Sol-gel derived CaCu3Ti4O12 ceramics: Synthesis, characterization and electrical properties

The giant dielectric constant material CaCu₃Ti₄O₁₂ (CCTO) has been synthesized by sol-gel method, for the first time, using nitrate and alkoxide precursor. The electrical properties of CCTO ceramics, showing an enormously large dielectric constant ? ∼ 60,000 (100 Hz at RT), were investigated in the temperature range from 298 to 358 K at 0, 5, 10, 20, and 40 V dc. The phases, microstructures, and impedance properties of final samples were characterized by X-ray diffraction, scanning electron microscopy, and precision impedance analyzer. The dielectric permittivity of CCTO synthesized by sol-gel method is at least three times of magnitude larger than that synthesized by other low-temperature method and solid-state reaction method. Furthermore, the results support the internal barrier layer capacitor (IBLC) model of Schottky barriers at grain boundaries between semiconducting grains.     

Effect of copper-oxide segregation on the dielectric properties of CaCu3Ti4O12 thin films fabricated by pulsed-laser deposition

We investigated the effects of post-deposition cooling conditions on the surface morphologies and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) thin films grown by pulsed-laser deposition on Pt/TiO₂/SiO₂/Si substrates. CCTO thin films cooled under the typical cooling parameters, i.e., slow cooling (3 °C/min) at high oxygen pressure (66 kPa) showed a severe segregation of nanoparticles near the grain boundaries, which was identified to be copper oxide from electron probe micro analyzer mapping. On the other hand, we could not observe any segregation on the film surface when the samples were cooled fast (∼ 20 °C/min) at relatively low oxygen pressure (100 Pa). The dielectric constant, ε_r, of CCTO thin films deposited at 750 °C with severe surface segregation (ε_r ∼ 750 at 10 kHz) was found to be much lower than that (ε_r ∼ 2000 at 10 kHz) of CCTO thin films with smooth surface. As the copper-oxide segregation becomes more serious, which preferentially occurs at relatively high ambient oxygen pressure and temperature, the degradation in the dielectric properties of CCTO films becomes larger. The variation of dielectric constant of CCTO films with no copper-oxide segregation could be related to the presence of an impurity phase at grain boundaries.     

Modified tunable dielectric properties by addition of MgO on BaZr0.25Ti0.75O3 ceramics

Phase composition, microstructure and tunable dielectric properties of (1 − x)BaZr_0.25Ti_0.75O₃-xMgO (BZTM) composite ceramics fabricated by solid-state reaction were investigated. It was found Mg not only existed in the matrix as MgO, there was also trace amount of Mg²⁺ ions dissolved in the BZT grains, which led to Curie temperature of the BZTM composites ceramics shifting to below −100 °C. Dielectric permittivity of the BZTM composite ceramics was reduced from thousands to hundreds by manipulating the content of MgO. Johnson's phenomenological equation based on Devonshire's theory was used to describe the nonlinear dielectric permittivity of the ceramics with increasing applied DC field. With increasing content of MgO, anharmonic constant α_(T) increased monotonously. Dielectric permittivity was 672, while dielectric tunability was as high as 30.0% at 30 kV/cm and dielectric loss was around 0.0016 for the 0.6BaZr_0.25Ti_0.75O₃-0.4MgO sample at 10 kHz and room temperature.     

Microstructural evolution and dielectric properties of Cu-deficient and Cu-excess CaCu3Ti4O12 ceramics

The microstructural evolution and dielectric properties of CaCu_3−xTi₄O_12−x (3 − x = 2.8-3.05) ceramics were investigated. Normal grain growth behavior was observed at Cu/Ca ≤ 2.9, while abnormal grain growth was observed at Cu/Ca ≥ 2.95. A CuO-rich intergranular liquid phase at Cu/Ca ≥ 2.95 and angular grain morphology were the main reasons for abnormal grain growth. However, the abundant intergranular liquid at Cu/Ca = 3.05 significantly affected the relative dielectric permittivity and dielectric loss. The CuO composition is the key parameter that determines the microstructure and dielectric properties of CCTO ceramics.     

