High dielectric constant and low-loss dielectric ceramics of Ba5LnZnNb9O30 (Ln = La,Nd and Sm)

Polycrystalline Ba₅LnZnNb₉O₃₀ (Ln = La, Nd and Sm) ceramics were prepared as single-phase materials through conventional solid-state ceramics route. The structure was characterized by X-ray diffraction methods and scanning electron microscopy (SEM) and the dielectric properties were measured from − 120 °C to 150 °C. All three compounds are paraelectric phases adopting the filled tetragonal tungsten–bronze (TB) structure at room temperature, and the Curie temperature (at 1 MHz) were − 60, − 25 and − 5 °C for Ba₅LaZnNb₉O₃₀, Ba₅NdZnNb₉O₃₀, and Ba₅SmZnNb₉O₃₀ respectively. At 1 MHz their dielectric constant (ε_r) varies from 258 to 310, dielectric loss (tanδ) from 0.0033 to 0.0068, and the temperature coefficients of the dielectric constant (τ_ε) from − 1220 to − 1390 ppm °C^− 1.     

Microwave dielectric properties of xNd(Zn1/2Ti1/2)O3–(1 − x)CaTiO3 ceramics

The microwave dielectric properties of xNd(Zn_1/2Ti_1/2)O₃–(1 − x)CaTiO₃ have been investigated. The system has been prepared by a conventional solid state ceramic route. Nd(Zn_1/2Ti_1/2)O₃ (NZT) possesses a dielectric constant (ε_r) of 32, a high quality factor (Q × f) of 170,000 GHz and a temperature coefficient of resonant frequency (τ_f) of − 42 ppm/°C. In order to produce a temperature-stable material, the addition of CaTiO₃ leads to a near-zero temperature variation of resonant frequency. In general, the microwave quality factor (Q × f) decreased as x increased and the temperature coefficient of resonant frequency (τ_f) was approximately linearly proportional to permittivity. The dielectric constant decreases from 77 to 32 as x varies from 0.2 to 1.0. The dielectric constant (ε_r) of 45, Q × f value of 56,000 (at 6 GHz) and temperature coefficient of resonant frequency (τ_f) of 0 ppm/°C were obtained for 0.5Nd(Zn_1/2Ti_1/2)O₃–0.5CaTiO₃ ceramics sintered at 1300 °C for 4 h. As the content of x increases, the highest Q × f value of 136,200 GHz for x = 0.8 is achieved at the sintering temperature 1300 °C.     

Piezoelectric and dielectric properties of 0.98(Na0.5K0.5)NbO3–0.02Ba(ZrxTi(1−x))O3 ceramics

Lead-free 0.98(Na_0.5K_0.5)NbO₃–0.02Ba(Zr_xTi_(1?x))O₃ (0.98NKN–0.02BZT) ceramics with Zr contents were fabricated by a conventional mixed-oxide method. The results indicate that the Zr/Ti ratio significantly influences the structural, piezoelectric, dielectric, and ferroelectric properties of 0.98NKN–0.02BZT ceramics. For the 0.98NKN–0.02BZT (x = 0) ceramics sintered at 1090 °C, the bulk density increased as the Zr contents decreased and showed a maximum value at x = 0. The Curie temperature of the 0.98NKN–0.02BZT ceramics slightly decreased as the Zr contents increased. The dielectric constant, piezoelectric constant, and electromechanical coupling factor of samples were maximized at x = 0, which might be due to the increase in density. A high d₃₃ = 194 pC/N, k_p = 38% were obtained for the 0.98NKN–0.02BZT ceramics sintered at 1090 °C for 4 h.     

Dielectric properties of Sb2O3-doped Ba0.672Sr0.32Y0.008TiO3

Sb₂O₃-doped Ba_0.672Sr_0.32Y_0.008TiO₃ (BSYT) dielectric ceramics were prepared by conventional solid state method, and their dielectric properties were investigated with variation of Sb₂O₃ doping content and sintering temperature. The X-ray diffraction patterns indicated that all the BSYT specimens possessed the perovskite polycrystalline structure. The experimental results reveal that the introduction of Sb₂O₃ into Ba_0.672Sr_0.32Y_0.008TiO₃ can control the grain growth, reduce the relative dielectric constant and dielectric loss, shift the Curie temperature to lower temperature and significantly improve the thermal stability of the BSYT ceramics. The samples doped with 1.6 wt.% Sb₂O₃ sintered at 1320 °C for 2 h exhibited attractive properties, including high relative dielectric constant (> 1500), low dielectric loss (< 40 × 10^− 4), low temperature coefficient of capacitor(< ± 35%) over a wide temperature range from − 25 °C to + 85 °C.     

