Giant dielectric, low dielectric loss, and non-ohmic properties of nanocrystalline CaCu3Ti4O12

A simple polymer pyrolysis method has been successfully used to prepare CaCu₃Ti₄O₁₂ (CCTO) nanoparticles by calcination the obtained precursor powder at a low temperature of 800 (CCTO-1) and 850 °C (CCTO-2) in air for 4 h. The XRD results show that both of the calcined powders (CCTO-1 and CCTO-2) are pure having perovskite structure with the crystallite sizes, as evaluated by the XRD line boardening technique, of 47.5 and 75 nm, respectively. The particle sizes as estimated from the bright field images of TEM were found to be in the range of 10–35 and 7–52 nm for CCTO-1 and CCTO-2, respectively. The further sintering of CCTO-1 and CCTO-2 at 1,050 °C in air for 6 h, CCTO-1A and CCTO-2A, are also pure with perovskite structure as indicated by the XRD results. The measurements of the dielectric constant ( $ \varepsilon^{\prime } $ ε ′ ) and the low loss tangent (tanδ) at 1 kHz and 20 °C of CCTO-2A were found to be ~11,472 and ~0.0438, respectively. In addition, the CCTO-2A sample shows a small temperature coefficients ( $ \left| {\Updelta \varepsilon^{\prime } } \right| < 15\,\% $ | Δ ε ′ | < 15 % ) in a wide temperature range from ?50 to 110 °C. The non-Ohmic properties non-linear coefficient (α) of CCTO-1A and CCTO-2A were observed and the non-linear coefficient (α) of them determined in the range of 1–10 mA cm^?2 were found to be 12.00 and 7.26, respectively. Moreover, the breakdown field (E _b ) of CCTO-1A and CCTO-2A ceramics obtained at J = 1 mA cm^?2 were calculated and found to be 811 and 1,342 V cm^?1, respectively.     

Sintering behavior and dielectric properties of polycrystalline CaCu3Ti4O12

Sintering behavior and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) have been studied. CCTO phase was formed at 950 °C. A two-step sintering method was employed. The pressed green body of CaCu₃Ti₄O₁₂ was first heated to 1,080 °C to achieve an intermediate density (>75% of theoretical density), then cooled down and held at 950 °C for 0–20 h until it was fairly dense. A slight grain growth was observed for 20 h holding time with a significant increase in density from 81% to 92% of theoretical density. The average grain size of dense ceramics was ~6 μm and the bulk density was 4.7 g/cm³. The normally sintered specimen at 1,070 °C exhibited slightly higher density (4.8 g/cm³, 95%) with bimodal grain size. Normal sintering also yielded higher dielectric constants than the specimens processed by the two-step sintering.     

Microstructure and dielectric properties of CaCu3Ti4O12 ceramic

CaCu₃Ti₄O₁₂ (CCTO) was prepared by the solid state technique. The sample was calcined at 900 °C/12 h and sintered at 1050 °C/24 h, then subjected to XRD to ensure CCTO formation. The microstructure was observed by SEM. XRD results identified both samples as single phase CCTO, whereas the microstructure shows abnormal grain growth and large pores. Sintering was studied in the temperature range of 950–1050 °C for 3–12 h. Increasing sintering temperature enhances the density and secondary formation of Cu₂O. A clear grain boundary and dense microstructure were observed. The results show that the sample sintered at 1040 °C/10 h yields a clearly uniform grain size with the highest ε_r (33,210).     

