺ ions were created, which were verified by X-ray photoelectron spectroscopy (XPS) and Raman experiments. In addition, the Raman shift, full width at half maximum (FWHM) value of the A_1g peak, and crystal microstrains were analyzed to gain a mechanistic understanding of the influence of structure on the dielectric properties. When x = 0.08, the Li_2xCu_1-xMoO₄ ceramic sintered at 675 °C exhibited optimal comprehensive properties with ε_r = 8.17, Qf = 68 476 GHz, and τ_f = ?25 ppm/°C, and good chemical stability between the ceramic and Al electrode was also achieved. These promising properties make Li_2xCu_1-xMoO₄ (x = 0.08) more suitable for ultra-low temperature co-fired ceramic (ULTCC) applications.     

Low-temperature sintering and microwave dielectric properties of Ca5Co4(VO4)6 ceramics

A novel low temperature firing high Q microwave dielectric ceramic Ca₅Co₄(VO₄)₆ was prepared by the conventional solid-state reaction method. The phase purity, microstructure, and microwave dielectric properties were investigated. The Ca₅Co₄(VO₄)₆ ceramic sintered at 875 °C exhibited excellent microwave dielectric properties: Qxf = 95,200 GHz (at 10.6 GHz), τ_f = −63 ppm/°C, ɛ_r = 10.1, and its ɛ_r corrected for porosity was calculated as 11.1.     

Microwave dielectric properties of multi-ions Ba(Zn,Ta)O3-based perovskite ceramics

In this study, Ba(Zn_1/3Ta_2/3)O₃-based complex perovskite compounds, including Ba(Zn_1/3Ta_2/3)O₃, Ba(Zn_1/3Ta_1/3Nb_1/3)O₃, Ba(Zn_1/6Co_1/6Ta_2/9Nb_2/9Sb_2/9)O₃, and Ba_1/2Sr_1/2(Zn_1/6Co_1/6Ta_2/9Nb_2/9Sb_2/9)O₃, were prepared and characterized. There was no second phase formation shown in the XRD patterns. Though it has been suggested that substitutions of multiple ions over A-site or B-site of the Ba(Zn_1/3Ta_2/3)O₃ ceramics may not be beneficial to their microwave dielectric properties, the Ba(Zn_1/6Co_1/6Ta_2/9Nb_2/9Sb_2/9)O₃ and Ba_1/2Sr_1/2(Zn_1/6Co_1/6Ta_2/9Nb_2/9Sb_2/9)O₃ ceramics in this study were found to perform in a fairly acceptable manner. The Ba(Zn_1/6Co_1/6Ta_2/9Nb_2/9Sb_2/9)O₃ ceramic (sintered at 1575 °C for 6 h) and the Ba_1/2Sr_1/2(Zn_1/6Co_1/6Ta_2/9Nb_2/9Sb_2/9)O₃ ceramic (sintered at 1550 °C for 6 h) reported the following characteristics after annealing at 1400 °C for 10 h: 24.9 and 27.0 for dielectric constants (?_r), 83,000 and 32,100 GHz for quality factors (Q × f) values and −12.8 and −22.6 ppm/°C for temperature coefficients of resonance frequency (τ_f).     

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.     

Phase transition,microstructure, and dielectric properties of Li/Ta/Sb co-doped (K,Na)NbO3 lead-free ceramics

Li/Ta/Sb co-doped lead-free (K_0.4425Na_0.52Li_0.0375)(Nb_0.93−xTa_xSb_0.07)O₃ (abbreviated KNLNST_x) piezoelectric ceramics, with Ta-doping ratio of x ranging from 0.0275 to 0.0675, were synthesized using the conventional solid-state reaction method at the sintering temperature of 1130 °C. The effects of Ta content on the microstructure, dielectric properties, and phase transition behavior of the prepared ceramics were systematically investigated. The X-ray diffraction results show that all KNLNST_x ceramics formed a secondary phase, which is assigned to the tetragonal tungsten-bronze type (TTB) structure phase, and showed a phase transition from an orthorhombic symmetry to a tetragonal symmetry across a composition region of 0.0375<x<0.0475. The grain shape and size that correspond to the phase structure transformations can be clearly observed in the scanning electron microscopy images. As x increased to 0.0475, the KNLNST_0.0475 ceramics changed from orthorhombic to tetragonal structure and showed excellent piezoelectric properties of d₃₃=313 pC/N, k_p=47%, and ε_r=1825. By contrast, samples of x=0.0375 with orthorhombic symmetry exhibited poor piezoelectric properties, with d₃₃=200 pC/N and ε_r=1015. These results indicate that phase structure is vital in the piezoelectric properties of KNN lead-free ceramics.     

