Colossal dielectric permittivity and electrical properties of the grain boundary of Ca1−3x/2YbxCu3−yMgyTi4O12 (x=0.05, y=0.05 and 0.30)

Dielectric properties of Ca_1−3x/2Yb_xCu_3−yMg_yTi₄O₁₂ (x=0.05, y=0.05 and 0.30) prepared using a modified sol–gel method and sintered at 1070 °C for 4 h were investigated. The mean grain sizes of the CaCu₃Ti₄O₁₂ and co-doped Ca_0.925Yb_0.05Cu_3−yMg_yTi₄O₁₂ (y=0.05 and 0.30) ceramics were ≈15.86, ≈3.37, and ≈2.32 μm, respectively. Interestingly, the dielectric properties can be effectively improved by co-doping with Yb³⁺ and Mg²⁺ ions to simultaneously control the microstructure and properties of grain boundaries, respectively. These properties were improved over those of single-doped and un-doped CaCu₃Ti₄O₁₂ ceramics. A highly frequency−independent colossal dielectric permittivity (≈10⁴) in the range of 10²–10⁶ Hz with very low loss tangent values of 0.018–0.028 at 1 kHz were successfully achieved in the co-doped Ca_0.925Yb_0.05Cu_3−yMg_yTi₄O₁₂ ceramics. Furthermore, the temperature stability of the colossal dielectric response of Ca_1−3x/2Yb_xCu_3−yMg_yTi₄O₁₂ was also improved to values of less than ±15% in the temperature range from −70 to 100 °C.     

A novel strategy to enhance dielectric performance and non-Ohmic properties in Ca2Cu2−xMgxTi4O12

A novel strategy to improve the dielectric and non-Ohmic properties of CaCu₃Ti₄O₁₂ ceramics that deliberately created a binary-phase system of CaCu_3−xMg_xTi₄O₁₂/CaTiO₃ was proposed and can be performed with a starting nominal formula of Ca₂Cu_2−xMg_xTi₄O₁₂. Mg²⁺ doping ions were preferentially incorporated only into the CaCu₃Ti₄O₁₂ phase. Substitution of Mg²⁺ into CaCu₃Ti₄O₁₂/CaTiO₃ can cause a significant increase in dielectric permittivity and a large reduction of the loss tangent to <0.015 at 1 kHz; while, retaining excellent temperature dielectric-stability. Sintering time had a slight influence on the dielectric properties, but remarkable effects upon the nonlinear electrical properties of CaCu_3−xMg_xTi₄O₁₂/CaTiO₃ ceramics. Degradation of nonlinear properties with increased sintering time is suggested to be the result of the dominant effect of oxygen vacancies. Impedance spectroscopy analysis demonstrated that improved dielectric and nonlinear properties could be attributed to the enhanced electrical responses of CaCu₃Ti₄O₁₂–CaTiO₃ and CaCu₃Ti₄O₁₂–CaCu₃Ti₄O₁₂ interfaces resulting from Mg²⁺ doping ions.     

Enhanced non-linear current-voltage response of Te-doped calcium copper titanate ceramics

The influence of partial replacement of Ti⁴⁺ ions by Te⁴⁺ in calcium copper titanate lattice on dielectric and non-linear current- voltage (I–V) characteristics was systematically studied. There was a remarkable increase in the values of the nonlinear coefficient (α) with Te⁴⁺ doping concentration in CaCu₃Ti_4-xTe_xO₁₂ (where, x=0, 0.1, 0.2).For instance, the α values increase from 2.9 (x=0) to 22.7 (x=0.2) for ceramics sintered at 1323 K/8 h. The room temperature value of current density (J) at the electrical field of 250 V/cm for CaCu₃Ti_3.8Te_0.2O₁₂ ceramics is almost 400 times higher than that of the pure CaCu₃Ti₄O₁₂ ceramics sintered at 1323 K. A systematic investigation into I–V behaviour as a function of temperature gave an insight into the conduction mechanisms of undoped and doped ceramics of calcium copper titanate (CCTO). The calculated potential barrier value for doped ceramics (~ 0.21 eV) dropped down to almost one third that of the undoped ceramics (~ 0.63 eV).     

