Phase developments in the Pb(Zn1/2W1/2)O3-Pb(Zn1/3Ta2/3)O3-Pb(Zn1/3Nb2/3)O3 pseudo-ternary system

The phase stability ranges in the B-site precursor (Zn_1/2W_1/2)O₂-(Zn_1/3Ta_2/3)O₂-(Zn_1/3Nb_2/3)O₂ were determined by X-ray diffraction (XRD), where wolframite, tri-αPbO₂, and columbite phases were identified. Next attempts were carried out (with the addition of PbO) for the system Pb(Zn_1/2W_1/2)O₃-Pb(Zn_1/3Ta_2/3)O₃-Pb(Zn_1/3Nb_2/3)O₃, where the perovskite phase did not develop in the entire compositions investigated. Instead, only the Pb₂WO₅ and pyrochlore phases (along with ZnO) resulted.     

Distribution of pyrochlore phase in Pb(Mg1/3Nb2/3)O3-PbTiO3 films and suppression with a Pb(Zr0.52Ti0.48)O3 interfacial layer

Thin films of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) on Pt/Ti/SiO₂/Si (Pt/Si) substrates both with and without a Pb(Zr_0.52Ti_0.48)O₃ (PZT) interfacial layer were investigated. Perovskite and pyrochlore coexistence was observed for PMN-PT thin films without a PZT interfacial layer. Interestingly, most of the pyrochlore phase was observed in single-coated films and in the first layer of multi-coated films. The pyrochlore phase exhibited grains with an average size of about 25 nm, which is smaller than those of the perovskite phase (about 90 nm). In contrast, for PMN-PT thin films grown on a PZT interfacial layer, the formation of a pyrochlore phase at the interface between PMN-PT layers and the substrate is completely suppressed. Moreover, small grains are not observed in the films with a PZT interfacial layer. The measured polarization-electric field (P-E) hysteresis loops of PMN-PT films with and without PZT layers indicate that enhanced electrical properties can be obtained when a PZT interfacial layer is used. These enhanced properties include an increase in the value of remanent polarization P_r from 2.7 to 5.8 μC/cm² and a decrease in the coercive field E_c from 60.5 to 28.0 kV/cm.     

Effect of Pb(Zn1 / 2W1 / 2)O3 introduction on perovskite development and dielectric properties of (Ba,Pb)TiO3

Powders of a Pb(Zn_1 / 2W_1 / 2)O₃-introduced BaTiO₃-PbTiO₃ system were prepared. A two-step calcination route of a B-site precursor method was employed to promote perovskite formation. The overall effects of the Pb(Zn_1 / 2W_1 / 2)O₃ incorporation on changes in crystalline aspects as well as dielectric properties were explored.     

The effect of Sb2O5 additions on the dielectric properties of Ag(Nb0.8Ta0.2)O3 ceramics

The sintering behavior and dielectric properties for perovskite Ag(Nb_0.8Ta_0.2)O₃ ceramic with Sb₂O₅ doping was explored. A small amount of Sb₂O₅ (2.5 wt.%) led to high densification at temperatures < 1060 °C. The dielectric constant increased and the temperature coefficient decreased with increasing concentration of Sb₂O₅, and the dielectric constant reached 673, combined with a low temperature coefficient of 147 ppm/°C, and dielectric loss of 0.0044 (at 1 MHz) for the sample with 3.5 wt.% Sb₂O₅ sintered at 1080 °C.     

Sintering behavior and microwave dielectric properties of Bi3(Nb1−xTax)O7 solid solutions

Solid solutions of Bi₃(Nb_1−xTa_x)O₇ (x = 0.0, 0.3, 0.7, 1) were synthesized using solid state reaction method and their microwave dielectric properties were first reported. Pure phase of fluorite-type could be obtained after calcined at 700 °C (2 h)⁻¹ between 0 ≤ x ≤ 1 and Bi₃(Nb_1−xTa_x)O₇ ceramics could be well densified below 990 °C. As x increased from 0.0 to 1.0, saturated density of Bi₃(Nb_1−xTa_x)O₇ ceramics increased from 8.2 to 9.1 g cm⁻³, microwave permittivity decreased from 95 to 65 while Q_f values increasing from 230 to 560 GHz. Substitution of Ta for Nb modified temperature coefficient of resonant frequency τ_f from −113 ppm °C⁻¹ of Bi₃NbO₇ to −70 ppm °C⁻¹ of Bi₃TaO₇. Microwave permittivity, Q_f values and τ_f values were found to correlate strongly with the structure parameters of fluorite solid solutions and the correlation between them was discussed in detail. Considering the low densified temperature and good microwave dielectric proprieties, solid solutions of Bi₃(Nb_1−xTa_x)O₇ ceramics could be a good candidate for low temperature co-fired ceramics application.     