Effect of BaCu(B2O5) on the sintering temperature and microwave dielectric properties of BaO–Ln2O3–TiO2 (Ln = Sm,Nd) ceramics

BaCu(B₂O₅) (BCB) ceramic powder was used to decrease the sintering temperatures of BaSm₂Ti₄O₁₂ (BST) and BaNd₂Ti₅O₁₄ (BNT) ceramics. The sintering temperature of the BST and BNT ceramics was reduced from approximately 1350 °C to 850 °C by the addition of BCB. The bulk density of the specimens increased and reached the saturated value with increasing BCB content. The variation of the dielectric constant (ɛ_r) was similar to that of the bulk density and, thus, the relative density plays an important role in determining the ɛ_r value of the specimens. The Q-value initially increased with the addition of BCB but decreased considerably when a large amount of BCB was added because of the presence of the liquid phase. Good microwave dielectric properties of Qxf = 4500 GHz, ɛ_r = 60 and τ_f = −30 ppm/°C were obtained for the 16.0 mol% BCB-added BST ceramics sintered at 875 °C for 2 h.     

Effect of V2O5 additive to 0.4SrTiO3–0.6La(Mg0.5Ti0.5)O3 ceramics on sintering behavior and microwave dielectric properties

The effect of V₂O₅ addition on the microwave dielectric properties and the microstructures of 0.4SrTiO₃–0.6La(Mg_0.5Ti_0.5)O₃ ceramics sintered for 5 h at different sintering temperature were investigated systematically. It was found that the sintering temperature was effectively lowered about 200 °C by increasing V₂O₅ addition content. The grain sizes, bulk density as well as microwave dielectric properties were greatly dependent on sintering temperature and V₂O₅ content. The 4ST–6LMT ceramics with 0.25% V₂O₅ sintered at 1400 °C for 5 h in air exhibited optimum microwave dielectric properties of ɛ_r = 50.7, Q × f = 15049.6 GHz, T_f = −1.7 ppm/°C.     

Synthesis of the giant dielectric constant oxide CaCu3Ti4O12 via ethylenediaminetetraacetic acid precursor

CaCu₃Ti₄O₁₂ powders were prepared via EDTA route and single-phase CaCu₃Ti₄O₁₂ was obtained at 800 °C for 2 h. DTA/TG and XRD were used to characterize the precursor and derived oxide powders. The dielectric properties of CaCu₃Ti₄O₁₂ ceramics were presented. Increasing sintering temperature leads to the increase in dielectric constant. CaCu₃Ti₄O₁₂ ceramics sintered at 1090 °C for 3 h exhibited giant dielectric constant of up to 2.1 × 10⁵ at room temperature and 100 Hz, which is significantly higher than those obtained from other chemical methods.     

Effect of B2O3 and CuO additives on the sintering temperature and microwave dielectric properties of Ba(Mg1/3Nb2/3)O3 ceramics

B₂O₃ added Ba(Mg_1/3Nb_2/3)O₃ (BBMN) ceramics cannot be sintered below 930 °C. However, when CuO was added to them, they were sintered even at 850 °C. The amount of the Ba₂B₂O₅ second phase, which was formed in the BBMN ceramics decreased with the addition of CuO. Therefore, the CuO additive is considered to react with the B₂O₃ inhibiting the reaction between B₂O₃ and BaO. A dense microstructure without pores developed with the addition of a small amount of CuO. The bulk density, dielectric constant (ɛ_r) and Q-value increased with the addition of CuO, but decreased when a large amount of CuO was added. Excellent microwave dielectric properties were obtained for the Ba(Mg_1/3Nb_2/3)O₃ + 2.0 mol% B₂O₃ + 10.0 mol% CuO ceramic sintered at 875 °C for 2 h, with values Q_xf = 21 500 GHz, ɛ_r = 31 and temperature coefficient of resonance frequency (τ_f) = 21.3 ppm/°C.     

