Microstructure-dependent giant dielectric response in CaCu3Ti4O12 ceramics

CaCu₃Ti₄O₁₂ ceramics were prepared at the sintering temperatures ranged from 1025 to 1125 °C, and the dielectric characteristics were evaluated together with the microstructures. The giant dielectric constant with the maximum of 53,120 was obtained in CaCu₃Ti₄O₁₂ ceramics at room temperature and 10 kHz, and strong processing and microstructure dependence of dielectric characteristics of the present ceramics was determined. The precipitation of the dispersed Cu-rich secondary phases of CuO and/or Cu₂O and their network structure provided the extrinsic origins of the enhanced giant dielectric response, and the present findings would offer the greater potential for enhancing the giant dielectric constant and controlling the dielectric loss in CaCu₃Ti₄O₁₂ ceramics by optimizing the microstructures.     

Observation of giant dielectric constant in CdCu3Ti4O12 ceramics

Although CdCu₃Ti₄O₁₂ is isostructural to CaCu₃Ti₄O₁₂, the room temperature low-frequency dielectric constant of the former compound was reported to be ∼400, only 1/25 of that of the latter material [M.A. Subramanian, et al., J. Solid State Chem. 151 (2000) 323]. In this communication, we report that the dielectric constant of CdCu₃Ti₄O₁₂ can be remarkably increased by elevating the sintering temperature. The room temperature dielectric constant at 100 kHz achieves 9000, almost as much as that of CaCu₃Ti₄O₁₂, for the sample sintered at 1283 K. The appearance of giant dielectric constant in CdCu₃Ti₄O₁₂ is explained in terms of internal barrier layer capacitance (IBLC) effect with the subgrain boundary as the barrier. Our result supplies an approach in searching for new giant-dielectric-constant materials in the CaCu₃Ti₄O₁₂ family.     

Ferroelectric properties of Pr6O11-doped Bi4Ti3O12

Praseodymium doped Bi₄Ti₃O₁₂ (BIT) ceramics with composition Bi_2.9Pr_0.9Ti₃O₁₂ (BPT) were prepared by solid state reaction. These samples have polycrystalline Bi-layered perovskite structure without preferred orientation, and consist of well-developed plate-like grains with random orientation. Pr doping into BIT causes a large shift of the Curie temperature (T_C) of the BIT from 675 to 398 °C. At an electric field of 87 kV/cm, the remanent polarization and the coercive field of the BPT ceramics are 30 μC/cm² and 52 kV/cm, respectively. Furthermore, the dielectric permittivity and the dissipation factor of the BPT ceramics are 300 and 0.003 at 1 MHz, 1 V, and room temperature. Ferroelectric properties of the BPT ceramics are superior to V-doped Bi₄Ti₃O₁₂ (∼20 μC/cm² and 80 kV/cm) and (Sr, Ta)-doped Bi₄Ti₃O₁₂ (∼12 μC/cm² and 71 kV/cm) ceramics. In addition, the dense ceramics of praseodymium-doped B₄Ti₃O₁₂ were obtained by sintering at 1100 °C, about 100-200 °C lower than those of the SrBi₂Ta₂O₉ system.     

Enhanced giant dielectric response in Mg-substituted CaCu3Ti4O12 ceramics

Effects of Mg-substitution on the giant dielectric response in CaCu₃Ti₄O₁₂ ceramics were investigated and discussed. A significantly enhanced giant dielectric response was obtained in Ca(Cu_1?xMg_x)₃Ti₄O₁₂ ceramics, and the dielectric constant step increased with increasing Mg-substitution content. The results of X-ray photoelectron analysis confirmed the obvious increase of Ti³⁺/Ti⁴⁺ ratio, and the enhanced giant dielectric response should originate from the corresponding modification of the mixed-valent structure. The present results have great scientific significance in deepening the understanding on the origin of giant dielectric response and modulating the giant dielectric constant step in CaCu₃Ti₄O₁₂.     