电极对CaCu3Ti4O12陶瓷介电性能的影响

通过研究在不同气氛(氮气和氧气),CaCu3Ti4O12(CCTO)陶瓷样品在一定温度下进行后处理后,不同功函数电极对其介电性质的影响,进而研究CCTO陶瓷的巨介电常数的起源问题.我们在空气中制备了CaCu3Ti4O12陶瓷,发现样品表面电阻率很大,样品表面呈现绝缘态,此时不同功函数电极以及不同电极制备方法对其介电性质几乎没有影响,说明CCTO的巨介电常数是由孪晶界或半导体晶粒与绝缘晶界所产生的内部阻挡电容(IBLC)所引起.但当样品在高温氮气中后处理后,样品表面电阻率明显下降,以较大功函数的金属作为电极的样品,其介电常数有了明显的提高,而以功函数小的金属作为电极的样品,其介电常数变化不大.从而进一步说明当CCTO样品表面处于半导态,表面电极效应也是CCTO巨介电常数来源之一.     

Non-Ohmic and dielectric properties of Ba-doped CaCu3Ti4O12 ceramics

The microstructure, dielectric and electrical properties of Ca_1?x Ba _x Cu₃Ti₄O₁₂ (where x = 0, 0.025, and 0.05) ceramics were investigated. Our microstructural analyses revealed that Ba²⁺ doping ions preferentially form in a secondary phase, and are not introduced into the CaCu₃Ti₄O₁₂ lattice. Grain growth rate of CaCu₃Ti₄O₁₂ ceramics was significantly inhibited by the Ba-related secondary phase particles, resulting in a large decrease in their mean grain size. The dielectric permittivity of CaCu₃Ti₄O₁₂ ceramics decreased with increasing Ba content. Their loss tangent decreased after addition of CaCu₃Ti₄O₁₂ with 2.5 mol% of Ba²⁺, and increased with increasing Ba contents to 5.0 mol%. The nonlinear coefficient and breakdown field of the Ca_1?x Ba _x Cu₃Ti₄O₁₂ ceramics were significantly enhanced by adding 2.5 mol% of Ba²⁺, followed by a slight decrease as Ba²⁺ concentration was increased to 5.0 mol%. Using impedance spectroscopy analysis, it was revealed that variations in dielectric and non-Ohmic properties are associated with electrical response of grain boundaries. This supports the internal barrier layer capacitor model.     

Effects of Kaolinite additions on sintering behavior and dielectric properties of CaCu3Ti4O12 ceramics

Commercial Kaolinite was employed as sintering aid to reduce the sintering temperature of CaCu₃Ti₄O₁₂ (CCTO) ceramics. The effects of Kaolinite content and sintering temperature on the densification, microstructure and dielectric properties of CCTO ceramics have been investigated. The density characterization results show that the addition of Kaolinite significantly enhanced the relative density of CCTO ceramics to about 92 %. X-ray diffraction results show CCTO ceramics with a low amount of Kaolinite exhibited perovskite-like structure, but 1.0 wt% Kaolinite additions resulted in the formation of a secondary phase, CaO–TiO₂–Al₂O₃–SiO₂ glass phase was formed and improved the dielectric constant of ceramics, which was supported by scanning electron microscopy–energy dispersive X-ray results. CCTO ceramic with 1.0 wt% Kaolinite addition possessed well temperature and frequency stability of dielectric constant. It was found that Kaolinite lowered the dielectric loss of the samples.     

Effect of coupling agents on the dielectric properties of CaCu3Ti4O12/PVDF composites

Phase-pure calcium copper titanate (CaCu₃Ti₄O₁₂, CCTO) ceramic particles were synthesized via a sol–gel route. The CCTO was treated by bis[3-(triethoxysilyl)propyl]tetrasulfide (Si69) to give CCTO@Si69. The dielectric composites based on CCTO (or CCTO@Si69) and polyvinylidene fluoride (PVDF) were molded with desirable dielectric properties by mechanical mixing process and hot-pressing. The structures of CCTO and CCTO@Si69 were investigated by scanning electron microscopy (SEM) energy spectrum, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy. The stretching vibration of SO at 1096 cm⁻¹ in FTIR is an indication that chemical bond was formed between Si69 and CCTO. The influence of Si69 on the preparation and the dielectric properties of CCTO/PVDF dielectric composites were discussed. When the content of Si69 was 0.1 mL (relative to 1 g of CCTO), the dielectric constant (ε) (at a frequency of 1 kHz) of CCTO@Si69/PVDF composites reached the maximum value of 84, this value is 5.25 times that of an equal amount of CCTO of CCTO/PVDF composites (ε ≈ 16). The CCTO/PVDF and CCTO@Si69/PVDF composites had very stable dielectric properties over a wide range of temperatures (20–160 °C). These composites can be applied as high-energy–density capacitors in electronic and electrical engineering fields.     