Structure and microwave dielectric characteristics of lithium-excess Ca0.6Nd0.8/3TiO3/(Li0.5Nd0.5)TiO3 ceramics

Compositions based on (1−x)Ca_0.6Nd_8/3TiO₃−x(Li_1/2Nd_1/2)TiO₃ + yLi (CNLNTx + yLi, x = 0.30–0.60, y = 0–0.05), suitable for microwave applications have been developed by systematically adding excess lithium in order to tune the microwave dielectric properties and lower sintering temperature. Addition of 0.03 excess-Li simultaneously reduced the sintering temperature and improved the relative density of sintered CNLNTx ceramics. The excess Li addition can compensate the evaporation of Li during sintering process and decrease the secondary phase content. The CNLNTx (x = 0.45) ceramics with 0.03 Li excess sintered at 1190 °C have single phase orthorhombic perovskite structure, together with the optimum combination of microwave dielectric properties of ɛ_r = 129, Q × f = 3600 GHz, τ_f = 38 ppm/°C. Obviously, excess-Li addition can efficiently decrease the sintering temperature and improve the microwave dielectric properties. The high permittivity and relatively low sintering temperatures of lithium-excess Ca_0.6Nd_0.8/3TiO₃/(Li_0.5Nd_0.5)TiO₃ ceramics are ideal for the development of low cost ultra-small dielectric loaded antenna.     

Sintering temperature-induced electrical properties of (Ba0.90Ca0.10)(Ti0.85Zr0.15)O3 lead-free ceramics

Effects of the sintering temperature on the microstructure and electrical properties of (Ba_0.90Ca_0.10)(Ti_0.85Zr_0.15)O₃ (BCTZ) lead-free piezoelectric ceramics have been studied, where these ceramics were prepared by the conventional oxide-mixed method at varied sintering temperatures from 1300 °C to 1500 °C. These BCTZ ceramics exhibits a phase transition from a rhombohedral phase to the coexistence of rhombohedral and tetragonal phases with an increase of sintering temperature. With an increase of sintering temperature, their relative density and average grain size gradually increase, and electrical properties are improved greatly. These BCTZ ceramics sintered at ～1440 °C have optimum electrical properties: d₃₃ ～ 442 pC/N and k_p ～ 48.9%, making it a promising material for lead-free piezoelectric ceramics.     

Influence of V2O5 additions to Ba(Mg1/3Ta2/3)O3 ceramics on sintering behavior and microwave dielectric properties

The microstructures and the microwave dielectric properties of barium magnesium tantalate ceramics prepared by conventional mixed oxide route have been investigated. The prepared Ba(Mg_1/3Ta_2/3)O₃ exhibited a mixture of cubic perovskite and a hexagonal superstructure with Mg and Ta showing 1:2 order in the B-site. It is found that low level doping of V₂O₅ (up to 0.5 wt.%) can significantly improve densification of the specimens and their microwave dielectric properties. The density of doped Ba(Mg_1/3Ta_2/3)O₃ ceramics can be increased beyond 95% of its theoretical value by 1500 °C-sintering, which is caused by the liquid-phase effect of V₂O₅ addition. The detected second phase Ta₂O₅ was mainly the result of V⁵⁺ substitution in the ceramics. Dielectric constant (ε_r) and temperature coefficient of resonant frequency (τ_f) were not significantly affected, while the unloaded quality factors Q were effectively promoted by V₂O₅ addition due to the increase in B-site ordering. The ε_r value of 24.1, Q×f value of 149,000 (at 10 GHz) and τ_f value of 7.2 ppm/°C were obtained for Ba(Mg_1/3Ta_2/3)O₃ ceramics with 0.25 wt.% V₂O₅ addition sintered at 1500 °C for 3 h.     

Microstructures and microwave dielectric properties of Ba4LiNb3O12–BaWO4 composite ceramics

Composite ceramics of (1 ? x)Ba₄LiNb₃O₁₂–xBaWO₄ (x = 0.36–0.69) had been synthesized by co-firing the mixtures of Ba₄LiNb₃O₁₂ and BaWO₄ powders. The structures and microwave dielectric properties of the ceramics were studied by XRD, SEM, and TEM. These ceramics consisted of hexagonal Ba₄LiNb₃O₁₂ and tetragonal BaWO₄. The two phases co-existed well in the ceramics, and there was not obvious reaction at interfacial areas among grains. These ceramics had low sintering temperatures and excellent microwave dielectric properties, especially the small temperature coefficients of resonant frequency (τ_f) and high quality factor (Q × f) values. For composition at x = 0.69, the ceramic sintered at 1070 °C had Q × f value of 75,500 GHz and τ_f value of +8.7 ppm/°C.     