Dielectric properties of lanthanum-doped CaCu3Ti4O12 synthesized by semi-wet route

Effect of La³⁺ doping at Ca²⁺ site in CaCu₃Ti₄O₁₂ has been examined. Compositions with x=0.10, 0.20 and 0.30 were synthesized in the system Ca_(1−3x/2)La_xCu₃Ti₄O₁₂ by semi-wet method. Powder X-ray diffraction confirmed the formation of monophasic compounds. The structure remains cubic similar to CaCu₃Ti₄O₁₂. Lattice parameter increases slightly with increasing La³⁺ concentration. Microstructure has been studied using scanning electron microscopy (SEM). Average grain size is in the range 2-4 μm for various compositions. Energy-dispersive spectrometer (EDS) studies confirm the stoichiometry of the synthesized materials. Dielectric constant, dielectric loss and conductivity of the samples decrease with increasing lanthanum concentrations.     

Fe掺杂CaCu3Ti4O12陶瓷的介电性能与弛豫特性研究

采用固相反应法制备了CaCu₃Ti_4-xFe_xO₁₂(0≤x≤0.2)陶瓷,通过X射线衍射、扫描电子显微镜、介电频谱和阻抗谱等手段研究了Fe对CaCu₃Ti₄O₁₂陶瓷的结构和介电性能的影响.研究发现：CaCu₃Ti_4-xFe_{x关键词： 巨介电常数 双阻挡层电容模型 界面极化}     

Effect of Cu-stoichiometry on the dielectric and electric properties in CaCu3Ti4O12 ceramics

CaCu_3+yTi₄O₁₂ (y=0, ±0.025, ±0.05, ±0.1 and −0.15) ceramics are prepared by the conventional solid-state reaction technique under sintering condition of 1050 ^°C, 10 h. X-ray diffraction shows that they all have the good crystalline structure. Cu-deficient ceramics exhibit the microstructures of uniform grain size distribution, whereas both Cu-stoichiometric and Cu-rich ceramics display microstructures of bimodal grain size distribution. The largeness of low-frequency dielectric permittivity at room temperature is found to be very sensitive to the Cu-stoichiometry. Upon raising the measuring temperature, all of the ceramics present commonly three semicircles in the complex impedance plane. It indicates that there exist three distinct contributions, which are ascribed to arising from domains, grain boundaries and domain boundaries. In addition, the influence of CuO segregation on the dielectric and electrical properties is also discussed.     

CaCu3Ti4O12块材和薄膜的巨介电常数

用固相反应法和脉冲激光沉积(PLD)制备了CaCu₃Ti₄O₁₂块材和薄膜，获得了相对介电常数ε′（1kHz,300K)高于14000的介电特性，是目前该体系最好的结果.报道了(00l)取向高质量CaCu₃Ti₄O₁₂外延薄膜及其介电性质.C aCu₃Ti₄O₁₂相对介电常数ε′在100—300K温度范围 内 关键词： 3Ti₄O₁₂')" href="#">CaCu₃Ti₄O₁₂ 巨介电常数 PLD     

Influence of sintering conditions and doping on the dielectric relaxation originating from the surface layer effects in CaCu3Ti4O12 ceramics

Detailed investigations into the dielectric dispersion phenomenon in the giant dielectric constant material CaCu₃Ti₄O₁₂ (CCTO) around room temperature revealed the existence of two successive dielectric relaxations. In the temperature domain, a new dielectric relaxation was clearly observed around 250 K, in addition to the well-investigated dielectric relaxation close to 100 K. The effect of sintering and doping (La³⁺) on the strength of these dielectric relaxations were studied in detail. The sintering temperature as well as its duration was found to have tremendous influence on the dielectric relaxation that was encountered around 250 K. This Maxwell-Wagner (M-W) type of relaxation was found to be originating from the surface layer containing the Cu-rich phase, which was ascribed to the difference in the oxygen content between the surface and the interior of the sample. Interestingly, this particular additional relaxation was not observed in La_2/3Cu₃Ti₄O₁₂, a low dielectric constant member of the CCTO family, in which the segregation of Cu-rich phase on the surface was absent. Indeed the correlation between the new relaxation and the presence of Cu-rich phase in CCTO ceramics was further corroborated by the absence of the same after removing the top and bottom layers.     

