(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.     

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.     

Microstructures and dielectric relaxation behaviors of pure and tellurium doped CaCu3Ti4O12 ceramics prepared via vibro-milling method

In this work, we have reported microstructures and the dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics doped with different proportions of TeO₂ dopant (mol%, x=0, 0.5%, 1.0%, 2.0%). The pure and tellurium doping CCTO ceramics were prepared by a conventional solid-state reaction method and the effects of TeO₂ doping on the electrical properties and microstructures of these ceramics were investigated. XRD analysis confirmed the formation of single-phase material in samples. Scanning electron microscopy (SEM) is used in the micro structural studies of the specimens, which showed that TeO₂ doping can reduce the mean grain size and increasing size of an abnormal grain growth. Lattice parameter increases slightly with tellurium doping in CCTO, the dielectric constant reached a value as high as 18,000 (at 1 kHz) at a tellurium-doping concentration of 2.0 mol% and showed temperature stability at high frequency. The loss tangent of Te-doped CCTO ceramics was less than 0.05 at 1 kHz region below 105 °C. The loss tangent properties could be interpreted by the internal barrier layer capacitor model and the impedance measurement data.     

CaCu3Ti4O12 ceramics from co-precipitation method: Dielectric properties of pellets and thick films

Dielectric properties of CaCu₃Ti₄O₁₂ (CCTO)-based ceramics and thick films (e ～50 μm) prepared from powders synthesized by a soft chemistry method (co-precipitation) are presented and discussed. The characteristics of pellets and thick films are compared.The pellets exhibit high values of the dielectric permittivity (?_r ～1.4 × 10⁵) and relatively small dielectric losses (tan δ ～0.16) at 1 kHz and room temperature. These properties are independent of the nature of the metallization of the electrodes. In addition, the dielectric permittivity decreases when the diameter of the electrodes of the pellets increases, while the losses remain constant. This result, which is strongly related to the nature of the dielectric material in between the electrodes, constitutes a strong indication that the high dielectric permittivity values observed in this material are not related to an interfacial (electrode material) related mechanism but is an internal barrier layer capacitor (IBLC) type.Very high values of the dielectric permittivity of CCTO thick films are measured (?_r ～5 × 10⁴). The differences in dielectric permittivity between thick films and dense pellets may be attributed to the difference in grain size due to different CuO contents, and to the different reactivity of the materials.     

Development of novel magnetic-dielectric ceramics for enhancement of reflection loss in X band

The purpose of this research was to develop BaFe_9.5Al_1.5CrO₁₉-xCaCu₃Ti₄O₁₂ nanocomposites (x=10%, 20%, 30%, 40%, 50%) and investigate their structural and magnetic features. The substituted barium hexaferrite (BaFe_9.5Al_1.5CrO₁₉) nanoparticles and calcium copper titanate (CaCu₃Ti₄O₁₂) particles were synthesized by the auto-combustion sol-gel method. The structural, chemical composition and morphology of CaCu₃Ti₄O₁₂ (CCTO) and the nanocomposites were investigated by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. The magnetic and microwave properties of nanocomposites were also investigated by vibrating sample magnetometer and vector network analyzer, respectively. The results confirmed that 1100 °C is the optimum synthesis temperature for CCTO, the mean particles size of the CCTO particles changing from 220 nm (at 850 °C) to 2.18 µm (1250 °C). The SEM micrograph revealed that in all of the BaM-xCCTO nanocomposites (x=10%, 20%, 30%, 40%, 50%), the CCTO dielectric particles were attached to the substituted barium hexaferrite nanoparticles, indicating the effectiveness of the adopted synthesis method. Due to the presence of a dielectric phase in the nanocomposites the saturation magnetization decreases from 22 emu/g to 12 emu/g. The coercive field was a slightly larger than substituted barium hexaferrite and increased from 5.558 kOe for substituted barium hexaferrite to 5.813 kOe for BaM-50CCTO due to hindered motion of the domain walls by the dielectric phase and also to the collective behavior of agglomerated barium ferrite nanoparticles. The BaM-30CCTO nanocomposite shows the highest value of reflection loss compared to other nanocomposites. The reflection dip frequency of BaM-30CCTO nanocomposite was −48.85 dB at 10.93 GHz.     