Effect of Sb5+ substitution on the dielectric properties of Ag(Nb0.8Ta0.2)O3 ceramics

Sb₂O₅ were selected to substitute (Nb_0.8Ta_0.2)₂O₅ and the effects of substitution on the dielectric properties of Ag(Nb_0.8Ta_0.2)O₃ ceramics were studied. The dielectric properties of Ag(Nb_0.8Ta_0.2)_1−xSb_xO₃ ceramics were found to be improved by the substitution of Sb for Nb/Ta. The ε value of Ag(Nb_0.8Ta_0.2)_1−xSb_xO₃ ceramics sintered at 1060 °C increased from 430 to 825 with x increasing from 0 to 0.08, the tanδ value decreased sharply from 0.0085 to 0.0023 (at 1 MHz) with x increasing from 0 to 0.04, and then kept to a lower tanδ value ∼ 0.0024 with x to 0.08. The TCC values decreased from + 1450 ppm/°C for x = 0 to − 38.5 ppm/°C for x = 0.08. The Ag(Nb_0.8Ta_0.2)_1−xSb_xO₃ ceramics with x = 0.08 sintered at 1050 °C exhibited the optimum dielectric properties of ε ∼ 854, tanδ ∼ 0.0024 (1 MHz), and TCC ∼ 36.86 ppm/°C.     

New dielectric materials of xSrTiO3–(1 − x)Ca(Mg1/3Nb2/3)O3 ceramic system at microwave frequency

The crystal structures and the microwave dielectric properties of the xSrTiO₃–(1 − x)Ca(Mg_1/3Nb_2/3)O₃ perovskite ceramic system have been investigated. In order to achieve a temperature-stable material, we studied a method of combining a positive temperature coefficient material with a negative one. SrTiO₃ has dielectric properties of dielectric constant ε_r ∼ 205, Q × f value ∼ 4200 GHz and a large positive τ_f value ∼ 1700 ppm/°C. Ca(Mg_1/3Nb_2/3)O₃ possesses high dielectric constant (ε_r ∼ 28), high quality factor (Q × f value ∼ 58,000 at 7 GHz) and negative τ_f value (− 48 ppm/°C). As the x value varies from 0.2 to 0.8, the xSrTiO₃–(1 − x)Ca(Mg_1/3Nb_2/3)O₃ system has the dielectric properties as follows: 40 < ε_r < 123, 4600 < Q × f < 33,400 and − 23 < τ_f < 600. A new microwave dielectric material, 0.3SrTiO₃–0.7Ca(Mg_1/3Nb_2/3)O₃, applicable in microwave devices is suggested and possesses the dielectric properties of a dielectric constant ε_r ∼ 46, a Q × f value ∼ 29,300 GHz (at 6.8 GHz) and a τ_f value ∼− 2 ppm/°C. A near-zero τ_f value can be achieved by adjusting the x value of xSrTiO₃–(1 − x)Ca(Mg_1/3Nb_2/3)O₃ ceramics.     

Effect of bond valence on microwave dielectric properties of (1 − x)CaTiO3–x(Li0.5La0.5)TiO3 ceramics

The origins of microwave dielectric properties (1 ? x)CaTiO₃–x(Li_0.5La_0.5)TiO₃ (0.2 ≤ x ≤ 0.8) ceramics, prepared by a conventional solid-state reaction method, were investigated based on the theory of bond valence. The XRD and SEM results showed that complete solid solutions with orthorhombic perovskite structure were formed in the whole investigated compositional range. The dielectric constant (?_r), quality factor (Q × f) and temperature coefficient of resonant frequency (τ_f) were closely related to B-site, A-site and the difference between A-site and B-site bond valences of ABO₃ perovskite compounds, respectively. As x value increased from 0.2 to 0.8, the dielectric constant increased from 198.3 to 276.8, the Q × f value decreased from 4340 to 1880 GHz, and the τ_f value varied from +489.7 to ?178 ppm/°C. For practical applications, excellent microwave dielectric properties of ?_r = 245, Q × f = 2750 GHz and τ_f = +0.75 ppm/°C were obtained for 0.4CaTiO₃–0.6(Li_0.5La_0.5)TiO₃ ceramics.     

The rock salt oxide Li2MgTiO4: Type I dielectric and ionic conductor

The exploration of the Li–Ti–Mg–O system, using both sol–gel technique and solid state reaction method, allowed a new phase, Li₂MgTiO₄, with disordered rock salt structure (a = 4.159 Å) to be synthesized. The latter is shown to be a good type I dielectric material, with a relative constant of 15 at high frequency and low dielectric loss (tanδ < 10⁻³) over the temperature range −60 to 160 °C. It is also observed that the sintering temperature of this phase is strongly lowered by adopting the sol–gel technique compared to solid state reaction (1150 °C instead of 1300 °C). Finally we show that this phase exhibits cationic conductivity above 400 °C (σ_600 °C = 9 × 10⁻⁵ S cm⁻¹).     