Modified giant dielectric properties of samarium doped CaCu3Ti4O12 ceramics

Effects of Sm³⁺ substitution on the microstructure and dielectric properties of CaCu₃Ti₄O₁₂ ceramics were investigated. The grain size of CaCu₃Ti₄O₁₂ ceramics was greatly decreased by doping with Sm³⁺, resulting from the ability of Sm³⁺ to inhibit the grain growth rate. This result can cause a decrease in the dielectric constant (?′) and loss tangent (tan δ) of CaCu₃Ti₄O₁₂ ceramics. Interestingly, high dielectric permittivity (?′ ～ 10,863) and low loss tangent (tan δ ～ 0.043 at 20 °C and 1 kHz) were observed in the Ca_0.925Sm_0.05Cu₃Ti₄O₁₂ ceramic. Nonlinear electrical properties of CaCu₃Ti₄O₁₂ ceramics were modified by doping with Sm³⁺. The dielectric relaxation behavior of Sm-doped CaCu₃Ti₄O₁₂ ceramics can be well ascribed based on the internal barrier layer capacitor model of Schottky barriers at the grain boundaries.     

CaCu3Ti4O12 nanoparticles using polyvinyl pyrrolidone: synthesis and dielectric properties

Nanocrystalline CaCu3Ti4O12 powders with particle sizes of 39.28 8.12 nm were synthesized by a simple modify sol-gel using PVP (Poly-vinyl-pyrrolidone). The synthesized precursor was characterized by TG-DTA to determine the thermal decomposition and crystallization temperature which was found to be at above 500 degrees C. The precursor was calcined at 800 degrees C in air for 8 h to obtain nanocrystalline powders of CaCu3Ti4O12. The calcined CaCu3Ti4O12 powders were characterized by XRD, FTIR, SEM and TEM. Sintering of the powders was conducted in air at 1100 degrees C for 16 h. The XRD results indicated that all sintered samples have a typical perovskite CaCu3Ti4O12 structure and a small amount of CaTiO3. SEM micrographs showed the average grain sizes of 1.86 +/- 0.69 /m for the sintered CaCu3Ti4O12 ceramic prepared using the CaCu3Ti4O12 powders calcined at 800 degrees C. The sintered samples exhibit a giant dielectric constant, epsilon' of approximately 10(3)-10(4). The large low-frequency dielectric permittivity at low temperature is closely related to sub-grain boundary distribution, including conductivity effect. Furthermore, the ceramic shows three semicircles in the complex impedance plane. However, at low frequency, semicircles of sub-grain boundary and grain boundary are considered to represent collapse different electrical mechanisms. The another is ascribed to the contribution of grain. The dielectric behavior at several frequencies and temperatures of these samples can be attributed to electronic inhomogeneities present in material and can be explained based on a microstructural model.     

