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.     

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).     

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.     

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.     

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.     

Dielectric permittivity and loss of CaCu3Ti4O12 (CCTO) substrates for microwave devices and antennas

The solid state procedure was used to produce bulk ceramics of CCTO (CaCu₃Ti₄O₁₂). The samples of the CCTO ceramic were studied by X-ray powder diffraction, infrared and Raman scattering spectroscopy. The infrared and Raman scattering spectroscopy confirm the formation of the CCTO phase as seen by X-ray diffraction analysis. For one experimental procedure one uses an organic binder in the process of shaping the samples. In the second procedure the samples were prepared without the presence of the organic phase. For the second situation, we had higher dielectric constant ( _r =7370) with high loss (D=0.2) at 1 KHz. For the first procedure one has the lower dielectric constant ( _r =1530) and lower loss (D=0.11) at 1 KHz. Simple rectangular antenna prototypes were also designed on substrate samples (C1, C2, P1 and P2). For the antennas (with P2, C1 and C2 as substrates), the bandwidth (BW) is 90 MHz (around 3%). The antenna with P1 substrate presented a surprisingly high BW of 270 MHz that corresponds to a 10% bandwidth. In the microwave range one observes that higher values of the _r in the range of 3 GHz antennas is also presented by the P1 sample ( _r =41.6), and the lowest one was presented by P2 ( _r =33.7). Sample P1 also presents the highest value for the loss (Q ^–1) which is around 0.1 compared to the other samples which is around 0.03. Therefore, these measurements confirm the potential use for small high dielectric planar antennas. These materials are also attractive for capacitor applications and certainly for microelectronics, and microwave devices (e.g., cell mobile phones), where the miniaturization of the devices is crucial.     

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。     

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.     

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.     

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.     

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.     

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.     

Low temperature fabrication of the giant dielectric material CaCu3Ti4O12 by oxalate coprecipitation m ethod

The giant-dielectric-constant material CaCu₃Ti₄O₁₂ (CCTO) has been successfully fabricated by oxalate coprecipitation method, which is done at lower temperature and shorter reaction time than the conventional solid-state reaction. The precipitation containing stoichiometric amounts of the metal cations was heat-treated to achieve single-phase CCTO. DTA/TGA was carried out on a dried precipitate to study the thermal decomposition process. The phases, microstructure and dielectric properties of the sample were characterized by X-ray diffraction, scanning electron microscopy and precision impedance analyzer.     

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.     

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 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.