High permittivity and low dielectric loss of Na0.5Bi0.5−xLaxCu3Ti4O12 ceramics

The phase structure, microstructure and dielectric properties of Na_0.5Bi_0.5?xLa_xCu₃Ti₄O₁₂ (NBLCTO) ceramics were investigated. La³⁺ substitution had a great influence on the phase structure and dielectric properties. The results showed that the pure phase could be more easily obtained when substituting La³⁺ for Bi³⁺. Under the same processing condition (970 °C for 7.5 h) and measuring condition (10 kHz around room temperature), NBLCTO ceramics with x = 0.10 possessed the highest permittivity (1.02 × 10⁴) and lowest dielectric loss (0.022). The obtained NBLCTO ceramics with x = 0.10 also had good frequency stability and good temperature stability (?1.87% to +3.27%) from ?60 °C to 120 °C at both 1 and 10 kHz. Complex impedance results revealed that the grain resistance R_g was 7.18 Ω cm and the grain boundary resistance R_gb was 1.19 × 10⁶ Ω cm.     

Enhanced densification and microwave dielectric properties of Mg2TiO4 ceramics added with CeO2 nanoparticles

We report the study of the effects of processing parameters and additive concentration on the structure, microstructure and microwave dielectric properties of MTO–CeO₂ (x wt.%) ceramics with x = 0, 0.5, 1.0 and 1.5 prepared by solid-state reaction method by adding CeO₂ nanoparticles as a sintering aid. The pure Mg₂TiO₄ ceramics were not densifiable below 1450 °C. However, when CeO₂ nanoparticles were added to MTO, the densification achieved at 1300 °C along with the increase in average grain size with the uniform microstructure and improved microwave dielectric properties. This is mainly driven by the large surface energy of CeO₂ nanoparticles and their defect energy during the sintering process. While the addition of CeO₂ nanoparticles in MTO ceramics does not change the dielectric constant (?_r), the unloaded quality factor (Q_u) was altered significantly. MTO–CeO₂ (1.5 wt.%) ceramics sintered at 1300 °C exhibit superior microwave dielectric properties (?_r ～ 14.6, Q × f₀ ～ 167 THz), as compared to the pure Mg₂TiO₄ ceramics. The observed results are correlated to the enhancement in density and the development of uniform microstructure with the enhanced grain size.     

Microwave dielectric properties of Ba3La2Ti2Nb2−xTaxO15 ceramics

High dielectric constant and low loss ceramics in the system Ba₃La₂Ti₂Nb_2−xTa_xO₁₅ (x = 0–2) have been prepared by conventional solid-state ceramic route. Ba₃La₂Ti₂Nb_2−xTa_xO₁₅ solid solutions adopted A₅B₄O₁₅ cation-deficient hexagonal perovskite structure for all compositions. The materials were characterized at microwave frequencies. They show a linear variation of dielectric properties with the value of x. Their dielectric constant varies from 49.8 to 45.1, quality factor Q_u × f from 22,000 to 31,040 GHz and temperature variation of resonant frequency from + 6.9 to − 13.4 ppm/°C as the value of x increases. These low loss ceramics might be used for dielectric resonator (DR) applications.     

Dopant influence on BST ferroelectric solid solutions family

Solid solutions of the Ba_1−xSr_xTiO₃ (BST) type are very attractive for applications in information technology, but also in microwaves for such electrically controlled devices as phase shifters, tunable filters, steerable antennas, varactors, etc. A family of solid solutions with x = 25, 50, 75, 90% was prepared by standard powder technology-solid state reaction and sintered at 1230 °C and 1260 °C. Dielectric permittivity and loss at low (1 kHz) and high frequency (1 ÷ 2 GHz) were measured on a large temperature range − 200 °C ÷ + 200 °C. The influence of Sr content and of 1 wt.% MgO and 1 wt.% MnO₂ doping on the complex dielectric constant was studied. The dielectric permittivity at high frequencies and room temperature considerably decreases with the increase of Sr content. Similarly, low frequency measurements showed a severe and almost linear decrease of the Curie Point with the increase of Sr fraction. At low Sr content, the measured ceramic densities slowly decrease with Sr fraction and represent about 92% of the X-ray density ρ(g/cm³) ≈ 5.99–0.99·x. At x = 90% Sr concentration, very low-density ceramics were obtained with both sintering temperatures.