SiO2/Al2O3 ratio dependence of microstructures and dielectric properties in barium strontium titanate glass ceramics

(Ba, Sr)TiO₃-Al₂O₃-SiO₂ glass ceramic system with various SiO₂/Al₂O₃ ratios was investigated by X-ray diffractometry (XRD), scanning electron microscopy (SEM), dielectric spectroscopy and impedance spectroscopy. The XRD results demonstrated that the proper SiO₂/Al₂O₃ ratio could promote the crystallization of the major crystalline phase from the glass matrix. The dielectric property investigations showed that the dielectric constant passes through a maximum value while the dielectric breakdown strength has a minimum value with increasing SiO₂/Al₂O₃ ratio. Meanwhile, the complex impedance analyses suggest the resistance of the glass-crystal interface rapidly decreases and the capacitance of the crystal slightly decreases with the increase of SiO₂/Al₂O₃ ratio. The relaxation mechanisms of the (Ba, Sr)TiO₃ glass ceramics changed from localized relaxation to long range conductivity as the SiO₂/Al₂O₃ ratio was increased from 1.43 to 1.83. The variations in the dielectric response and the activation energy of the glass-crystal interface in the (Ba, Sr)TiO₃ glass ceramics with the ratio of 2.40 could be attributed to the crystallization of fresnoite phase.     

Structure and microwave dielectric properties of ALn4(MoO4)7 (A = Ba,Sr, Ca,Ln = La,Pr, Nd,and Sm) ceramics

ALn₄(MoO₄)₇ (A = Ba, Sr, Ca, Ln = La, Pr, Nd, Sm) ceramics are prepared by solid state ceramic route and the structural properties have been studied using powder X-ray diffraction and laser Raman spectroscopy. All the ceramics under study are phase pure except BaLn₄(MoO₄)₇ (Ln = Pr, Nd, Sm). Scanning electron micrographs of the sintered ceramics show closely packed microstructure with phase homogeneity. BaLa₄(MoO₄)₇ ceramic has a maximum density of 4.5 g/cm³ at 710°C together with ԑ_r = 11.8, Q_u x f = 39 300 GHz, and τ_f = −68 ppm/^oC. SrLa₄(MoO₄)₇ ceramic exhibited a maximum density of 4.4 g/cm³, ԑ_r = 11.7, Q_u x f = 44 200 GHz, and τ_f = −83 ppm/^°C at 740°C whereas CaLa₄(MoO₄)₇ ceramic possess a maximum density of 4.2 g/cm³, ԑ_r = 11.4, Q_u x f = 30 200 GHz and τ_f = −90 ppm/^oC at 750°C at microwave frequencies. The chemical compatibility of the BaLa₄(MoO₄)₇, SrLa₄(MoO₄)₇ and CaLa₄(MoO₄)₇ ceramics with silver electrode have been studied using powder X-ray diffraction of the co-fired samples and is further examined with energy dispersive X-ray spectroscopy.     

Low-temperature sintering and microwave dielectric properties of 3Z2B glass–Al2O3 composites

A potential low temperature co-fired ceramics system based on zinc borate 3ZnO–2B₂O₃ (3Z2B) glass matrix and Al₂O₃ filler was investigated with regard to phase development and microwave dielectric properties as functions of the glass content and sintering temperature. The densification mechanism for 3Z2B–Al₂O₃ composites was reported. The linear shrinkage of 3Z2B glass–Al₂O₃ composites exhibited a typical one-stage densification behavior. XRD patterns showed that a new crystalline phase, ZnAl₂O₄ spinel, formed during densification, indicating that certain chemical reaction took place between the 3Z2B glass matrix and the alumina filler. Meanwhile, several zinc borate phases, including 4ZnO·3B₂O₃, crystallized from the glass matrix. Both of the reaction product phase and crystallization phases played an important role in improving the microwave dielectric properties of composites. The optimal composition sintered at 850–950 °C showed excellent microwave dielectric properties: ?_r = ∼5.0, Q·f₀ = ∼8000 GHz, and τ_f = ∼−32 ppm/°C at ∼7.0 GHz.     