Effects of Fe2O3 doping on the microstructure and piezoelectric properties of 0.55Pb(Ni1/3Nb2/3)O3-0.45Pb(Zr0.3Ti0.7)O3 ceramics

0.55Pb(Ni_1/3Nb_2/3)O₃-0.45Pb(Zr_0.3Ti_0.7)O₃(PNN-PZT) ceramics with different concentration of xFe₂O₃ doping (where x = 0.0, 0.8, 1.2, 1.6 mol%) were synthesized by the conventional solid state sintering technique. X-ray diffraction analysis reveals that all specimens are a pure perovskite phase without pyrochlore phase. The density and grain size of Fe-doped ceramics tend to increase slightly with increasing concentration of Fe₂O₃. Comparing with the undoped ceramics, the piezoelectric, ferroelectric and dielectric properties of the Fe-doped PNN-PZT specimens are significantly improved. Properties of the piezoelectric constant as high as d₃₃ ~ 956 pC/N, the electromechanical coupling factor k_p ~ 0.74, and the dielectric constant ε_r ~ 6095 are achieved for the specimen with 1.2 mol% Fe₂O₃ doping sintered at 1200 °C for 2 h.     

Abnormal dielectric behaviors in Mn-doped CaCu3Ti4O12 ceramics and their response mechanism

Mn-doped CaCu₃Ti₄O₁₂ (CCTO) polycrystalline ceramics have been prepared by the conventional solid state sintering. Our results indicate that 10% Mn doping can decrease the dielectric permittivity in CaCu₃Ti₄O₁₂ by about 2 orders of magnitude (from 10⁴ to 10²). The grain and grain boundary activation energies show an obvious increase from 0.054 eV to 0.256 eV, and decrease from 0.724 eV to 0.258 eV with increasing the Mn doping concentration, respectively, which may be caused by the variation of Cu and Ti valence states in the CCTO samples evidenced by the X-ray absorption spectra. The similar grain and grain boundary activation energies result in invalidation of the internal boundary layer capacitance effect for the 10% Mn-doped CCTO sample, and thus result in the dramatic decrease of dielectric permittivity.     

Influence of rare-earth addition on microstructure and dielectric behavior of Ba0.6Sr0.4TiO3 ceramics

Ba_0.6Sr_0.4TiO₃ (BST) ceramics with 0.5 mol% various trivalent rare-earth additions prepared by a solid-state route are investigated. A strong correlation is observed between the microstructure, dielectric properties and rare-earth element dopant. The results display that comparing with the lattice constants of undoped and doped rare-earth BST, the structure transforms from cubic to tetragonal structure. In addition, the dopant improves the tetragonal distortion with the ionic radius of rare earth decreasing, and then deteriorates it with further decreasing. Large ions rare-earth additions effectively suppress the grain growth of BST. It is found that the temperature-permittivity characteristics for the BSTR (R, namely, rare earth) system could be controlled using various rare-earth elements. Especially, such as Sm, Eu, Gd dopants are effective to satisfy the tunable microwave devices application due to the decrease of permittivity and the improvement of dissipation factors of BST ceramic with the accompanying high-tunability.     

Microstructure, electrical and optical characteristics of Mg(Zr0.05Ti0.95)O3 thin films grown on Si substrate by sol-gel method

Optical properties and microstructures of Mg(Zr_0.05Ti_0.95)O₃ thin films prepared by sol-gel method on n-type Si(100) substrates at different annealing temperatures have been investigated. The surface structural and morphological characteristics analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscope (AFM) were found to be sensitive to the deposition conditions, such as annealing temperature (600-800 °C). The optical transmittance spectra of the Mg(Zr_0.05Ti_0.95)O₃ thin films were measured by using UV-visible recording spectro-photometer. The diffraction pattern showed that the deposited films exhibited a polycrystalline microstructure. All films exhibited Mg(Zr_0.05Ti_0.95)O₃ peaks orientation perpendicular to the substrate surface and the grain size with the increase in the annealing temperature. The dependence of the microstructure and dielectric characteristics on annealing temperature was also investigated.     