Dielectric and pyroelectric anisotropy in melt-quenched BaBi2(Nb1 − xVx)2O9 ceramics

The (0 0 l) textured BaBi₂(Nb_1 − xV_x)₂O₉ (where x = 0, 0.03, 0.07, 0.1 and 0.13) ceramics were fabricated via the conventional melt-quenching technique followed by high temperature heat-treatment (800-1000 °C range). The influence of vanadium content and sintering temperature on the texture development and relative density were investigated. The samples corresponding to the composition x = 0.1 sintered at 1000 °C for 10 h exhibited the maximum orientation of about 67%. The Scanning electron microscopic studies revealed the presence of platy grains having the a-b planes perpendicular the pressing axis. The dielectric constant and the pyroelectric co-efficient values in the direction perpendicular to the pressing axis were higher. The anisotropy in the dielectric constant is about 100 (at 100 kHz) at the dielectric maximum temperature and anisotropy in the pyroelectric co-efficient is about 50 μC cm⁻² °C⁻¹ in the vicinity of pyroelectric anomaly for the sample corresponding to the composition x = 0.1 sintered at 1000 °C. Higher values of the dielectric loss and electrical conductivity were observed in the direction perpendicular to the pressing axis which is attributed to the high oxygen ion conduction in the a-b planes.     

Study of the dielectric properties in the NaNbO3 -KNbO3-In2O3 system using AC impedance spectroscopy

We report a comparative study of the dielectric properties of solid-state (ceramic method) synthesized NaNbO₃ (NN), Na_0.75K_0.25NbO₃ (K25NN), K_0.5Na_0.5NbO₃ (KNN) and some composite materials containing In₂O₃ and NN or KNN using an AC impedance method. Powder X-ray diffraction (PXRD) was employed to investigate the phase purity. No significant amount of impurity phase was observed for NN, K25NN, and KNN. Substitutions of 10, 15 and 25 mol% In³⁺ for Nb⁵⁺ in KNN and NN using solid-state reactions at 1150 °C resulted in composite materials. AC impedance studies of NN, KNN and K25NN in the temperature range of 500-800 °C showed a single semicircle (attributed to the bulk property) in the high-frequency range of 10³ to 10⁶ Hz. The individual contributions from the bulk and grain boundary on the dielectric properties were resolved and quantified from the impedance data. The calculated dielectric values for NN were consistent with previously reported in the literature. 10% Indium based KNN composite materials had the lowest dielectric loss 0.585 and the dielectric constant of 233 at 100 kHz at the temperature of 650 °C.     

Electrical properties tailoring in Ni-particle-dispersed (Ba0.95Ca0.05)(Ti0.96Zr0.04)O3 composites

Ni-particle-dispersed (Ba_0.95Ca_0.05)(Ti_0.96Zr_0.04)O₃ (BCTZ/Ni) piezoceramic composites were prepared via sintering at 1300 °C in industrial N₂ gas. Structural characterizations showed that the metallic Ni was not oxidized and the BCTZ preserved the perovskite structure. The Ni particles were uniformly distributed in the BCTZ ceramic matrix. The relative dielectric constant ?_r of the BCTZ/Ni composites increased from 1362 to 3910 with increasing Ni content from 0 to 20 vol.%, which is explained by the Maxwell equation as well as the micro-capacitor model. The percolation theory of insulator–metal transitions is also applied to correlate the rapid increase of dielectric constant with Ni content. The piezoelectric constant d₃₃ gradually decreased from 230 to 50 pC N⁻¹, giving a gradient profile of piezoelectric property. We demonstrate that the electrical properties can be effectively tailored by dispersing metal particles into piezoceramics.     

Comparative investigation of structure and dielectric properties of Pb(Mg1/3Nb2/3)O3-PbTiO3 (65/35) and 10% PbZrO3-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 (65/35) ceramics prepared by a modified precursor method

Relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) and 10% PbZrO₃-doped Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramics were both prepared by a modified precursor method, which was based on the high-temperature synthesis of an oxide precursor that contained all the B-site cations for the consideration of B-site homogeneity. The dielectric properties of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramic was more of normal ferroelectric behavior, but the high dielectric constant (?_m = 34,200 at 1 kHz) and piezoelectric constant (d₃₃ = 709 pC/N) were observed for this composition close to the morphotropic phase boundary. Comparatively, introduction of 10% PbZrO₃ into Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramics enhanced the diffuse phase transition as well as the rhombohedral to tetragonal phase transition temperature, while it also kept the high dielectric constant (?_m = 29,600 at 1 kHz) and piezoelectric constant (d₃₃ = 511 pC/N).     

