Dielectric relaxation behaviors of pure and Pr6O11-doped CaCu3Ti4O12 ceramics in high temperature range

Pure and Pr₆O₁₁-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics were prepared by conventional solid-state reaction method. The compositions and structures were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The influences of Pr-ion concentration on dielectric properties of CCTO were measured in the ranges of 60 Hz-3 MHz and 290-490 K. The third phase of Ca₂CuO₃ was observed from the XRD of CCTO ceramics. From SEM, the grain size was decreased obviously with high valence Pr-ion (mixing valence of Pr³⁺ and Pr⁴⁺) substituting Ca²⁺. The room temperature dielectric constant of Pr-doped CCTO ceramics, sintered at 1323 K, was an order of magnitude lower than the pure CCTO ceramics due to the grain size decreasing and Schottky potential increasing. The dielectric spectra of Pr-doped CCTO were flatter than that of pure CCTO. The loss tangent of Pr-doped CCTO ceramics was less than 0.20 in 2 × 10²-10⁵ Hz region below 440 K. The complex impedance spectra of pure and Pr-doped CCTOs were fitted by ZView. From low to high frequency, three semicircles were observed corresponding to three different conducting regions: electrode interface, grain boundary and grain. By fitting the resistors R and capacitors C, the activation energies of grain boundary and electrode contact were calculated. All doped CCTOs showed higher activation energies of grain boundary and electrode than those of pure CCTO ceramics, which were concordant with the decreasing of dielectric constant after Pr₆O₁₁ doping.     

Phase evolution, crystal structure and dielectric behavior of (1 − x)Nd(Zn0.5Ti0.5)O3 + xBi(Zn0.5Ti0.5)O3 compound ceramics

The phase evolution, crystal structure and dielectric properties of (1 − x)Nd(Zn_0.5Ti_0.5)O₃ + xBi(Zn_0.5Ti_0.5)O₃ compound ceramics (0 ≤ x ≤ 1.0, abbreviated as (1 − x)NZT-xBZT hereafter) were investigated. A pure perovskite phase was formed in the composition range of 0 ≤ x ≤ 0.05. The B-site Zn²⁺/Ti⁴⁺ 1:1 long range ordering (LRO) structure was detected by both XRD and Raman spectra in x ≤ 0.05 samples. However, this LRO structure became gradually degraded with an increase in x. The dielectric behaviors of the compound ceramic at various frequencies were investigated and correlated to its chemical composition and crystal structure. A gradually compensated τ_f value was obtained in (1 − x)NZT-xBZT microwave dielectrics at x = 0.03, which was mainly due to the dilution of dielectric constant in terms of Claussius-Mossotti differential equation.     

Microstructures and electrical responses of pure and chromium-doped CaCu3Ti4O12 ceramics

Pure and chromium-doped CCTO (CaCu₃Ti₄O₁₂) ceramics were prepared by a conventional solid-state reaction method, and the effects of chromium doping on the microstructures and electrical properties of these ceramics were investigated. Efficient crystalline phase formation accompanied by dopant-induced lattice constant expansion was confirmed through X-ray diffraction studies. Scanning electron microscopy (SEM) results show that doping effectively enhanced grain growth or densification, which should increase the complex permittivity. The dielectric constant reached a value as high as 20,000 (at 1 kHz) at a chromium-doping concentration of 3%. The electrical relaxation and dc conductivity of the pure and chromium-doped CCTO ceramics were measured in the 300-500 K temperature range, and the electrical data were analyzed in the framework of the dielectric as well as the electric modulus formalisms. The obtained activation energy associated with the electrical relaxation, determined from the electric modulus spectra, was 0.50-0.60 eV, which was very close to the value of the activation energy for dc conductivity (0.50 ± 0.05 eV). These results suggest that the movement of oxygen vacancies at the grain boundaries is responsible for both the conduction and relaxation processes. The short-range hopping of oxygen vacancies as “polarons” is similar to the reorientation of the dipole and leads to dielectric relaxation. The proposed explanation of the electric properties of pure and chromium-doped CCTO ceramics is supported by the data from the impedance spectrum.     