Enhancement microwave dielectric properties of La(Mg0.5Sn0.5)O3 ceramics by Substituting Mg for Co

The microwave dielectric properties of La(Mg_0.5−xCo_xSn_0.5)O₃ ceramics were examined with a view to exploiting them for mobile communication. The La(Mg_0.5−xCo_xSn_0.5)O₃ ceramics were prepared using the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La(Mg_0.4Co_0.1Sn_0.5)O₃ ceramics revealed that La(Mg_0.4Co_0.1Sn_0.5)O₃ is the main crystalline phase, which is accompanied by small extent of La₂Sn₂O₇ as the second phase. Formation of this Sn-rich second phase was attributed to the loss of MgO upon ignition. Increasing the sintering temperatures seemed to promote the formation of La₂Sn₂O₇. An apparent density of 6.67 g cm⁻³, a dielectric constant (?_r) of 20.3, a quality factor (Q.F.) of 70,500 GHz, and a temperature coefficient of resonant frequency (τ_f) of −77 ppm °C⁻¹ were obtained for La(Mg_0.4Co_0.1Sn_0.5)O₃ ceramics that were sintered at 1550 °C for 4 h.     

Influence of ZnO additions to 0.8(Mg0.95Co0.05)TiO3–0.2Ca0.6La0.8/3TiO3 ceramics on sintering behavior and microwave dielectric properties

The effects of ZnO addition on the microstructures and microwave dielectric properties of 0.8(Mg_0.95Co_0.05)TiO3–0.2Ca_0.6La_0.8/3TiO₃ ceramics were investigated. ZnO was selected as liquid phase sintering aids to lower the sintering temperature of 0.8(Mg_0.95Co_0.05)TiO3–0.2Ca_0.6La_0.8/3TiO₃ ceramics. With ZnO additives, the densification temperature of 0.8(Mg_0.95Co_0.05)TiO₃–0.2Ca_0.6La_0.8/3TiO₃ can be effectively reduced from 1450 to 1200–1325 °C. The crystalline phase exhibited no phase difference at low addition levels (0.25–2 wt.%). It is found that low-level doping of ZnO (0.25–2 wt.%) can significantly improve the density and dielectric properties of 0.8(Mg_0.95Co_0.05)TiO₃–0.2Ca_0.6La_0.8/3TiO₃ ceramics. The quality factors Q × f were strongly dependent upon the amount of additives. Q × f values of 36 000 and 13 000 GHz could be obtained at 1200–1325 °C with 1 and 2 wt.% ZnO additives, respectively. During all additives ranges, the relative dielectric constants were significantly different and ranged from 23.1 to 27.96. The temperature coefficient varies from 14.1–24.3 ppm/°C.     

Preparation and dielectric properties of BaCu(B2O5)-doped SrTiO3-based ceramics for energy storage

BaCu(B₂O₅) (BCB) was used as sintering aids to lower the sintering temperature of multi-ions doped SrTiO₃ ceramics effectively from 1300 °C to 1075 °C by conventional solid state method. The effect of BCB content on crystalline structures, microstructures and properties of the ceramics was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and dielectric measurements, respectively. The addition of BCB enhanced the breakdown strength (BDS) while did not sacrifice the dielectric constant. The enhancement of BDS should be due to the modification of microstructures, i.e., smaller and more homogeneous grain sizes after BCB addition. The dielectric constant of BCB-doped ceramics maintained a stable value with 1.0 mol% BCB, which was dominated by the combination of two opposite effects caused by the presence of second phases and the incorporation of Cu²⁺ and Ba²⁺, while further increase was owing to the increase of dissolved Ba²⁺ ions when the content of BCB is more than 2.0 mol%. The multi-ions doped SrTiO₃ ceramics with 1.0 mol% BCB addition showed optimal dielectric properties as follows: dielectric constant of 311.37, average breakdown strength of 28.78 kV/mm, discharged energy density of 1.05 J/cm³ and energy efficiency of 98.83%.     

Effects of Y2O3 addition on microwave dielectric characteristics of Al2O3 ceramics

Microwave dielectric characteristics of alumina ceramics with yttria addition were investigated. The sintering temperature was lowered, and the dielectric constant (ε_r) did not remarkably change by adding yttria. The microwave dielectric loss (tan δ) increased from 8.4 × 10^− 5 to 2.2 × 10^− 4, due to the presence of Al₅Y₃O₁₂ secondary phase. The grain size had significant effects on the dielectric loss, and there was an optimum grain size where the dielectric loss reached the minimum.     