Vanadium doping effects on microstructure and dielectric properties of barium titanate ceramics

V-doped barium titante ceramics were prepared by conventional solid state reaction method. XRD patterns show that V⁵⁺ ions have entered into the tetragonal perovskite structure of solid solution to substitute for Ti⁴⁺ ions on the B sites. Addition of vanadium accelerates grain growth of BTO ceramics and there is abnormal grain growth of barium titanate ceramics with higher vanadium concentration. Vanadium doping can increase the Curie temperature and decrease the dielectric loss of barium titanate ceramics. As vanadium concentration increases, the remnant polarization of V-doped BTO ceramics begins to increase and reaches the maximum and then decreases. The coercive electric field for V-doped barium titanate ceramics decreases with the increasing of vanadium concentration. As temperature rises, the remnant polarization and the coercive electric field of V-doped barium titanate ceramics decrease simultaneously.     

Phase formation and microwave dielectric properties of BiMVO5 (M = Ca,Mg) ceramics potential for low temperature co-fired ceramics application

Two low-firing BiMVO₅ (M = Ca, Mg) ceramics were prepared in the sintering temperature range of 760-850°C. Their differences in phase formation, sintering behavior, and dielectric performances were investigated. BiCaVO₅ formed a single phase with an orthorhombic structure, while BiMgVO₅ crystallized in a monoclinic structure that needs longer dwelling time to obtain single phase. The optimized microwave dielectric properties were obtained with ε_r = 15.70, Q × f = 55 000 GHz (at 10.6 GHz), and τ_f = −71 ppm/°C for BiCaVO₅, ε_r = 18.55, Q × f = 86 860 GHz (at 9.63 GHz), and τ_f = −65 ppm/°C for BiMgVO₅. In addition, the large negative τ_f values of BiMVO₅ (M = Ca, Mg) ceramics were successfully adjusted by forming composite ceramics with CaTiO₃ and near-zero τ_f values of +2 ppm/°C and −3 ppm/°C were obtained in 0.92BiCaVO₅-0.08CaTiO3 and 0.94BiMgVO₅-0.06CaTiO₃, respectively. Both ceramics exhibited good chemical compatibility with Ag electrode. The results demonstrate BiMVO₅ (M = Ca, Mg) ceramics to be attractive candidates in LTCC technology.     

Microwave dielectric properties of temperature-stable zircon-type (Bi,Ce)VO4 solid solution ceramics

In the (Bi_1 − xCe_x)VO₄ (0 ≤ x ≤ 1) system, we found that the (Bi_1 − xCe_x)VO₄ (0 ≤ x ≤ 0.1) belongs to the monoclinic scheelite phase and the (Bi_1 − xCe_x)VO₄ (0.7 ≤ x ≤ 1) belongs to the tetragonal zircon phase, while the (Bi_1 − xCe_x)VO₄ (0.1 < x < 0.7) belongs to the mixed phases of both monoclinic scheelite and tetragonal zircon structure. Interestingly, two components with near-zero temperature coefficient of resonant frequency (TCF) appeared in this system. In our previous work, a near-zero TCF of ~+15 ppm/°C was obtained in a (Bi_0.75Ce_0.25)VO₄ ceramic with a permittivity (ε_r) of ~47.9 and a Qf (Q = quality factor = 1/dielectric loss; f = resonant frequency) value of ~18 000 GHz (at 7.6 GHz). Furthermore, in the present work, another temperature-stable microwave dielectric ceramic was obtained in (Bi_0.05Ce_0.95)VO₄ composition sintered at 950°C and exhibits good microwave dielectric properties with a ε_r of ~11.9, a Qf of ~22 360 GHz (at 10.6 GHz), and a near-zero TCF of ~+6.6 ppm/°C. The results indicate that this system might be an interesting candidate for microwave device applications.     