Piezoelectric and dielectric properties of Dy2O3-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ + x wt% Dy₂O₃ with x = 0-0.3 ceramics were synthesized by conventional solid-state processes. The effects of Dy₂O₃ on the microstructure, the piezoelectric and dielectric properties were investigated. X-ray diffraction pattern confirmed that the coexistence of tetragonal and rhombohedral phases in the (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ composition was not changed by adding 0.05-0.3 wt% Dy₂O₃. SEM images indicate that all the ceramics have pore-free microstructures with high density, and that doping of Dy₂O₃ inhibits the grain growth of the ceramics. The addition of Dy₂O₃ shows the double effects on decreasing the piezoelectric and dielectric properties for 0 < x < 0.15 when Dy³⁺ ions substitute B-site Ti⁴⁺ ions, and increasing the properties for 0.15 < x < 0.3 when Dy³⁺ ions enters into A-site of the perovskite structure. The optimum electric properties of piezoelectric constant d₃₃ = 170 pC/N and the dielectric constant ?_r = 1900 (at a frequency of 1 kHz) are obtained at x = 0.3.     

Effect of dwell time during sintering on piezoelectric properties of (Ba0.85Ca0.15)(Ti0.90Zr0.10)O3 lead-free ceramics

In this letter, the effect of dwell time (1-6 h) during sintering on the piezoelectric properties is investigated for the (Ba_0.85Ca_0.15)(Ti_0.90Zr_0.10)O₃ ceramics. All ceramics sintered at different dwell time are of a pure phase, and its structure distortion is induced by too long dwell time. Their dielectric constant and remanent polarization increases and the coercive field decreases with increasing dwell time. An enhanced piezoelectric behavior (d₃₃ ∼ 492 pC/N and k_p ∼ 51.5%) is demonstrated for the BCTZ ceramic with an optimum dwell time of 5 h, owing to the structure distortion together with a dense microstructure and a larger grain size.     

Microwave properties of Ba(Zn1/3Ta2/3)O3 dielectric resonators

Ba(Zn_1/3Ta_2/3)O₃ (BZT) dielectric resonators were prepared by solid-state reaction. The starting materials were BaCO₃, ZnO, and Ta₂O₅ powders with high purity. The double calcined BZT pellets were sintered in air at temperatures of 1575, 1600, 1625, and 1650 °C for 4 h. The X-ray diffraction data allowed the study of the unit cell distortion degree and the presence of the secondary phases. A long-range order with a 2:1 ratio of Ta and Zn cations on the octahedral positions of the perovskite structure was observed with the increase of the sintering temperature. The dielectric constant of BZT resonators measured around 6 GHz was between 26 and 28. High values of Q × f product (120 THz) were obtained for BZT resonators sintered at 1650 °C/4 h. The temperature coefficient of the resonance frequency exhibits positive values less than 6 ppm/°C. The achieved dielectric parameters recommend BZT dielectric resonators for microwave and millimeter wave applications.     

High permittivity and low dielectric loss of the Ca1−xSrxCu3Ti4O12 ceramics

The Ca_1−xSr_xCu₃Ti₄O₁₂ (CSCTO) giant dielectric ceramics were prepared by conventional solid-state method. X-ray diffraction patterns revealed that a small amount of Sr²⁺ (x < 0.2) had no obvious effect on the phase structure of the CSCTO ceramics, while with increasing the Sr²⁺ content, a second phase of SrTiO₃ appeared. Electrical properties of CSCTO ceramics greatly depended on the Sr²⁺ content. The Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics exhibited a higher permittivity (71,153) and lower dielectric loss (0.022) when measured at 1 kHz at room temperature. The ceramics also performed good temperature stability in the temperature range from −50 °C to 100 °C at 1 kHz. By impedance spectroscopy analysis, all compounds were found to be electrically heterogeneous, showing semiconducting grains and insulating grain boundaries. The grain resistance was 1.28 Ω and the grain boundary resistance was 1.31 × 10⁵ Ω. All the results indicated that the Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics were very promising materials with higher permittivity for practical applications.     

Effect of CaTiO3 addition on microwave dielectric properties of Mg2(Ti0.95Sn0.05)O4 ceramics

The microwave dielectric properties of CaTiO₃-added Mg₂(Ti_0.95Sn_0.05)O₄ ceramics prepared by the mixed oxide route have been investigated. The combination of spinel-structured Mg₂(Ti_0.95Sn_0.05)O₄ and perovskite-structured CaTiO₃ forms a two-phase system (1 − x)Mg₂(Ti_0.95Sn_0.05)O₄-xCaTiO₃, which was confirmed by the XRD patterns and the EDX analysis and it also leads to a zero τ_f. The microwave dielectric properties of the ceramics can be effectively controlled by varying the x value. For practical applications, a new microwave dielectric material 0.91Mg₂(Ti_0.95Sn_0.05)O₄-0.09CaTiO₃ is suggested and it possesses a good combination of dielectric properties with an ?_r of ∼18.01, a Q × f of ∼92,000 GHz, and a τ_f of ∼0 ppm/°C, which makes it is a very promising candidate material for high frequency applications.     