Ba2Ti9O20-Ba1.85Sm4.1Ti9O24 layered dielectric resonators with adjustable effective dielectric constant

The layered dielectric resonator structures composed of Ba₂Ti₉O₂₀ (BTO) and Ba_1.85Sm_4.1Ti₉O₂₄ (BSTO) ceramic pellets were introduced to design new microwave dielectric materials with adjustable dielectric constant between 50 and 70. Good combination of microwave dielectric properties (?_r,eff = 50 ~ 70, Qf = 11,700-19,100 GHz and τ_f = − 4.3 to − 1.5 ppm/°C) was obtained by the present approach, and such combination could be optimized by adjusting the volume fraction of BSTO and stacking scheme. For practical applications, the BTO and BSTO layers could be bonded by low-loss adhesive, and the effects of the adhesive on the microwave dielectric properties were limited.     

Synthesis and properties of Ba(Zn1/3Ta2/3)O3 for microwave and millimeter wave applications

High dielectric materials have gained an important position in microwave electronics by reducing the size and cost of components for a wide range of applications from mobile telephony to spatial communications. Ba(Zn_1/3Ta_2/3)O₃ (BZT) is an A(B′B″)O₃ type perovskite material, showing ultra high values of the quality factor Q. Ceramic-based BZT dielectric materials were prepared by solid state reaction. The samples were sintered at temperatures in the range 1400 ÷ 1600 °C for 4 h. Compositional, structural and morphological characterization were performed by using XRD, SEM and EDX analysis. The dielectric properties were measured in the microwave range (6 ÷ 7 GHz). An additional annealing at 1400 °C for 10 h has improved some dielectric parameters. For samples sintered at temperatures higher than 1500 °C, the permittivity values were obtained in the interval 30 ÷ 35 and almost do not change the value after the annealing. The Q × f product substantially increases up to about 135,000 GHz, exhibiting a low temperature coefficient of the resonant frequency (τ_f) in microwaves. The best parameters were obtained for the samples sintered at 1600 °C with additional annealing. The achieved high values of the Q × f product recommend these materials for microwave and millimeter wave applications.     

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.     

Microwave dielectric characteristics of Ba(Mg1/3Ta2/3)O3 ceramics sintered at low-temperatures

The microwave dielectric properties and microstructures of Ba(Mg_1/3Ta_2/3)O₃ (BMT) ceramics sintered at low temperatures with 2–3 wt.% NaF additives were investigated. BMT ceramics sintered at 1340 °C for 3–12 h showed dielectric constants (_r) of 25.5–25.7, Qf values of 41 500–50 400 GHz and temperature coefficients of the resonator frequency (τ_f) of 10.9–21.4 ppm °C⁻¹. The variation of sintering time almost had no effect on the dielectric constant. The Qf value increased and the τ_f decreased with increasing sintering time. The ordering degree of Mg²⁺ and Ta⁵⁺ at B-sites increased with increasing sintering time.     

Phase diagrams and polarization of single-domain epitaxial Pb(Zr1-xTix)O3 thin films

Within the framework of modified Landau-Devonshire thermodynamic theory, the equilibrium polarization states and physical properties of single-domain Pb(Zr_1-xTi_x)O₃ (PZT) thin films epitaxially grown on dissimilar cubic substrates are investigated. The “misfit strain-temperature” phase diagrams are obtained for several different compositions (x = 0.75, 0.65 and 0.55) of PZT films. The presence of stability range of the monoclinic phase is the characteristic feature of these phase diagrams, which separates the stability ranges of the tetragonal phase and the orthorhombic phase. Further analysis shows that the monoclinic phase widens with the increase of Zr content, and meanwhile the center shifts from positive values of the misfit strain towards zero.     

The study on electrical behavior of Gd2O3-WO3 complex ceramics at high temperature

Gd₂O₃-WO₃ complex ceramics are fabricated by the conventional solid-state reaction process. The electrical characteristics and dielectric properties of the samples were measured at various ambient temperatures in a low electric field (E < 150 V/mm). As the temperature increases, the dielectric constant and the loss tangent show an obvious change at about 50 °C and 330 °C. When the temperature is above 200 °C, the samples display stable nonlinear electrical properties characterized by semiconductivity, and the nonlinearity increases along with increasing temperature. XRD analysis reveals that Gd₂W₂O₉ is the main phase and Gd₂O₃ is the secondary phase. Based on the phase transition of tungsten trioxide, these electrical properties of Gd₂O₃-WO₃ complex ceramics can be simply explained.