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.     

Microstructural evolution and dielectric properties of SiO2-doped CaCu3Ti4O12 ceramics

The abnormal grain growth (AGG) behavior of undoped and SiO₂-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics were investigated. With the addition of 2 wt.% SiO₂, the AGG-triggering temperature decreased from 1100 to 1060 °C, and the temperature for obtaining a uniform and coarse microstructure decreased from 1140 to 1100 °C. The lowering of the AGG temperature by SiO₂ addition was attributed to the formation of a CuO-SiO₂-rich intergranular phase at lower temperature. The apparent dielectric permittivity of coarse SiO₂-doped CCTO ceramics was ∼10 times higher than that of fine SiO₂-doped CCTO ceramics at the frequency of 10³–10⁵ Hz. The doping of SiO₂ to CCTO ceramics provides an efficient route of improving the dielectric properties via grain coarsening. The correlation between the microstructure and apparent permittivity suggests the presence of a barrier layer near the grain boundary.     

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.     

Low temperature preparation of CaCu3Ti4O12 ceramics with high permittivity and low dielectric loss

Low temperature preparation of CaCu₃Ti₄O₁₂ ceramics with large permittivity is of practical interest for cofired multilayer ceramic capacitors. Although CaCu₃Ti₄O₁₂ ceramics have been prepared at low temperatures as previously reported, they have rather low permittivity. This work demonstrates that CaCu₃Ti₄O₁₂ ceramics can not only be prepared at low temperatures, but they also have large permittivity. Herein, CaCu₃Ti₄O₁₂ ceramics were prepared by the solid state reaction method using B₂O₃ as the doping substance. It has been shown that B₂O₃ dopant can considerably lower the calcination and sintering temperatures to 870 °C and 920 °C, respectively. The relative permittivity of the low temperature prepared CaCu₃Ti_4−xB_xO₁₂ ceramics is about 5 times larger than the previously reported results in the literature. Furthermore, the dielectric loss of the CaCu₃Ti_4−xB_xO₁₂ ceramics is found to be as low as 0.03. This work provides a beneficial base for the future commercial applications of CaCu₃Ti₄O₁₂ ceramics with large permittivity for the cofired multilayer ceramic capacitors.     

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.     

Evolution of the intergranular phase during sintering of CaCu3Ti4O12 ceramics

CaCu₃Ti₄O₁₂ (CCTO) ceramics have been processed by solid state reaction and sintered at 1100 °C for different times. A clear increase of the dielectric constant of the material up to values of 6 × 10⁴ has been observed with the sintering time. This increase is accompanied by a limited grain growth and intergranular Cu-oxide phase thickness reduction. The disappearance of the Cu-oxide phase is caused by the incorporation of Cu cations into the grains, contributing to the increase of the dielectric constant. Raman spectroscopy shows the decrease of TiO₆ octahedral rotational modes with the sintering time due to the incorporation of Cu cations into the CCTO grains. XANES measurements show that the Cu main oxidation state is Cu²⁺ and does not change with the sintering time. The fitting of the experimental dielectric constant to the Internal Barrier Layer Capacitance (IBLC) model reveals the change of the intergranular phase dielectric constant, caused by a compositional change due to the incorporation of Cu into the CCTO grains.     

Effects of strontium/lanthanum co-doping on the dielectric properties of CaCu3Ti4O12 prepared by reactive sintering

The extremely high dielectric constant of the cubic perovskite CaCu₃Ti₄O₁₂ (CCTO) has attracted increasing attention for a variety of capacitive elements in microelectronic device applications. In this research, the influence of Sr and La replacing Ca and Cu, respectively, to simultaneously controlling the intrinsic properties of grain boundaries in a co-doped CCTO ceramic has been investigated. The preparation was done using high purity compounds milled and mixed by mechano-synthesis and further consolidated by reactive sintering without calcination. Characterization by XRD confirmed the formation of single-phase CCTO ceramic and a residual amount CaTiO₃. The microstructure and composition analyzed by SEM/EDX showed a smaller grain size for the co-doped CCTO. Impedance measurements indicated the smallest dielectric loss for the co-doped ceramics compare to pure and single-doped CCTO, while reaching a higher dielectric permittivity than single-doped ceramics. The CCTO-SrLa sample also showed high thermal stability of the dielectric permittivity between 100 and 470?K, and the lowest loss between 200 and 300?K. This behavior was attributed to the lower bulk resistance exhibited by the co-doped sample.     