Low-temperature preparation and microwave dielectric properties of cold sintered Li2Mg3TiO6 nanocrystalline ceramics

This study aims to fabricate Li₂Mg₃TiO₆ ceramics with ultrafine grains using a novel cold sintering process combined with a post-annealing treatment at a temperature <?950?°C. In this study, phase composition, sintering behavior, microstructure evolution, and microwave dielectric properties of the resultant nanocrystalline ceramics were investigated for the first time. The as-compacted green pellets at 180?°C yielded a high relative density of ~ 90% and the ceramics that were post-sintered over a broad temperature range (800–950?°C) possessed highly dense microstructure with a relative density of ~ 96%. The average grain size varied from 100 to 1200?nm for the samples sintered at 800–950?°C. Furthermore, the quality (Q × f) values of the obtained specimens exhibited a strong positive dependency on the grain size, which increased from 17,790 to 47,960?GHz for grain sizes ranging between 100 and 1200?nm, while the dielectric permittivity (ε_r) and temperature coefficient of the resonant frequency (τ_f) values did not undergo any significant changes over this range of grain size.     

Effects of non-stoichiometric defects on the dielectric properties of (Ba0.5Sr0.5)xTiO3-ZnGa2O4 composite ceramics

In order to explore the effects of non-stoichiometric defects on the dielectric properties of composite ceramics, 70 wt% (Ba_0.5Sr_0.5)_xTiO₃-30 wt%ZnGa₂O₄ ((BS)_xT50-ZG, x = (Ba + Sr)/Ti = 0.99, 1.00, 1.01 and 1.05) composite ceramics were fabricated by the traditional sintering technique. The association between structure and dielectric properties has been studied. The results show that the distortion of the crystal lattice brought by the partial Schottky defects, namely [V″_Ba,Sr–V^˙˙_O]^× and [V′′′′_Ti–2V^˙˙_O]^×, induces a decrease in the Curie temperature of (BS)_xT50-ZG composite ceramics. The orientation of the elastic dipoles brought by oxygen vacancies causes the pinning of the domain walls, which reduces the dielectric loss at low frequencies. Tunability is related to the dipole polarization caused by [V″_Ba,Sr–V^˙˙_O]^× and [V′′′′_Ti–2V^˙˙_O]^× defect complexes. In addition, compared with the composite ceramic with x = 1, the Q values of the composite ceramics with x < 1 and x > 1 decreases due to the deterioration of the microstructure homogeneity and the enhancement of the disorder of the B-site cations in (BS)_xT50.     

Structural and dielectric properties of B2O3/Li2O-added Ba0.6Sr0.4TiO3 multilayer ceramics for tunable devices

B₂O₃ and Li₂O (B/L)-added Ba_0.6Sr_0.4TiO₃ (BST) ceramics sintered at 940 °C exhibited a dense microstructure with large grains. The amount of B/L additive was 4.5 wt% with a B/L ratio of 1.5:1. The B/L-related liquid phase assisted the densification of the BST ceramics. This BST ceramic displayed a large dielectric constant (ε_r) of 2834 with a low dielectric loss (tan δ) of 0.21% at 1.0 MHz. It also displayed a large tunability (28.2% at 10 kV/cm) and a high figure of merit (FOM) of 134. BST thick-films were synthesized using the tape casting method. The thick-film densified at 940 °C exhibited a large tunability of 18.7% at 10.0 kV/cm and an FOM of 208; these are higher than the values reported in the literature. Multilayer ceramics (MLCs) consisting of five layers of 40-μm-thick BST thick-films and Ag electrodes were also fabricated at 940 °C. No diffusion occurred between the Ag electrode and BST thick-film. A large tunability of 67.6% at 52 kV/cm with a high FOM of 294 was obtained from this MLC. This verified that the B/L-added BST ceramic is effective for application in tunable multilayer devices.     

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.     

ZnLi2/3Ti4/3O4: A new low loss spinel microwave dielectric ceramic

A new low loss spinel microwave dielectric ceramic with composition of ZnLi_2/3Ti_4/3O₄ was synthesized by the conventional solid-state ceramic route. The ceramic can be well densified after sintering above 1075 °C for 2 h in air. X-ray diffraction data show that ZnLi_2/3Ti_4/3O₄ ceramic has a cubic structure [Fd-3m (227)] similar to MgFe₂O₄ with lattice parameters of a = 8.40172 Å, V = 593.07 Å³, Z = 8 and ρ = 4.43 g/cm³. The best microwave dielectric properties can be obtained in ceramic with relative permittivity of 20.6, Q × f value of 106,700 GHz and τ_f value of −48 ppm/°C. The addition of BaCu(B₂O₅) (BCB) can effectively lower the sintering temperature from 1075 °C to 900 °C and does not induce much degradation of the microwave dielectric properties. Compatibility with Ag electrode indicates that the BCB added ZnLi_2/3Ti_4/3O₄ ceramics are good candidates for LTCC applications.     

