CaCu3Ti4O12 陶瓷松弛损耗机理研究

CaCu₃Ti₄O₁₂介电损耗较大且损耗机理尚不明确, 因此限制了其应用.本文采用固相法和共沉淀法合成CaCu₃Ti₄O₁₂陶瓷, 利用宽带介电温谱研究在交流小信号作用下, 双Schottky势垒耗尽层边缘深陷阱的电子松弛过程、 载流子松弛过程以及CaCu₃Ti₄O₁₂陶瓷的介电损耗性能. 研究发现, 在低频下以跳跃电导和直流电导的响应为主, 而高频下主要为深陷阱能级的松弛过程所致, 特别是活化能为0.12 eV的深陷阱浓度, 这是决定CaCu₃Ti₄O₁₂陶瓷高频区介电损耗的重要因素.降低直流电导, 有利于降低低频区介电损耗; 而高频区介电损耗的降低, 需要降低深陷阱浓度或增大晶粒尺寸. 共沉淀法制备的CaCu₃Ti₄O₁₂陶瓷, 有效降低直流电导及控制深陷阱浓度, 介电损耗降低明显. 关键词： 3Ti₄O₁₂陶瓷')" href="#">CaCu₃Ti₄O₁₂陶瓷 介电损耗 松弛过程 Schottky势垒     

CaCu3Ti4O12 陶瓷介电模量响应特性的研究

由于CaCu₃Ti₄O₁₂巨介电常数陶瓷的低频区直流电导较大, 本文采用模量 M"-f频谱表征与分析了低频和高频的两个松弛极化过程. 研究认为, 这两个特征峰属于晶界区Schottky 势垒耗尽层边缘深陷阱的电子松弛过程, 其中高频松弛峰起源于晶粒本征缺陷的电子松弛过程, 而低频松弛峰则为与氧空位有关的松弛极化过程. 对于CaCu₃Ti₄O₁₂这类低频下具有高直流电导的陶瓷材料, 采用模量频谱能更有效地分析研究其损耗极化机理. 关键词： 3Ti₄O₁₂陶瓷')" href="#">CaCu₃Ti₄O₁₂陶瓷 模量 松弛过程 电导     

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}     

巨介电常数氧化物CaCu3Ti4O12的介电和阻抗特性

采用固相烧结法合成了单相巨介电常数氧化物CaCu₃Ti₄O₁₂（CCTO）.用阻抗分析仪分析了10—420 K温度范围内的介电频谱和阻抗谱特性,并结合ZVIEW软件进行了模拟.结果表明：温度高于室温时,频谱出现两个明显的弛豫台阶,低频弛豫介电常数随温度升高而显著增大,表现出热离子极化特点;温度低于室温时,频谱表现出类德拜弛豫,且高、低平台介电常数值基本不随温度变化,表现出界面极化特点和较好的温度稳定性.频谱中依次出现的介电弛豫对应于阻抗谱中 关键词： 3Ti₄O₁₂')" href="#">CaCu₃Ti₄O₁₂ 介电频谱 阻抗谱 Cole-Cole半圆弧     

直流老化对CaCu3Ti4O12陶瓷介电性能的影响

在电场为3.5 kV/cm的条件下, 对CaCu₃Ti₄O₁₂陶瓷进行了60 h的直流老化, 研究了老化过程对CaCu₃Ti₄O₁₂陶瓷介电性能和电气特性的影响. J-E特性测试结果表明, 直流老化导致CaCu₃Ti₄O₁₂陶瓷击穿场强、非线性系数和势垒高度明显降低. 介电性能测试结果表明, 低频介电常数和介电损耗明显增大, 并且介电损耗随频率的变化遵从Debye弛豫理论, 可分解为直流电导损耗和弛豫损耗, 直流老化主要导致了电导损耗的增加. 在低温233 K, 介电损耗谱中出现两个弛豫峰, 其活化能分别为0.10, 0.50 eV, 认为对应着晶粒和畴界的弛豫过程, 且不随直流老化而变化. 通过电模量谱对CaCu₃Ti₄O₁₂陶瓷的弛豫过程进行了表征, 发现直流老化导致的界面空间电荷在外施交变电场的作用下符合Maxwell-Wagner极化效应, 并在低频区形成新的弛豫峰. 在高温323-473 K的阻抗谱中, 晶界弛豫峰在直流老化后明显向高频移动, 其对应的活化能从1.23 eV 下降到0.72 eV, 晶界阻抗值下降了约两个数量级. 最后, 建立了CaCu₃Ti₄O₁₂陶瓷的阻容电路模型, 分析了介电弛豫过程与电性能之间的关联.     