Effect of cesium and cerium substitution on the dielectric properties of CaCu3Ti4O12 ceramics

In this study, CaCu₃Ti₄O₁₂ (CCTO) ceramics were doped with cesium and cerium atoms to possibly improve the electrical properties of these widely used ceramics. In all cases, pure phase perovskites were produced where cesium doping enhanced the grain growth and cerium doping produced grain growth inhibition. The cesium doping showed an improvement in loss tangent performance, in contrast to the cerium doping which showed a negative result. A high dielectric constant >15,000 with a dielectric loss lower than 0.06 was observed for cesium 2.0 mol% doped at high frequencies. These results were related to the change in microstructure and the properties of grain boundary after doping.     

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).     

Dielectric behaviour of Hf-doped CaCu3Ti4O12 ceramics obtained by conventional synthesis and reactive sintering

CaCu₃(Ti_4?xHf_x)O₁₂ ceramics (x = 0.04, 0.1 and 0.2) were prepared by conventional synthesis (CS) and through reactive sintering (RS), in which synthesis and sintering of the material take place in one single step. The microstructure and the dielectric properties of Hf-doped CCTO (CCTOHf) have been studied by XRD, FE-SEM, AFM, Raman and impedance spectroscopy (IS) in order to correlate the structure, microstructure and the electrical properties. Samples prepared by reactive sintering show slightly higher dielectric constant than those prepared by conventional synthesis in the same way than the pure CCTO. Dielectric constant and dielectric losses decrease slightly increasing Hf content. For CCTOHf ceramics with x > 0.04 for CS and x > 0.1 for RS, a secondary phase HfTiO₄ appears. As expected, the reactive sintering processing method allows a higher incorporation of Hf in the CCTO lattice than the conventional synthesis one.     

Effects of multiwall carbon nanotubes on dielectric and mechanical properties of CaCu3Ti4O12 composite

This work reports the synthesis of calcium copper titanate (CaCu₃Ti₄O₁₂)/multiwall carbon nanotubes (MWCNT) composites using ultrasonic technique followed by sintering in a high vacuum furnace. The effect of MWCNT content (0.05, 0.1, 0.15, and 0.2 wt%) on the structural, dielectric, and mechanical properties of CaCu₃Ti₄O₁₂ (abbreviated as CCTO) were investigated by TEM, XRD, FTIR, FESEM-EDAX, dielectric measurement, as well as tensile strength and flexural strength tests. XRD patterns revealed that the MWCNT loading did not affect the phase structure; however, the average crystallite size (D) was reduced from 60.88 nm to 40.79 nm. The samples had porous structures and the porosity reduced from 45.57% to 40.73% with MWCNT loading. The dielectric and mechanical properties of CCTO were enhanced with an increase in MWCNT loading. An important observation was that the CCTO mixed with 0.2 wt% MWCNT exhibited the highest dielectric permittivity (ε_r = 27,768) and the lowest dielectric loss (tan δ = 0.52) at 1 kHz. With the addition of 0.2 wt% MWCNT, the values of load, tensile, and flexural strength increased to 10.38 kN, 101.88 MPa, and 275.07 MPa, respectively, due to improvement in densification. These outcomes have values for the fabrication of CCTO and the optimization of its performance for electronic devices such as capacitors and antennas.     

Dielectric properties of conventional and microwave sintered Lanthanum doped CaCu3Ti4O12 ceramics for high-frequency applications

The colossal dielectric response of La-doped CaCu₃Ti₄O₁₂ ceramics has been probed at room temperature for a frequency of 1Hz–20 MHz. In this work, the La-doped (CaCu₃Ti₄O₁₂)_x samples for x = 0.1, 0.2, and 0.3 have been sintered at 1100 °C using two different heating modes. SEM and EDS analysis investigated the microstructural chrysalis, grain size distribution, and the inhibitions of Cu-rich phase segregation into grain boundaries by the effect of La³⁺. The presence of main cubic single-phase of CCTO and the diminutive Bragg peak shift due to ion size effect of La³⁺ and Ca²⁺ have been identified by XRD for both conventional (CS) and microwave sintered (MWS) samples. XPS study revealed the effect of La³⁺ on the binding energies of Cu and Ti in CCTO. The dielectric properties namely dielectric constant (?), tan δ, and dielectric relaxation peaks were measured using BDS in which CS and MWS La-doped samples demonstrated (?) ～ >10⁴ and ～ >10³ along with low tan δ for x ≥ 0.1 at medium and high frequency (10⁴–10⁷Hz) than pure CCTO.     