Microstructure and electrical properties of Y(NO3)3·6H2O-doped ZnO-Bi2O3-based varistor ceramics

Y(NO₃)₃·6H₂O-doped ZnO-Bi₂O₃-based varistor ceramics were prepared using a solid reaction route. The microstructure, electrical properties, degradation coefficient (D_V), and dielectric characteristics of varistor ceramics were studied in this paper. With increasing amounts of Y(NO₃)₃·6H₂O in the starting composition, Y-containing Bi-rich, Y₂O₃, and Sb₂O₄ phases were formed, and the average grain size decreased. Results also showed that with the addition of 0.16 mol% Y(NO₃)₃·6H₂O, Y(NO₃)₃·6H₂O -doped ZnO-based varistor ceramics exhibit comparatively better comprehensive electrical properties, such as a threshold voltage of 425 V/mm, a nonlinear coefficient of 73.9, a leakage current of 1.78 μA, and a degradation coefficient of 1.7. The dielectric characteristics and lightning surge test also received the same additional content of Y(NO₃)₃·6H₂O. The results confirmed that doping with rare earth nitrates instead of rare earth oxides is very promising route in preparing high-performance ZnO-Bi₂O₃-based varistor ceramics.     

Structure and dielectric characterization of xNd(Mg1/2Ti1/2)O3-(1 − x)Ca0.6La0.8/3TiO3 in the microwave frequency range

The crystal structures, phase compositions and the microwave dielectric properties of the xLa(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.8Sr_0.2TiO₃ composites prepared by the conventional solid state route have been investigated. The formation of solid solution is confirmed by the XRD patterns. Doping with B₂O₃ (0.5 wt.%) can effectively promote the densification and the dielectric properties of xNd(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics. It is found that xNd(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics can be sintered at 1375 °C, due to the liquid phase effect of B₂O₃ addition observed by Scanning Electronic Microscopy. At 1375 °C, 0.4Nd(Mg_1/2Ti_1/2)O₃-0.6Ca_0.6La_0.8/3TiO₃ ceramics with 1 wt.% B₂O₃ addition possesses a dielectric constant (?_r) of 49, a Q × f value of 13,000 (at 8 GHz) and a temperature coefficients of resonant frequency (τ_f) of 1 ppm/°C. As the content of Nd(Mg_1/2Ti_1/2)O₃ increases, the highest Q × f value of 20,000 GHz for x = 0.9 is achieved at the sintering temperature 1400 °C.     

Structure, dielectric and electrical properties of cerium doped barium zirconium titanate ceramics

Rare-earth doped barium zirconium titanate (BZT) ceramics, Ba(Zr_0.25Ti_0.75)O₃ + xCeO₂, (x = 0-1.5 at%) were obtained by a solid state reaction route. Perovskite-like single-phase compounds were confirmed from X-ray diffraction data and the lattice parameters were refined by the Rietveld method. It is found that, integrating with the lattice parameters and the distortion of crystal lattice, there is an alternation of substitution preference of cerium ions for the host cations in perovskite lattice. Morphological analysis on sintered samples by scanning electron microscopy shows that the addition of rare-earth ions affects the growth of the grain and remarkably changes the grain morphology. The effect of rare-earth addition to BZT on dielectric and electrical properties is analyzed. High values of dielectric tunability are obtained for cerium doped BZT. Especially, the experimental results on the effect of the contents of rare-earth addition on the resistivity of BZT ceramics were investigated, demonstrating that the samples with x = 0.4 and x = 0.6 could be semiconducting in air atmosphere.     