Effects of LiF addition on microstructure and dielectric properties of CaCu3Ti4O12 ceramics

The effects of small amounts of lithium fluoride sintering aid on the microstructure and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics were investigated. CCTO polycrystalline ceramics with 0.5 and 1.0 mol% LiF, and without additive were prepared by solid state synthesis. Good densification (>90% of the theoretical density) was obtained for all prepared materials. Specimens without the sintering aid and sintered at 1090 °C exhibit secondary phases as an outcome of the decomposition reaction. The mean grain size is controlled by the amount of LiF in specimens containing the additive. Impedance spectroscopy measurements on CaCu₃Ti₄O₁₂ ceramics evidence the electrically heterogeneous nature of this material consisting of semiconductor grains along with insulating grain boundaries. The activation energy for grain boundary conduction is lower for specimens prepared with the additive, and the electric permittivity reached 53,000 for 0.5 mol% LiF containing CCTO.     

Dielectric properties of CaCu3Ti4O12 improved by chromium/lanthanum co-doping

The dielectric properties of Cr + La co-doped CaCu₃Ti₄O₁₂ ceramics prepared by a solid-state reaction method were evaluated and compared to Cr-doped, La-doped, and parent CaCu₃Ti₄O₁₂ (CCTO). Their structure and grain size were evaluated by X-ray diffraction and scanning electron microscopy, respectively. No secondary phase was detected based on the XRD analysis. The results show that, the room temperature dielectric loss of the co-doped samples is reduced to 43% compared to CCTO and their dielectric permittivity is higher than the un-doped, Cr-doped, and La-doped samples at frequencies over 325 kHz, 30 kHz, and 12 Hz, respectively. Furthermore, the temperature stability of the co-doped sample is significantly more convenient than that of CCTO, and its dielectric loss is three times lower. The results also indicated that the co-doping method is effective in reducing the dielectric loss, still maintaining the high dielectric permittivity.     

Effects of Bi4Ti3O12 addition on the microstructure and dielectric properties of modified BaTiO3 under a reducing atmosphere

The effects of Bi₄Ti₃O₁₂ addition on the microstructure and dielectric properties of Mn-modified BaTiO₃ were investigated to develop low temperature fired BaTiO₃-based ceramics with stable temperature characteristics. The sintering temperature of Mn-doped BaTiO₃ could be reduced to 1200 °C by adding more than 1 mol% Bi₄Ti₃O₁₂. TEM results show an apparent core–shell structure with 2 mol% Bi₄Ti₃O₁₂ addition. However, it was destroyed when the Bi₄Ti₃O₁₂ content increased from 2 to 4 mol%. The permittivity decreased and the Curie temperature shifted to higher temperature when the Bi₄Ti₃O₁₂ content increased from 0 to 3 mol%. The temperature characteristic of capacitance was very close to the EIA X8R specification when 2 mol% Bi₄Ti₃O₁₂ was added due to the presence of the core–shell grain structure and raised Curie temperature. With adequate Bi₄Ti₃O₁₂ addition, the BaTiO₃-based system shows great potential for applications in EIA X8R-type multilayer ceramic capacitors.     

(Na,K)NbO3–CaCu3Ti4O12 perovskite composites for supercapacitor based piezoelectric devices

The supercapacitor based piezoelectric material composite (Na,K)NbO₃–CaCu₃Ti₄O₁₂ (NKN–CCTO) is investigated for possible application in piezoelectric devices. (1−x)NKN–xCCTO (0.015≤x≤0.06) with different sintering conditions is researched for supercapacitor based piezoelectric applications. The 0.94NKN–0.06CCTO composite sintered at 975 °C shows the highest dielectric permittivity of 796. Clear SEM images of (1−x)NKN–xCCTO reveal that these compositions have high density well-crystallized structures. The composition and sintering temperature dependence of dielectric permittivities and piezoelectric coefficients, plotted in three dimensions, show that the 0.985NKN–0.015CCTO composite sintered at 1025 °C has a moderate dielectric permittivity of 405 and a piezoelectric constant of 98 pC/N.     