CaCu3Ti4O12陶瓷的介电特性与弛豫机理

本文采用Novocontrol宽频介电谱仪在-100 ℃–100 ℃温 度范围内、0.1 Hz–10 MHz频率范围内测量了表面层打磨前 后CaCu₃Ti₄O₁₂陶瓷的介电特性, 分析了CaCu₃Ti₄O₁₂陶瓷的介电弛豫机理. 首先, 基于对宏观“壳-心”结构的定量分析, 排除了巨介电常数起源于表面层效应的可能性; 其次, 基于经典Maxwell-Wagner夹层极化及其活化能物理本质的分析, 排除了巨介电常数起源于经典Maxwell-Wagner极化的可能性; 最后, 依据晶界Schottky势垒与本征点缺陷的本质联系, 提出了巨介电常数起源于Schottky势垒边界陷阱电子弛豫的新机理. 陷阱电子弛豫机理反映了CaCu₃Ti₄O₁₂陶瓷本征点缺陷、 电导、介电常数之间的本质关系. 关键词： 3Ti₄O₁₂')" href="#">CaCu₃Ti₄O₁₂ 介电弛豫 Schottky势垒 点缺陷     

Low-temperature sintering and microwave dielectric properties of Ca2Zn4Ti15O36 ceramics

The sintering behavior, microstructures, and microwave dielectric properties of Ca₂Zn₄Ti₁₅O₃₆ ceramics with B₂O₃ addition were investigated. The crystalline phases and microstructures of Ca₂Zn₄Ti₁₅O₃₆ ceramics with 0-10 wt% B₂O₃ addition were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS). The sintering temperature of Ca₂Zn₄Ti₁₅O₃₆ ceramic was lowered from 1170 to 930 °C by 10 wt% B₂O₃ addition. Ca₂Zn₄Ti₁₅O₃₆ ceramics with 8 wt% B₂O₃ addition sintered at 990 °C for 2 h exhibited good microwave dielectric properties, i.e., a quality factor (Qf) 11,400 GHz, a relative dielectric constant (ε_r) 41.5, and a temperature coefficient of resonant frequency (τ_f) 94.4 ppm/°C.     

氧含量对CaCu3Ti4O12巨介电常数和介电过程的影响

本文研究了在真空、空气和氧气中烧结制备的三种 CaCu₃Ti₄O₁₂陶瓷材料的介电特性. 交流阻抗测量结果表明在10—300 K温度范围, 三种样品的介电温谱中均出现三个平台, 其电阻实部和电容虚部在相应温度出现损耗峰, 真空条件烧结的样品具有较高的介电平台和较明显的电阻实部与电容虚部峰值, 表明氧含量和氧空位对CaCu₃Ti₄O₁₂的介电性质具有重要影响, 介电温谱出现的三个平台分别源于晶粒、晶界及氧空位陷阱.温谱分析表明晶粒的激活能与烧结气氛有较大关系,氧空位引起的电子短程跳跃及跳跃产生的极化子是晶粒电导和电容的主要起源.氧空位陷阱的激活能基本与烧结气氛无关,约为0.46 eV. 氧空位对载流子的陷阱作用是CaCu₃Ti₄O₁₂ 低频高介电常数的重要起源.     