添加Nb对CaCu3Ti4O12陶瓷介电性能的影响

采用固相反应法制备了CaCu₃Ti_4-xNb_xO₁₂(x=0，0.01，0.04，0.08，0.2)陶瓷，样品在x取值范围内形成了连续固溶体.在40Hz—110MHz频率范围对样品进行了介电频谱分析，实验结果表明，与纯CaCu₃Ti₄O₁₂不同，含Nb试样除了在频率大于10kHz范围内出现的德拜弛豫 关键词： 巨介电常数 德拜弛豫 阻挡层电容 等效电路     

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     

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     

简化共沉淀法制备CaCu3Ti4O12陶瓷及其介电性能研究

具有巨介电常数的CaCu₃Ti₄O₁₂陶瓷是一种理想的高储能密度电容器材料.本文以草酸为沉淀剂、以乙酸铵为调节pH值的定量缓冲剂,获得制备CaCu₃Ti₄O₁₂陶瓷的简化共沉淀法.确定了pH=30为制备前驱粉料的最佳反应条件.通过显微分析和介电性能测量,发现在1040℃—1100℃范围内,随着烧结温度的提高,陶瓷的品粒尺寸增大,非线性系数上升,电位梯度和介电损耗下降,1100℃烧结的试样tanδ最低达到0.04.认为CaCu₃Ti₄O₁₂陶瓷介电损耗包含直流电导分量、低频松弛损耗和高频松弛损耗.低频松弛活化能为0.51 eV.,对应于晶界处的Maxwell-Wagner松弛极化;高频松弛过程活化能为0.10 eV,对应晶粒内部的氧空位缺陷.烧结温度的升高导致晶界电阻下降.     

CaCu3Ti4O12-MgTiO3陶瓷的介电性能与I-V非线性特征

采用固相反应法制备了一系列CaCu₃Ti₄O₁₂-xMgTiO₃(x = 0, 0.25, 0.5, 1.0)复相陶瓷,研究了MgTiO₃掺杂对CaCu₃Ti₄O₁₂(CCTO)陶瓷相结构、显微组织、介电性能和I-V非线性特征的影响.研究发现:MgTiO₃掺杂不仅使CC 关键词： I-V非线性系数')" href="#">I-V非线性系数 巨介电常数 压敏电压     

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.     

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.     

Ti deficiency effect on the dielectric response of CaCu3Ti4O12 ceramics

Single phase ceramics CaCu₃Ti_4.0O₁₂ and CaCu₃Ti_3.9O₁₂ have been prepared using the traditional solid-state reaction method. Compared with the stoichiometric ceramics CaCu₃Ti_4.0O₁₂, Ti-deficient ceramics CaCu₃Ti_3.9O₁₂ have the larger lattice parameter, the higher force constant, and smaller dielectric constant and the lower dissipation factor, although their fundamental characters of dielectric response are similar. Their characteristic relaxation frequencies are not well fitted with the Arrhenius Law but a tentatively supposed relation. With the Cole-Cole Law, the fitted broadened factors of dissipation peaks are 0.5433 and 0.8651 for CaCu₃Ti_3.9O₁₂ and CaCu₃Ti_4.0O₁₂, respectively. All facts mentioned above imply that mutually correlated motion of Ti ions or defects may be expected to be responsible for the giant dielectric constant and high dissipation factor of CaCu₃Ti_4.0O₁₂.     

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.     

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.     

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.     

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.     

Dielectric property of CaCu3Ti4O12 thin film grown on Nb-doped SrTiO3(100) single crystal

Thin film of CaCu₃Ti₄O₁₂ (CCTO) has been deposited on Nb-doped SrTiO₃(100) single crystal using pulsed laser deposition. The dielectric constant and AC conductivity of CCTO film in the metal–insulator–metal capacitor configuration over a wide temperature (80 to 500 K) and frequency (100 Hz to 1 MHz) range have been measured. The small dielectric dispersion with frequency observed in the lower temperature region (<300 K) indicates the presence of small defects in the deposited CCTO thin film. The frequency-dependent AC conductivity at lower temperature indicates the hopping conduction. The dielectric dispersion data has been analyzed in the light of both conductivity relaxation and Debye type relaxation with a distribution of relaxation times. Origin of dielectric dispersion is attributed to the distribution of barrier heights such that some charge carriers are confined between long-range potential wells associated with defects and give rise to dipolar polarization, while those carriers which do not encounter long-range potential well give rise to DC conductivity.