Enhanced intrinsic permittivity and bulk response in Y2/3Cu3Ti4+xO12 ceramics

Considering the contribution of the mixed valence structure of Ti³⁺ and Ti⁴⁺ to the semiconductivity of grain, compositions with the formula of Y_2/3Cu₃Ti_4+xO₁₂ were designed and prepared. The dielectric bulk responses of Y_2/3Cu₃Ti_4+xO₁₂ ceramics were explored in detail. Changing Ti stoichiometry gives rise to an increase of the intrinsic permittivity. Y_2/3Cu₃Ti_3.925O₁₂ ceramic exhibits a higher intrinsic permittivity of ~120 at 60 MHz than that of pure Y_2/3Cu₃Ti₄O₁₂ ceramics (87 at 60 MHz). Additionally, the activation energies of bulk responses are significantly enhanced by changing Ti stoichiometry, which is closely linked with the increase of Ti³⁺/Ti⁴⁺.     

Decrease in the dielectric loss of CaCu3Ti4O12 at high frequency by Ru doping

CaCu_3−xRu_xTi₄O₁₂ (x=0, 0.03, 0.05 and 0.07) electronic ceramics were fabricated using a conventional solid-state reaction method. The microstructure, grain sizes and dielectric properties as well as the impedance behaviours of the ceramics were carefully investigated. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) results indicate that ruthenium (Ru) dopant inhibits the growth of grains during the sintering process by promoting the formation of high melting point oxides of Ca and Ti. The study on the frequency dependence of dielectric properties suggests that Ru doping shifts the dielectric loss peak of CCTO to a much lower frequency, thereby reducing the dielectric loss of CCTO at high frequency (f>1.0 MHz) accordingly. When doped with proper amount of Ru, the high frequency dielectric loss of CCTO is reduced to a very low value (tanδ<0.05). Our study conclusively suggests that Ru-doped CCTO, with sufficiently low dielectric loss and decent permittivity, presents potential applications at high frequency.     

The relationship between the micro-mechanism and macroscopic dielectric properties in Ba1−xBixTi1−x−yZn0.75xW0.25x+yO3+y systems

A novel lead-free, high dielectric constant, ultra-wide temperature stable dielectric ceramic Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO_3+y (0.22≤x≤0.30, y=0.015) was synthesized by the traditional solid-state reaction method. The phase composition, electric and dielectric properties of the Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO₃ ceramics were investigated. The P-V-L dielectric theory was introduced. And, the chemical bond energy was calculated to track the changes in micro-structure. The relationships between chemical bond energy and the macroscopic dielectric properties(ε_r, dielectric stability and dielectric loss) in Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO_3+y ceramics were discussed systematically. Owing to the inhomogeneous micro-structure and the diffusion in phase transition, Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO_3+y ceramics showed a stable permittivity (~800±15%) over a ultra-wide temperature range (−30 to 375 °C). Moreover, dielectric loss was less than 0.02 and the insulation resistance was over 10¹² Ω cm. These features suggested that the Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO_3+y ceramic could be considered as a promising candidate material for energy storage applications in harsh environment.     

Temperature-independent permittivity of xBaTiO3–(1−x)(0.5Bi(Mg1/2Ti1/2)O3–0.5BiScO3) ceramics

xBaTiO₃–(1−x)(0.5Bi(Mg_1/2Ti_1/2)O₃-0.5BiScO₃) or xBT–(1−x)(0.5BMT–0.5BS) (x=0.45–0.60) ceramics were prepared by using the conventional mixed oxide method. Perovskite structure with pseudo-cubic symmetry was observed in all the compositions. Dielectric measurement results indicated that all the samples showed dielectric relaxation behavior. As the content BaTiO₃ was decreased from 0.60 to 0.45, temperature coefficient of permittivity (TCε) in the range of 200–400 °C was improved from −706 to −152 ppm/°C, while the permittivity at 400 °C was increased from 1208 to 1613. The temperature stability of permittivity was further improved by using 2 mol% Ba-deficiency. It was found that lattice parameter and grain size of the 2 mol% Ba-deficient ceramics were smaller than those of their corresponding stoichiometric (S) counterparts, with TCε in the range of 200–400 °C to be improved noticeably. For example, TCε of the Ba-deficiency sample with x=0.45 was −75 ppm/°C in the temperature range of 200–400 °C and the permittivity was 1567 at 400 °C. The results obtained in this work indicated that xBT–(1−x)(0.5BMT–0.5BS) ceramics are very promising candidates for high temperature capacitor applications.     