CaCu3Ti4O12多晶块材的巨介电常数

采用固相反应法制备了CaCu3Ti4O12单相多晶块材,系统地研究了其介电常数与温度（ε（T））和频率（ε（f））的依赖关系,结果表明,CaCu3Ti4O12多晶块材在温度为300K、频率为1kHz时,ε高达14000;在1kHz、100～340K温区内ε的数值基本不变．CaCu3Ti4O12多晶块材的介电特性很难用位移型铁电体的相关理论描述,可能源于在纳米尺度的畴区内极化弛豫的动态变化．在1kHz交流电场作用下,温度低于100K时,CaCu3Ti4O12多晶块材ε的急剧下降与其中氧空位引起Ti离子变价所产生的极化子的热激活相关。     

Microstructural and dielectric properties of donor doped (La3+) CaCu3Ti4O12 ceramics

The effect of La³⁺ doping on Ca²⁺ sites in CaCu₃Ti₄O₁₂ (CCTO) was examined. Polycrystalline samples in the chemical formula Ca_(1-x)La_(2/3)x Cu₃Ti₄O₁₂ with x = 0, 0.5, 1 were synthesized via the conventional solid state reaction route. X-ray powder diffraction analysis confirmed the formation of the monophasic compounds and indicated the structure to be remaining cubic with a small increase in lattice parameter with increase in La³⁺ doping. The dielectric and impedance characteristics of Ca_(1-x)La_(2/3)x Cu₃Ti₄O₁₂ were studied in the 100 Hz–10 MHz frequency range at various temperatures (100–475 K). A remarkable decrease in grain size from 50 μm to 3–5 μm was observed on La³⁺ substitution. The dielectric constant of CaCu₃Ti₄O₁₂ decreased drastically on La³⁺ doping. The frequency and temperature responses of dielectric constant of La³⁺ doped samples were found to be similar to that of CaCu₃Ti₄O₁₂. The effects of La³⁺ doping on the electrical properties of CaCu₃Ti₄O₁₂ were probed using impedance spectroscopy. The conducting properties of grain decreased while that of the grain boundary increased on La³⁺ doping, resulting in a decrease of the internal barrier layer effect. A decrease in grain boundary capacitance and stable grain response in La³⁺ doped CCTO ceramics were unambiguously established by modulus spectra studies.     

The electrode/sample contact effects on the dielectric properties of the CaCu3Ti4O12 ceramic

In this paper, the contact effects at the electrode/sample interfaces on the dielectric properties of the CaCu₃Ti₄O₁₂ (CCTO) ceramic were studied. The experimental results provide clear evidence that the colossal dielectric constant in CCTO is related to the ceramic itself; however, it may also partly originated from the electrode/sample contact effects which depends on the surface resistivity of the sample. When the surface resistivity of the ceramic is as high as 1.2 × 10⁸ Ω cm, no obvious mobile space charges can be observed, and the dielectric properties of the sample is inert to the different metal electrodes and various sample thicknesses, indicating the colossal dielectric constant (near 2000 at 10 kHz) at room temperature is due to the true properties of the ceramic itself. However, after the surface resistivity is lowered to 3.1 × 10⁷ Ω cm through post-annealing the sample in N₂ atmosphere at 750 °C, obvious mobile space charges can be observed, and the dielectric properties of the sample become sensitive to the different types of contacts. The dielectric constant of the sample with Pt electrode shows a significant enhancement (up to 5000 at 10 kHz), comparing with that of the sample with Ag electrode. Clearly, in this case, the extrinsic contact contributes partly to the colossal dielectric constant of CCTO ceramic.     

CaCu3Ti4O12 ceramics from different methods: microstructure and dielectric

CaCu₃Ti₄O₁₂ (CCTO) ceramics were synthesized by methods of sol–gel, traditional solid-state reaction, and thermal decomposition of organic solution. The results exhibit that the microstructures and electric characteristics are affected by the methods of synthesis. The X-ray diffraction patterns show that all samples have a perovskite-like CCTO phase. Moreover, CCTO ceramic from traditional solid-state reaction have the phases of TiO₂ and CuO. The scanning electron microscopy images show that CCTO ceramics from different methods have different grain sizes, grain boundaries, and densities. Dielectric properties of the CCTO ceramics were characterized in a broad frequency range (10–10⁷ Hz) at room temperature. The CCTO ceramics from thermal decomposition of organic solution have the dielectric constant of more than 5 × 10⁴ at 10 Hz. The nonlinear relationship between the current density and the electric field strength can be observed in all the three samples.     