Reduced dielectric loss and leakage current in CaCu3Ti4O12/SiO2/CaCu3Ti4O12 multilayered films

The CaCu₃Ti₄O₁₂/SiO₂/CaCu₃Ti₄O₁₂ (CCTO/SiO₂/CCTO) multilayered films were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition method. It has been demonstrated that the dielectric loss and the leakage current density were significantly reduced with the increase of the SiO₂ layer thickness, accompanied with a decrease of the dielectric constant. The CCTO film with a 20 nm SiO₂ layer showed a dielectric loss of 0.065 at 100 kHz and the leakage current density of 6×10⁻⁷ A/cm² at 100 kV/cm, which were much lower than those of the single layer CCTO films. The improvement of the electric properties is ascribed to two reasons: one is the improved crystallinity; the other is the reduced free carriers in the multilayered films.     

La substitution in four-layers Aurivillius phase SrBi4Ti4O15

Ceramics with the nominal composition of SrBi_4−xLa_xTi₄O₁₅ have been prepared within the range of 0≤x≤1.8, and the dielectric properties are investigated. Single phase SrBi_4−xLa_xTi₄O₁₅ solid solution exists until the secondary phase of La_2/3TiO₃ appears at x=1.6. The Curie temperature is 520 °C for pure SrBi₄Ti₄O₁₅, and it shifts to low temperature with increasing x, which is due to the smaller structural distortion caused by La³⁺ substitution. In addition, the dielectric constant anomaly is suppressed with the substitution. No dielectric relaxation behavior is observed. When x≥1.2, the paraelectric state is attained in the present ceramics. La³⁺ substitution effects on the SrBi₄Ti₄O₁₅ ceramics are also compared with the previous work on Bi_4−xLa_xTi₃O₁₂.     

Electrical properties of neodymium doped CaBi4Ti4O15 ceramics

Neodymium doped bismuth layer structure ferroelectrics (BLSFs) ceramics CaBi_4−xNd_xTi₄O₁₅ (x=0, 0.25, 0.50, 0.75) were prepared by solid-state reaction method. X-ray diffraction pattern showed that single phase was formed when x=0-0.75. The refined lattice parameters showed that a (b) axes decrease at x=0.25 and increase with more Nd³⁺ dopant. The effects of Nd³⁺ doping on the dielectric and ferroelectric properties of CaBi₄Ti₄O₁₅ ceramics are studied. Nd³⁺ dopant decreased the Curie temperature linearly, and the dielectric loss, tan δ, as well. The remnant polarization of Nd³⁺ doped CaBi₄Ti₄O₁₅ ceramics was increased by 80% at x=0.25, while more Nd³⁺ dopant decreased the remnant polarization. CaBi_3.75Nd_0.25Ti₄O₁₅ ceramics had the largest piezoelectric constant d₃₃. The structure and properties of CaBi_4−xNd_xTi₄O₁₅ ceramics showed that Nd³⁺ may occupy different crystal locations when Nd³⁺ content x is less than 0.25 and more than 0.50.     

CaCu3Ti4O12陶瓷的微观结构及直流导电特性

采用传统固相反应法制备了CaCu₃Ti₄O₁₂陶瓷.XRD证实其CaCu₃Ti₄O₁₂相;SEM观察到明显的晶粒晶界结构,晶界区亦由小晶粒构成;结合EDS结果,判定晶界区小晶粒为CuO.在较宽的温度范围内,CaCu₃Ti₄O₁₂陶瓷的介电常数保持在10⁵左右;当频率为10³ Hz温度小于150 K时,介电常数迅速下降.在173—373 K温度范围内,通过其I-V特性,得到CaCu₃Ti₄O₁₂陶瓷直流电导随温度的变化：直流电导与温度的关系可分为三部分,对应的活化能分别为0.681 eV,0.155 eV和0.009 eV,这与CuO陶瓷直流电导活化能一致.可以认为晶界区的CuO小晶粒在CaCu₃Ti₄O₁₂陶瓷的直流电导中占主导,这为解释CaCu₃Ti₄O₁₂陶瓷反常的介电性能提供了新的思路. 关键词： 3Ti₄O₁₂')" href="#">CaCu₃Ti₄O₁₂ 微观结构 直流电导 介电特性     