Defects characterization of Dy-doped BaTiO3 ceramics via electron paramagnetic resonance

The point defects and the structural and dielectric properties of Dy-doped BaTiO₃ ceramics prepared at 1400 °C were investigated. The solubility of Dy in the self-compensation mode was determined to be x = 0.07 for (Ba_1−xDy_x)(Ti_1−xDy_x)O₃, and no EPR signals associated with the Dy³⁺ Kramers ion or the Ba and Ti vacancies were detected using the electron paramagnetic resonance (EPR) technique. As x increases, the dielectric behavior changed from a first-order phase transition to a diffuse phase transition to a Y7R dielectric-temperature stability. A strong EPR signal at g = 1.974, which is rare among rare-earth-doped BaTiO₃ ceramics appeared unexpectedly in the single-phase (Ba_1−xDy_x)Ti_1−x/4O₃ ceramics with deliberately designed Ti vacancies. This signal was attributed to ionized Ba vacancy defects. A preference for the self-compensation mode of Dy³⁺ ions is responsible for the appearance of Ba vacancies. The real formula of the nominal (Ba_1−xDy_x)Ti_1−x/4O₃ is expressed as (Ba_1−xDy_3x/4)(Ti_1−x/4Dy_x/4)O₃. In addition, the defect chemistry is discussed.     

Dielectric properties and tunability of Ba(ZrxTi1−x)O3 ceramics under high DC electric field

Ba(Zr_xTi_1−x)O₃ (BZT) (x = 0.25, 0. 3, 0.35, 0.4) ceramics were prepared by the traditional ceramic processing and their structural, surface morphological, dielectric properties, tunable properties as well as the mechanism of their nonlinear dielectric constant under DC electric field were systemically examined. The Zr ions substitution of Ti ions has a strong effect on the dielectric properties and the grain sizes. The results show Ba(Zr_xTi_1−x)O₃ (x = 0.25, 0.3, 0.35) ceramics to be promising candidates for the DC electric field tunable materials for microwave electronics application, because they exhibit high tunability (27.6%, 26.3%, 19.4%, respectively) as the strength of electric field is up to 2 kV/mm, low dielectric loss (0.001–0.002, 0.001–0.002, 0.004–0.005, respectively) at 10 kHz at room temperature and low temperature coefficient of capacitance.     

(Al3+, Nb5+) co–doped CaCu3Ti4O12: An extended approach for acceptor–donor heteroatomic substitutions to achieve high–performance giant–dielectric permittivity

Substitution of (Al³⁺, Nb⁵⁺) co–dopants into TiO₆ octahedral sites of CaCu₃Ti₄O₁₂ ceramics, which were prepared by a solid state reaction method and sintered at 1090 °C for 18 h, can cause a great reduction in a low–frequency loss tangent (tanδ≈0.045–0.058) compared to those of Al³⁺ or Nb⁵⁺ single–doped CaCu₃Ti₄O₁₂. Notably, very high dielectric permittivities of 2.9 ? 4.1 × 10⁴ with good dielectric–temperature stability are achieved. The room–temperature grain boundary resistance (R_gb≈0.37–1.17 × 10⁹ Ω.cm) and related conduction activation energy (E_gb≈0.781–0.817 eV), as well as the non–Ohmic properties of the co–doped ceramics are greatly enhanced compared to single–doped ceramics (R_gb≈10⁴–10⁶ Ω cm and E_gb≈0.353–0.619 eV). The results show the importance of grain boundary properties for controlling the nonlinear–electrical and giant–dielectric properties of CaCu₃Ti₄O₁₂ ceramics, supporting the internal barrier layer capacitor model of Schottky barriers at grain boundaries.     

Complex permittivity and relaxation processes in CaCu3Ti(4−x)MnxO12

The effects of Mn-doping on CaCu₃Ti₄O₁₂ (CCTO), i.e. the electrical properties of CaCu₃Ti_(4−x)Mn_xO₁₂ were studied in order to get a deep insight into the origin of the colossal dielectric constant of CCTO. It was found that 1 mol% substitution of Mn for Ti decreases the dielectric constant largely to a factor of 1/100, supporting the point of view that the native defects are responsible for the dielectric response of CCTO.     