Phenomenological model of grain boundary behaviour under a bias field in Nb-doped CaCu3Ti4O12 ceramics

In this work, the dielectric behaviour and capacitance-voltage (C-V) curves under an applied DC bias field of 1 wt% Nb-doped CaCu₃Ti₄O₁₂ ceramics have been studied. The dielectric properties reveal the existence of grain boundaries of different electrical nature. A new model is proposed to simultaneously explain the presence of insulating and conducting grain boundaries. At low frequency, the capacity curve of the material exhibits a double metal oxide semiconductor (MOS) capacitor-like behaviour and as the frequency is increased, the curve suffers an inversion showing a ferroelectric-like response. This behaviour does not correspond to ferroelectric domain movement phenomena but seems associated to charge accumulation on grain boundary regions.     

High-dielectric-constant and low-loss microwave dielectric in the (1 − x)La(Mg0.5Ti0.5)O3-x(Ca0.8Sr0.2)TiO3 solid solution system

The microwave dielectric properties and microstructures of (1 − x)La(Mg_0.5Ti_0.5)O₃-x(Ca_0.8Sr_0.2)TiO₃ ceramics, prepared by a mixed oxide route, have been investigated. The forming of solid solutions was confirmed by the XRD patterns and the measured lattice parameters for all compositions. A near zero τ_f was achieved for samples with x = 0.5, although the dielectric properties varied with sintering temperature. The Q × f value of 0.5La(Mg_0.5Ti_0.5)O₃-0.5(Ca_0.8Sr_0.2)TiO₃ increased up to 1475 °C, after which it decreased. The decrease in dielectric properties was coincident with the onset of rapid grain growth. The optimum combination of microwave dielectric properties was achieved at 1475 °C for samples where x = 0.5 with a dielectric constant ?_r of 47.12, a Q × f value of 35,000 GHz (measured at 6.2 GHz) and a τ_f value of −4.7 ppm/°C.     

Effects of lanthanum doping on the preferred orientation, phase structure and electrical properties of sol-gel derived Pb1-3x/2Lax (Zr0.6Ti0.4)O3 thin films

Pb_1-3x/2La_x (Zr_0.6Ti_0.4)O₃ thin films (0 ≤ x ≤ 0.08) were prepared on the Pt (1 1 1)/Ti/SiO₂/Si (1 0 0) substrates by a sol-gel method. The morphology, preferred orientation, phase structure, dielectric and ferroelectric properties of the films have been investigated. Our results show that lanthanum doping is favorable to enhance crystalline and obtain (1 0 0)-preferred orientation of the films. Meanwhile, it is suggested that the films undergo a structure change from “rhombohedral” phase to monoclinic phase as the lanthanum-doped content is increased to x ≈ 0.05. Results of dielectric properties and ferroelectric properties indicate that lanthanum doping contributes to improve film dielectric constant and dielectric loss while it brings about a striking decrease in remnant polarization value. Possible explanations for the variations of electrical properties have been discussed in terms of preferred orientation, phase structure and large lattice distortion.     

Dielectric and piezoelectric properties of Sb doped (NaBi)0.38(LiCe)0.05[]0.14Bi2Nb2O9 ceramics

Sb⁵⁺-doped (NaBi)_0.38(LiCe)_0.05[]_0.14Bi₂Nb₂O₉ (represented as NBNLCS-x, where [] represents A-site vacancies) ceramics were prepared by the conventional solid-state route. The ceramics well sintered to approach ∼98.5% theoretical density and the tetragonality of crystal structure increased with Sb⁵⁺ additions. However, the Curie temperature (T_C) and the piezoelectric coefficient (d₃₃) of Sb⁵⁺-modified ceramics gradually decreased. The 3 mol% Sb⁵⁺-doped samples exhibited optimum properties with a d₃₃ value of ∼22 pC/N planar electromechanical coupling factor (k_p) of ∼11.2% and relatively high T_C of ∼765 °C. These results indicate that NBNLCS-x material is a promising candidate for high-temperature piezoelectric applications.     

Effect of CuO on the sintering temperature and piezoelectric properties of MnO2-doped 0.75Pb(Zr0.47Ti0.53)O3-0.25Pb(Zn1/3Nb2/3)O3 ceramics

The sintering temperature of 0.75Pb(Zr_0.47Ti_0.53)O₃-0.25Pb(Zn_1/3Nb_2/3)O₃ ceramics containing 1.5 mol% MnO₂ was decreased from 930 to 850 °C with the addition of CuO. The CuO reacted with the PbO and formed a liquid phase during the sintering, which assisted the densification of the specimens. Most of the Cu²⁺ ions existed in the CuO second phase, thereby preventing any possible hardening effect from the Cu²⁺ ions. Variations of the k_p, Q_m, ?₃^T/?₀ and d₃₃ values with CuO were similar to that of the relative density. The specimen containing 0.5 mol% CuO sintered at 850 °C showed the good piezoelectric properties of k_p = 0.5, Q_m = 1000, ?₃^T/?₀ = 1750 and d₃₃ = 300 pC/N.     