Effect of ZnO doping on the microstructure and microwave dielectric properties of 0.2CaTiO3-0.8(Li0.5Sm0.5)TiO3 ceramics

0.2CaTiO₃-0.8(Li_0.5Sm_0.5)TiO₃-xZnO(x = 0, 0.3, 0.6, 0.9, 1.2 wt%, 0.2CT-0.8LST-xZnO) with orthogonal perovskite structure were fabricated by the solid state method. The effects of ZnO additives on the microwave dielectric properties of 0.2CT-0.8LST ceramics were systematically investigated. With increasing the dopant (x) concentration, the dielectric constant (ε_r) and the temperature co-efficient of resonance frequency (τ_f) decreased, however, the Q × f values increased. The relationship between vibration mode and microwave dielectric properties was studied using Raman spectroscopy. The Q × f value of ceramics was related to the half-height width of Raman scattering. Narrower Raman scattering peaks corresponded to longer microwave energy propagation decay times and higher Q × f value. Based on X-ray photoelectron spectroscopy (XPS), the addition of Zn²⁺ ions limited the reduction of Ti⁴⁺ cations. The excellent dielectric properties were obtained when x = 1.2 wt% with ε_r = 100.25, Q × f = 6525 GHz, and τ_f = ?12.12 ppm/°C.     

Effects of in situ BiScO3 nanoparticles on the microstructure and dielectric properties of Ba0.7Sr0.3Ti0.9925Tm0.0103@BiScO3 ceramics

Ba_0.7Sr_0.3Ti_0.9925Tm_0.01O₃ (BST) and core-shell structured BST@BiScO₃ ceramics were prepared via a sol-precipitation and conventional sintering method. The single perovskite structure of the BST@BiScO₃ ceramic powder and bulk materials were confirmed via X-ray diffraction. Additionally, transmission electron microscopy analysis revealed that the surface of the BST powder was successfully coated in situ with amorphous BiScO₃ nanoparticles. Scanning electron microscopy analysis indicated that the grain sizes of the BST@x mol.% BiScO₃ (x = 1, 2, 3) ceramics decreased with increasing coating amounts. For x = 4 mol.%, the grain size of the BST@BiScO₃ ceramic significantly increased relative to that of BST@x mol.% BiScO₃ (x = 1, 2, 3), and some smaller particles were found to have precipitated. The results revealed that the dielectric constants of the BST@BiScO₃ ceramics decreased at room temperature, but remained above 10000, and that the dielectric loss was significantly reduced. In addition, the Curie peak of BST@x mol.% BiScO₃ (x = 1, 2, 3, 4) broadened and shifted to a higher temperature. The Curie peak of the BST@4 mol.% BiScO₃ ceramic material was nearly a flat line. In this work, dielectric materials with high dielectric constants and low dielectric losses were successfully prepared; thus, they met the requirements of miniaturization and temperature stability for dielectric ceramics.     

Colossal dielectric permittivity and relevant mechanism of Bi2/3Cu3Ti4O12 ceramics

Bi_2/3Cu₃Ti₄O₁₂ (BCTO) ceramics with pure perovskite phase were successfully prepared by traditional solid-state reaction technique. Uniformly distributed and dense grains with the grain size of 2–3 μm were observed by SEM. A giant low-frequency dielectric permittivity of ~3.3×10⁵ was obtained. The analysis of complex impedance revealed that Bi_2/3Cu₃Ti₄O₁₂ ceramics are electrically heterogeneous. There are three kinds of dielectric response detected in Bi_2/3Cu₃Ti₄O₁₂ ceramics, which existed in the low-frequency range, middle-frequency range, and high-frequency range, respectively. Through the study of dielectric spectrum at different temperatures, the relatively low activation energy of 0.30 eV for middle-frequency dielectric response was calculated, which suggested that this Middle-frequency dielectric response can be ascribed to grain boundaries response. In view of the analysis of dielectric spectrum at low temperatures, the activation energy of 0.07 eV for high frequency dielectric response was found. This value illustrated that dielectric response at high frequencies was associated with grains polarization effect. The comparison of dielectric spectra of Bi_2/3Cu₃Ti₄O₁₂ ceramics with different types of electrodes revealed that giant low-frequency dielectric constant was attributed to the electrode polarization effect.