Tunable and microwave dielectric properties of Ba0.5Sr0.5TiO3-BaWO4 composite ceramics doped with Co2O3

Co₂O₃ doped BaWO₄-Ba_0.5Sr_0.5TiO₃ composite ceramics, prepared by solid-state route, were characterized systematically, in terms of their phase compositions, microstructure and microwave dielectric properties. Doping of Co₂O₃ promoted grain growth, reduced Curie temperature and broadened phase-transition temperature range of BaWO₄-Ba_0.5Sr_0.5TiO₃, which were attributed mainly to the substitution of Co³⁺ for Ti⁴⁺ at B site in the perovskite lattice. Dielectric diffusion behaviors of the composite ceramics were discussed. The composite ceramics all had dielectric tunability of higher than 10% at 30 kV/cm and 10 kHz, with promising microwave dielectric properties. Specifically, the sample doped with 0.2 wt.% Co₂O₃ exhibited a tunability of 20%, permittivity of 225 and Q of 292 (at 1.986 GHz), making it a suitable candidate for applications in electrically tunable microwave devices.     

Dielectric and tunable characteristics of Ba0.4Sr0.6TiO3-BaWO4 composite ceramics for microwave applications

Phase compositions, microstructure and microwave dielectric properties, of BaWO₄ (BW)-Ba_0.4Sr_0.6TiO₃ (BST) composite ceramics, prepared by the traditional solid-state route, were systematically characterized. Meanwhile, mechanism of dielectric tunability of those materials was discussed. Dielectric properties of the BW-BST composites at a DC bias field near the phase transition temperature could be interpreted by using Johnson's phenomenological equation. The sample with x = 0.60 exhibited a tunability of 29.5%, a dielectric permittivity of 192 and a Q value of 231 (at 2.700 GHz), which make it a promising candidate for applications in electrically tunable microwave devices.     

Temperature compensated Sr2Al2SiO7 ceramic for microwave applications

The Sr–Gehlenite (Sr₂Al₂SiO₇) ceramic has been prepared by the conventional solid-state ceramic route. Phase pure Sr₂Al₂SiO₇ (SAS) ceramic sintered at 1525 °C for 4 h has ?_r = 7.2 and Q_u × f = 33,000 GHz. The SAS showed large negative τ_f of −37.0 ppm/ °C. A low value of τ_f was achieved by preparing SAS–CaTiO₃ composite. The composite with 0.04 volume fractions (V_f) CaTiO₃ sintered at 1500 °C for 4 h showed good microwave dielectric properties: ?_r = 8.6, Q_u × f = 20,400 GHz and τ_f = +8.5 ppm/°C.     

Effect of MgWO4 content on properties of Ba0.5Sr0.5TiO3 composite ceramics for tunable microwave applications

xMgWO₄-(1 − x) Ba_0.5Sr_0.5TiO₃ (x = 0.0, 5.0, 15.0, 25.0 and 35.0 wt%) composite ceramics were prepared via solid state reaction processing. Their structural and dielectric properties were systematically characterized. A significant increase in grain size was observed with increasing MgWO₄ content, which was accompanied by obvious variations in dielectric properties of the composite ceramics. It is found that the permittivity peaks of the samples gradually shifted to low temperatures with increasing MgWO₄ content. At the same time, tunabilities of the composite ceramics decreased, but their Q values increased. The sample with 35 wt% MgWO₄ possesses a high tunability of 16.8% (∼10 kHz), a low permittivity of 65 and an appropriate Q value of 309 (∼4.303 GHz), which meet the requirements of high power and impedance matching, thus making it a promising candidate for applications as electrically tunable microwave devices.     

Optimized microwave dielectric properties of Co- and Ca-substituted Mg0.6Zn0.4TiO3

The system of (1 − y)(Mg_0.6Zn_0.4)_1−xCo_xTiO₃-yCaTiO₃ was investigated to optimize its microwave dielectric properties by adopting appropriate contents of Co and Ca and by controlling sintering conditions. The effect of Co substitution was to enhance densification and Qf value, while the addition of CaTiO₃ resulted in increases of dielectric constant and TCF. As an optimal compositions, 0.93(Mg_0.6Zn_0.4)_0.95Co_0.05TiO₃-0.07CaTiO₃ successfully demonstrated a dielectric constant of 23.04, a Qf of 79,460 GHz and a TCF value of +1.4 ppm/°C after firing at a relatively lower sintering temperature of 1200 °C. The increase of sintering temperature beyond 1200 °C tended to degrade overall microwave dielectric properties presumably due to Zn volatilization as evidenced by the presence of a Zn-deficient phase (MgTi₂O₅) at 1400 °C. An attempt to establish the correlation between microstructure characteristics and dielectric properties was made in this dielectric system where the extensive range of firing temperature up to 1400 °C was evaluated.     