Microwave dielectric properties of temperature stable Li2ZnxCo1−xTi3O8 ceramics

The Li₂Zn_xCo_1−xTi₃O₈ (x = 0.2-0.8) solid solution system has been synthesized by the conventional solid-state ceramic route and the effect of Zn substitution for Co on microwave dielectric properties of Li₂CoTi₃O₈ ceramics has also been investigated. The microwave dielectric properties of these ceramics show a linear variation between the end members for all compositions. The optimized sintering temperatures of Li₂Zn_xCo_1−xTi₃O₈ ceramics increase with increasing content of Zn. The specimen with x = 0.4 sintered at 1050 °C/2 h exhibits an excellent combination of microwave dielectric properties with ?_r = 27.7, Q_u × f = 57,100 GHz and τ_f = −1.0 ppm/°C.     

Improved dielectric and non-ohmic properties of Ca2Cu2Ti4O12 ceramics prepared by a polymer pyrolysis method

Non-ohmic and dielectric properties of Ca₂Cu₂Ti₄O₁₂ (CaCu₃Ti₄O₁₂/CaTiO₃ composite) ceramics prepared by a polymer pyrolysis method (PP-ceramic samples) are investigated. The PP-ceramics show a highly dense structure and improved non-ohmic and dielectric properties compared to the ceramics obtained by a solid state reaction method (SSR-ceramic samples). ?′ (tan δ) of the PP-ceramic samples is found to be higher (lower) than that of the SSR-ceramic samples. Interestingly, the PP-ceramic sintered at 1050 °C for 10 h exhibits the high ?′ of 2530 with weak frequency dependence below 1 MHz, the low tan δ less than 0.05 in the frequency range of 160 Hz-177 kHz, and the little temperature coefficient, i.e., |Δ?′| ≤ 15 % in the temperature range from −55 to 85 °C. These results indicate that the CaCu₃Ti₄O₁₂/CaTiO₃ composite system prepared by PP method is a promising high-?′ material for practical capacitor application.     

Low temperature processing of (Zr0.8Sn0.2)TiO4 ceramics with improved Q factor

Polycrystalline (Zr_0.8Sn_0.2)TiO₄ (ZST) ceramics have been synthesized by solid-sate reaction method. The effect of B₂O₃, ZnO-B₂O₃ or 5ZnO-2B₂O₃ glass addition (0.2-1.0 wt.%) on microwave dielectric properties of ZST ceramics are investigated. The increase in average grain size via growth of large grains and dissolution of small grains is explained by Ostwald ripening phenomena. The highest Q × f_o values are found to be 61,500, 48,500 and 51,900 GHz for the ZST dielectric resonators added with B₂O₃, ZnO-B₂O₃ and 5ZnO-2B₂O₃ respectively. The effect of liquid phase sintering on microstructure and microwave dielectric properties of ZST ceramics is discussed.     

Reaction-sintering method for ultra-low loss (Mg0.95Co0.05)TiO3 ceramics

Microwave dielectric properties and microstructures of (Mg_0.95Co_0.05)TiO₃ ceramics prepared by a new sintering method (reaction-sintering method) were investigated. A pure phase of (Mg_0.95Co_0.05)TiO₃ was obtained by the new method and excellent dielectric properties were observed due to uniformities of the microstructure and the phase. In contrast, the secondary phase (Mg_0.95Co_0.05)Ti₂O₅ was observed in samples prepared by conventional sintering method. In order to study the influence of secondary phase on the microwave dielectric properties quantitatively, the weight fraction of (Mg_0.95Co_0.05)Ti₂O₅ was calculated on the basis of Rietveld refinement. The pore-free?_r values of specimens prepared by two different methods indicated that porosity plays an important role in the ?_r values of (Mg_0.95Co_0.05)TiO₃ ceramics. Specimens sintered by reaction-sintering method at 1350 °C for 4 h possess excellent dielectric properties with an ?_r of 16.3, a Q × f value of 244,500 GHz, and a τ_f value of −53.5 ppm/°C.