Dielectric Characteristics of UV‐Curable CaCu3Ti4O12 Composite Thick Film Capacitors on Cu Foils

Dielectric composite thick films containing a high dielectric constant CaCu₃Ti₄O₁₂ (CCTO) filler in a UV‐cured polymer matrix were investigated as flexible planar capacitors on Cu foils. Dielectric performance depended on the volume fraction and size of CCTO particles dispersed in the cured polymer matrix. As a result, the thick films containing 33.3 vol.% CCTO with an average particle size of 0.47 μm exhibited a dielectric constant of ~80 and a dielectric loss of ~0.06 at 10 kHz. The effective medium theory model incorporating a morphology fitting parameter has been proven to be most close to the experimental values.     

Colossal permittivity and impedance analysis of tantalum and samarium co-doped TiO2 ceramics

In this study, (Ta_0.5Sm_0.5)_xTi_1−xO₂ (x = 0, 0.02, 0.06, 0.15) ceramics (referred to as TSTO) were fabricated by a standard solid-state reaction. As revealed by the X-ray diffraction (XRD) spectra, the TSTOs exhibit a tetragonal rutile TiO₂ structure. All the TSTO ceramics display colossal permittivity (~ 10²–10⁵). Moreover, the optimal ceramic, (Ta_0.5Sm_0.5)_0.02Ti_0.98O₂, exhibits high performance over a wide temperature range from 20 °C to 160 °C. At 1 kHz, the dielectric constant and dielectric loss are 2.30 × 10⁴ and 0.11 at 20 °C; they are 3.85 × 10⁴ and 0.64 at 160 °C. Dielectric and impedance spectra analyses for the TSTO ceramics indicate that the CP behavior over a broad temperature range in (Ta+Sm) co-doped TiO₂ could be explained by the internal barrier layer capacitance (IBLC) model, which consists of semiconducting grains and insulating grain boundaries.     

Structural and dielectric properties,and nonlinear electrical response of the CaCu3-xZnxTi4O12 ceramics: Experimental and computational studies

CaCu_3-xZn_xTi₄O₁₂ ceramics (x = 0, 0.05, 0.10) were successfully prepared by a conventional solid-state reaction method. Their structural and dielectric properties, and nonlinear electrical response were systematically inspected. The X-ray diffraction results indicated that single-phase CaCu₃Ti₄O₁₂ (JCPDS no. 75–2188) was obtained in all sintered ceramics. Changes in the lattice parameter are well-matched with the computational result, indicating an occupation of Zn²⁺ doping ions at Cu²⁺ sites. The overall tendency shows that the average grain size decreases when x increases. Due to a decrease in overall grain size, the dielectric permittivity of CaCu_3-xZn_xTi₄O₁₂ decreases expressively. Despite a decrease in the dielectric permittivity, it remains at a high level in the doped ceramics (~3,406–11,441). Besides retention in high dielectric permittivity, the dielectric loss tangent of x = 0.05 and 0.10 (~0.074–0.076) is lower than that of x = 0 (~0.227). A reduction in the dielectric loss tangent in the CaCu_3-xZn_xTi₄O₁₂ ceramics is closely associated with the enhanced grain boundary response. Increases in grain boundary resistance, breakdown electric field, and conduction activation energy of grain boundary as a result of Zn²⁺ substitution are shown to play a crucial role in improved grain boundary response. Furthermore, the XPS analysis shows the existence of Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺, indicating charge compensation due to the loss of oxygen lattice. Based on all results of this work, enhanced dielectric properties of the Zn-doped CCTO can be explained using the internal barrier layer capacitor model.