Effect of Pb(Fe1/2Nb1/2)O3 modification on dielectric and piezoelectric properties of Pb(Mg1/3Nb2/3)O3-PbZr0.52Ti0.48O3 ceramics

10 mol% Pb(Fe_1/2Nb_1/2)O₃ (PFN) modified Pb(Mg_1/3Nb_2/3)O₃-PbZr_0.52Ti_0.48O₃ (PMN-PZT) relaxor ferroelectric ceramics with compositions of (0.9 − x)PMN-0.1PFN-xPZT (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9) were prepared. X-ray diffraction investigations indicated that as-prepared ceramics were of pure perovskite phase and the sample with composition of x = 0.8 was close to morphotropic phase boundary (MPB) between rhombohedral and tetragonal phase. Dielectric properties of the as-prepared ceramics were measured, and the Curie temperature (T_c) increased sharply with increasing PZT content and could be higher than 300 °C around morphotropic phase boundary (MPB) area. At 1 kHz, the sample with composition of x = 0.1 had the largest room temperature dielectric constant ?_r = 3519 and maximum dielectric constant ?_m = 20,475 at T_m, while the sample with composition of x = 0.3 possessed the maximum dielectric relaxor factor of γ = 1.94. The largest d₃₃ = 318 pC/N could be obtained from as-prepared ceramics at x = 0.9. The maximum remnant polarization (P_r = 28.3 μC/cm²) was obtained from as-prepared ceramics at x = 0.4.     

Effect of B2O3-Bi2O3-SiO2-ZnO glass on the sintering and microwave dielectric properties of 0.83ZnAl2O4-0.17TiO2

The 0.83ZnAl₂O₄-0.17TiO₂ (ZAT) ceramics were synthesized by solid state ceramic route. The effect of 27B₂O₃-35Bi₂O₃-6SiO₂-32ZnO (BBSZ) glass on the microwave dielectric properties of ZAT was investigated. The crystal structure and the microstructure of the ceramic-glass composites were studied by X-ray diffraction and scanning electron microscopic techniques. The low frequency dielectric loss was measured at 1 MHz. The dielectric properties of the sintered samples were measured in the microwave frequency range by the resonance method. Addition of 0.2 wt% of BBSZ improved the dielectric properties with quality factor (Q_u × f) > 120,000 GHz, temperature coefficient of resonant frequency (τ_f) = −7.3 ppm/°C and dielectric constant (?_r) = 11.7. Addition of 10 wt% of BBSZ lowered the sintering temperature to about 950 °C with Q_u × f > 10,000 GHz, ?_r = 10 and τ_f = −23 ppm/°C. The reactivity of 10 wt% BBSZ added ZAT with silver was also studied. The results show that ZAT doped with suitable amount of BBSZ glass is a possible material for low-temperature co-fired ceramic (LTCC) application.     

Influence of Bi2O3 and CuO addition on low-temperature sintering and dielectric properties of Ba0.6Sr0.4TiO3 ceramics

In this study, we tried to lower the sintering temperature of Ba_0.6Sr_0.4TiO₃ (BST) ceramics by several kinds of adding methods of Bi₂O₃, CuO and CuBi₂O₄ additives. The effects of different adding methods on the microstructures and the dielectric properties of BST ceramics have been studied. In the all additive systems, the single addition of CuBi₂O₄ was the most effective way for lowering the sintering temperature of BST. When CuBi₂O₄ of 0.6 mol% was mixed with starting BST powders and sintered at 1100 °C, the derived ceramics demonstrated dense microstructure with a low dielectric constant (? = 4240), low dielectric loss (tan δ = 0.0058), high tunability (Tun = 38.3%) and high Q value (Q = 251). It was noteworthy that the sintering temperature was significantly lowered by 350 °C compared with no-additive system, and the derived ceramics maintained the excellent microwave dielectric properties corresponding to pure BST.     