Effect of grain-boundary behavior on the dc electric conduction in Rb-doped CaCu3Ti4O12

Ca_1?x Rb _x Cu₃Ti₄O₁₂ (x = 0, 0.03, 0.05, 0.07 and 0.09) ceramics have been synthesized by the sol–gel method. The results of X-ray diffraction, scanning electron microscopy and energy dispersive X-ray analysis indicate that a small amount of CuO and the grain boundary layers with Cu-rich and Ti-poor compositions are formed in the Rb-doped ceramic samples. The curves of dc electrical current density versus electric field strength have been collected at different temperatures, and the electrical conduction behaviors at grain boundary have been studied in detail based on the grain-boundary Schottky model. The results show that the formation of the Cu-rich and Ti-poor grain boundaries greatly affects the properties of grain-boundary Schottky potential barrier. For example, the barrier width increases with the increase on doping concentration x, and the barrier height (Ф_B) is also greatly enhanced as the concentration of dopants is very small, but as x is larger than 0.05, the Ф_B values reduce. These results should be ascribed to the second phases at grain boundary and the change of electronic structure.     

Dielectric properties of bismuth doped CaCu3Ti4O12 ceramics

Ca_1?3x/2Bi_xCu₃Ti₄O₁₂ (x = 0.0–0.3) ceramics were prepared by the conventional solid-state reaction method. X-ray powder diffraction analysis confirmed the formation of cubic CCTO phase except for subtle peaks of CuO. SEM micrographs suggested that the morphologies of doped CCTO ceramics had been sheet-like for high Bi-doping amount, and the dominant grain size decreasing could be seen for the small content of Bi-doping CCTO. Dielectric properties of pure and doped CCTO were investigated in a broad temperature range of 20–420 K. The results showed that bismuth doping could decrease the dielectric loss but suppress the dielectric temperature stability at the same time. Bi doped CCTO ceramics presented different relaxation properties. As to pure CCTO and BCCTO (x = 0.3) only one MW relaxation (Relaxation I) could be found, which moves to higher frequency with temperature increasing. However, two relaxation processes (Relaxation I and II) appear for BCCTO (x = 0.1–0.2). By means of complex impedance spectra analysis and Arrhenius fitting, we successfully separated the different conductive segments and explained the mechanisms of the two relaxation processes. Relaxation I appeared at low temperature could be attributed to the V_O doping energies inside CCTO grains which did not showed significant changing of activation energy after bismuth doping. For Relaxation II at higher temperature than Relaxation I, with activation energy obviously depending on the Bi-ion concentration, may be related with the V_O point defects at the grain boundaries.     

Effect of sintering temperature on the properties of modified mechanical alloyed CaCu3Ti4O12

This paper presents the effects of calcination time and sintering temperature on the properties of CaCu(3)Ti(4)O(12). Electroceramic material of CaCu(3)Ti(4)O(12) was prepared using a modified mechanical alloying technique that covers several processes, which are preparation of raw material, mixing and ball milling for 5 hours, calcination, pellet forming and, sintering. The objective of this modified technique is to enable the calcination and sintering processes to be carried out at a shorter time and lower temperature. The x-ray diffraction (XRD) analysis result shows that a single-phase of CaCu(3)Ti(4)O(12) was completely formed by calcination at 750 degrees C for 12 hours. Meanwhile, the grain size of a sample sintered at 1050 degrees C for 24 hours is extremely large, in the range of 20-50 mum obtained from field emission scanning electron microscopy (FESEM) images. The dielectric constant value of 14,635 was obtained at 10 kHz by impedance (LCR) meter in the sintered sample at 1050 degrees C. However, the dielectric constant value of samples sintered at 900 and 950 degrees C is quite low, in the range of 52-119.