CaCu3Ti4O12陶瓷的微观结构和电学性能

利用传统的固相反应工艺，在不同的烧结温度下制备了一系列的CaCu₃Ti₄O₁₂陶瓷样品，考察了其微观结构以及介电和复阻抗方面的电学性质.研究发现这些样品在微观结构方面可分为三种类型，高介电性与微观结构有着密切的关联性.室温下，样品的低频介电常数随陶瓷晶粒尺寸的增大而提高.随着测试温度的升高，不同微观结构类型的样品呈现出不同的电学性质的变化，但其中也存在着一些相同的特征.高温下，介电频谱呈现出一个低频介电响应和两个类Debye型弛豫色散，复阻抗谱呈现出三个Cole-Cole半圆弧.将实验上观测到的电学性质的起因归于陶瓷多晶微结构中的晶畴、晶界和晶粒内的缺陷. 关键词： 3Ti₄O₁₂')" href="#">CaCu₃Ti₄O₁₂ 微观结构 电学性质     

First principles study of the electron structures of CaCu3Mn4O12 and CaCu3Ti4O12

The electronic structures of CaCu₃Mn₄O₁₂ and CaCu₃Ti₄O₁₂ are investigated from HF SCF LCAO calculation. In CaCu₃Mn₄O_12, the band and the density of states show a spin asymmetric ferrimagnetic character with a small energy gap. The Mn spin is anti-aligned with the Cu spin, and the total spin moment is 9 μ_B. Our calculation correctly reproduces the observed antiferromagnetic insulating character of CaCu₃Ti₄O₁₂. The gap in the band structure, which is 2.15 eV, reasonably agrees with the experimental value 1.5 eV. The electron density populations at different planes show clearly that the electron density has symmetric character. A tilted Mn(Ti) orbital implies a typical tilted three-dimensional network of MnO₆ (TiO₆) octahedra due to doping of the Jahn–Teller ion Cu. There is no covalency between Ca, Cu and Mn(Ti) atoms. In contrast, there are stronger bonds and somewhat likely covalency between Cu and O atoms, and also between Mn(Ti) and O atoms.     

Compression of CdCu3Ti4O12 perovskite to 55 GPa

Synchrotron x-ray diffraction measurements of CdCu₃Ti₄O₁₂ (CDCTO) were performed up to 55.5 GPa. There is no structural phase transformation in this pressure range. The irregular curvature shifts of the P-V curve are attributed to the grain surface effect. Analysis indicates that the grain surface of CDCTO is stiffer than the grain interior at higher pressures. We point out that the atoms on grain surfaces must be either densely packed or have a strong correlation with the gain interior in order to have a high dielectric constant, as in CaCu₃Ti₄O₁₂. The derived bulk modulus of CDCTO is approximately 235±7 GPa with K^′=5.1±0.4.     

Colossal dielectric constants: A common phenomenon in CaCu3Ti4O12 related materials

In the present work we demonstrate that in addition to the well-known colossal-dielectric-constant material CaCu₃Ti₄O₁₂ various members of the series Ln_2/3Cu₃Ti₄O₁₂ with Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Tm also exhibit giant values of the dielectric constant. Just as CaCu₃Ti₄O₁₂, all these materials show a Maxwell–Wagner type relaxation process. For the best material, Pr_2/3Cu₃Ti₄O₁₂, we provide a detailed investigation of its dielectric properties in a broad frequency range up to 1 GHz. Polarization at internal barriers, most likely grain boundaries, seems to be the reason for the observed very high values of the dielectric constant. Taking into account the present results and those reported in the literature, we conclude that CaCu₃Ti₄O₁₂ is not exceptional at all and there seem to be various isostructural materials with similar dielectric properties.