Neodymium substituted CaBi4Ti4O15 bismuth layered compound

In the present work, CaBi_4−xNd_xTi₄O₁₅ (0 ≤ x ≤ 1) ceramics were prepared and characterized. Although the substitution of Nd³⁺ for Bi³⁺ led to a decrease of tolerance factor t, the ferroelectricity in CaBi_4−xNd_xTi₄O₁₅ was not enhanced but weakened. With increasing x, the Curie temperature of CaBi_4−xNd_xTi₄O₁₅ was lowered and the peak of dielectric constant was significantly suppressed. Besides, the variation of lattice parameters of CaBi_4−xNd_xTi₄O₁₅ showed an approach of a and b, which revealed a development trend from ferroelectric orthorhombic structure to the prototype tetragonal structure with the substitution. This strongly suggested that Bi³⁺ is crucial for the ferroelectricity in four-layered CaBi₄Ti₄O₁₅, just like found in two-layered Bi₃TiNbO₉ and three-layered Bi₄Ti₃O₁₂ compounds. The importance of Bi³⁺ to the ferroelectricity should be due to the special electron configuration of Bi³⁺ but not its relatively small size, since Nd³⁺ is even smaller than Bi³⁺. The size mismatch between A-site cations and the provskite cuboctahedral cavity, indicated by t, seemed to play a secondary role in the contribution to the ferroelectricity of CaBi₄Ti₄O₁₅ and its analogues. The dielectric properties of CaBi_4−xNd_xTi₄O₁₅ ceramics were also investigated at microwave resonant frequency.     

Modified Ba6−3xNd8+2xTi18O54 microwave dielectric ceramics

In order to improve the microwave dielectric properties of Ba_6−3xNd_8+2xTi₁₈O₅₄ solid solution ceramics, the effects of Bi₂O₃ and Bi₄Ti₃O₁₂ additives were determined. The results of SEM and EDS analyses suggested that the present ceramics with Bi₄Ti₃O₁₂ additives consisted of Ba_6−3xNd_8+2xTi₁₈O₅₄ solid solution matrix phase, and secondary phase of BaTi₄O₉, but this was not the situation of Bi₂O₃ added ceramics. XRD analysis also revealed that the unit cell volume of the matrix phase increased with increasing the amount of Bi₄Ti₃O₁₂ additive. With addition of Bi₄Ti₃O₁₂ into the present ceramics, the dielectric constant increased and the temperature coefficient of resonator frequency decreased, while the Qf value slightly decreased. The excellent microwave dielectric characteristics (ε=94·9, Qf=5620 GHz, τ_f=21·4 ppm/°C could be achieved in the present ceramics through the microstructure control.     

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.     

Microwave dielectric properties and microstructures of Nd(Mg0.5Sn0.5−xTix)O3 ceramics

This study elucidates the microwave dielectric properties and microstructures of Nd(Mg_0.5Sn_0.5?xTi_x)O₃ ceramics with a view to their potential for microwave devices. The Nd(Mg_0.5Sn_0.5?xTi_x)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the Nd(Mg_0.5Sn_0.4Ti_0.1)O₃ ceramics revealed no significant variation of phase with sintering temperatures. A dielectric constant (?_r) of 21.1, a quality factor (Q × f) of 50,000 GHz, and a temperature coefficient of resonant frequency (τ_f) of ?60 ppm/°C were obtained for Nd(Mg_0.5Sn_0.4Ti_0.1)O₃ ceramics that were sintered at 1550 °C for 4 h.     

Origin of significantly enhanced dielectric response and nonlinear electrical behavior in Ni2+-doped CaCu3Ti4O12: Influence of DC bias on electrical properties of grain boundary and associated giant dielectric properties

CaCu_3-xNi_xTi₄O₁₂ (x?=?0, 0.05, and 0.10) powders were synthesized using a solid state reaction method. Phase structure and microstructure analyses revealed that all sintered CaCu_3-xNi_xTi₄O₁₂ ceramics were of a pure phase. The CaCu₃Ti₄O₁₂ ceramics had a dense microstructure and grain sizes were enlarged by doping with Ni²⁺. Interestingly, the dielectric permittivity was significantly enhanced, whereas the loss tangent was greatly suppressed to ～0.046–0.034 at 1?kHz. All sintered ceramics exhibited non-Ohmic characteristics. Clarification of the influences of DC bias showed that the dielectric permittivity and loss tangent values were increased by DC bias. The resistance of grain boundaries and the associated conduction activation energy of CaCu_3-xNi_xTi₄O₁₂ ceramics were reduced as the DC bias voltage increased. Therefore, the observed non-Ohmic behavior and significantly enhanced dielectric properties should be closely related to variation in the Schottky barriers at the grain boundaries.