Improved high-Q microwave dielectric resonator using CuO-doped MgNb2O6 ceramics

The microwave dielectric properties and the microstructures of MgNb₂O₆ ceramics with CuO additions (1-4 wt.%) prepared with conventional solid-state route have been investigated. The sintered samples exhibit excellent microwave dielectric properties, which depend upon the liquid phase and the sintering temperature. It is found that MgNb₂O₆ ceramics can be sintered at 1140 °C due to the liquid phase effect of CuO addition. At 1170 °C, MgNb₂O₆ ceramics with 2 wt.% CuO addition possesses a dielectric constant (ε_r) of 19.9, a Q×f value of 110,000 (at 10 GHz) and a temperature coefficient of resonant frequency (τ_f) of −44 ppm/°C. The CuO-doped MgNb₂O₆ ceramics can find applications in microwave devices requiring low sintering temperature.     

Dielectric properties of (1−x)(Mg0.95Co0.05)TiO3-xCaTiO3 ceramic system at microwave frequency

The microwave dielectric properties and the microstructures of the (1−x)MgTiO₃-xCaTiO₃ ceramic system were investigated. With partial replacement of Mg by Co, dielectric properties of the (1−x)(Mg_0.95Co_0.05)TiO₃-xCaTiO₃ ceramics can be promoted. The microwave dielectric properties are strongly correlated with the sintering temperature. At 1275°C, the 0.95(Mg_0.95Co_0.05)TiO₃-0.05CaTiO₃ ceramics possesses excellent microwave dielectric properties: a dielectric constant ε_r of 20.3, a Q×f value of 107 000 ( at 7 GHz) and a τ_f value of −22.8 ppm/°C. By appropriately adjusting the x value in the (1−x)(Mg_0.95Co_0.05)TiO₃-xCaTiO₃ ceramic system, zero τ_f value can be achieved. With x=0.07, a dielectric constant ε_γ of 21.6, a Q×f value of 92 000 (at 7 GHz) and a τ_f value of −1.8 ppm/°C was obtained for 0.93(Mg_0.95Co_0.05)TiO₃-0.07CaTiO₃ ceramics sintered at 1275°C for 4 h.     

Study on properties of BaxSmyTi7O20 ceramics with CaO-SiO2-B2O3 glass

The effect of CaO-SiO₂-B₂O₃ (CSB) glass addition on the sintering temperature and dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics has been investigated using X-ray diffraction, scanning electron microscopy and differential thermal analysis. The CSB glass starts to melt at about 970 °C, and a small amount of CSB glass addition to Ba_xSm_yTi₇O₂₀ ceramics can greatly decrease the sintering temperature from about 1350 to about 1260 °C, which is attributed to the formation of liquid phase. It is found that the dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics are dependent on the amount of CSB glass and the microstructures of sintered samples. The product with 5 wt% CSB glass sintered at 1260 °C is optimal in these samples based on the microstructure and the properties of sintering product, when the major phases of this material are BaSm₂Ti₄O₁₂ and BaTi₄O₉. The material possesses excellent dielectric properties: ?_r = 61, tan δ = 1.5 × 10⁻⁴ at 10 GHz, temperature coefficient of dielectric constant is −75 × 10⁻⁶ °C⁻¹.     

Improved microwave dielectric properties of B2O3-doped Nd(Co1/2Ti1/2)O3 ceramics with near zero temperature coefficient of resonant frequency

The microwave dielectric properties and the microstructures of Nd(Co_1/2Ti_1/2)O₃ ceramics prepared by conventional solid-state route have been studied. The prepared Nd(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. It is found that low-level doping of B₂O₃ (up to 0.75 wt.%) can significantly improve the density and dielectric properties of Nd(Co_1/2Ti_1/2)O₃ ceramics. Nd(Co_1/2Ti_1/2)O₃ ceramics with additives could be sintered to a theoretical density higher than 98.5% at 1320 °C. Second phases were not observed at the level of 0.25-0.75 wt.% B₂O₃ addition. The temperature coefficient of resonant frequency (τ_f) was not significantly affected, while the dielectric constants (?_r) and the unloaded quality factors Q were effectively promoted by B₂O₃ addition. At 1320 °C/4 h, Nd(Co_1/2Ti_1/2)O₃ ceramics with 0.75 wt.% B₂O₃ addition possesses a dielectric constant (?_r) of 27.2, a Q × f value of 153,000 GHz (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of 0 ppm/°C. The B₂O₃-doped Nd(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.