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     

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     

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.     

EELS characterisation of bulk CaCu3Ti4O12 ceramics

CaCu3Ti4O12 (CCTO) is a cubic perovskite phase and sintered ceramics exhibit high permittivity at room temperature. Electron energy-loss spectroscopy (EELS) and energy dispersive X-ray spectrometry (EDS) data have been collected from samples of CCTO to relate the observed electrical properties to the microstructure and chemistry on the nanoscale. CCTO ceramics were sintered for 24h at 1115 degrees C in air, giving a grain size of 50-300 microm. Ti L(2,3)-, Cu L(2,3)- and O K-edge EEL data were collected for bulk CCTO (within grain) and compared with well characterised Ti-oxides, CaTiO3 and BaTiO3 perovskites. The bulk metal L(2,3)-edge data for CCTO suggest that Cu is divalent and Ti is present as Ti4+. The O K-edge of CCTO shows increased near-edge structure (NES) compared to those of the simple perovskites.     

磁控溅射法制备的CaCu3Ti4O12薄膜

采用溅射方法成功地制备了CaCu3Ti4O12薄膜,用原子力显微镜、x射线衍射(XRD)仪和LCR分析仪对样品进行形貌、物相结构和介电性质的研究.XRD表明,薄膜比块体的晶格常数小但晶格畸变较大;LCR测量结果显示,在相同温度下薄膜比块体的相对介电常数低,薄膜相对介电常数由低到高转变时对应的温度较高且激活能较大.分析表明:薄膜的相对介电常数较低是样品中晶相含量较低、缺陷较多使内部阻挡层电容大量减小、致密度不高引起的;薄膜中激活能的增大由膜和基底间晶格的不匹配造成膜中的内应力增大、微结构、缺陷和畴等因素决定;介电常数在低频时的急剧增大,意味着存在界面极化,它与界面的缺陷、悬挂键有关.     

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.     

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     

Mechanochemical synthesis and giant dielectric properties of CaCu3Ti4O12

CaCu₃Ti₄O₁₂ powder has been synthesized by mechanochemical milling (C-m) and solid-state reaction (C-ssr) techniques. C-m powder has a grain size of ~24 nm as determined from X-ray diffraction and FE-SEM measurements. The grain size of C-m ceramics has increased to 20 μm compared to a size of 3 μm for C-ssr ceramics after sintering at 1,050 °C for 10 h. Giant dielectric constant was observed in both ceramics with that of C-m larger than that of C-ssr. Impedance results show that the grain conductivity of C-m is more than two orders of magnitude lower than that of C-ssr, whereas its grain boundary conductivity is larger than that of C-ssr. These results are supported by the EDX results that show Cu-enriched grain boundaries in C-m ceramics.     

Evidence of the Fano resonance in a temperature dependent Raman study of CaCu3Ti4O12 and SrCu3Ti4O12

Phononic excitations have been investigated using Raman scattering studies on CaCu(3)Ti(4)O(12) and SrCu(3)Ti(4)O(12) compounds as a function of temperature down to 10 K. Evidence of the Fano resonance effect is found in the A(g)(1) mode with an asymmetric phonon line shape that occurs because of composite electron-phonon scattering due to the onset of metallic fractions in the system. The evolution of the Fano line shape with temperature affirms the existence of nanoscale phase separation and the prominence of orbitally disrupted metallic regions above 100 K. Anomalies in the evolution of the line width of the A(g)(1) Raman mode with temperature are observed around 100 K where these compounds show an orbital order/disorder transition. These anomalies manifest mutual coupling of orbital degrees of freedom to lattice degrees of freedom.     

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.     

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CaCu3Ti4O1 2 块材和薄膜 ,获得了相对介电常数ε′( 1kHz ,3 0 0K)高于140 0 0的介电特性 ,是目前该体系最好的结果 .报道了 ( 0 0l)取向高质量CaCu3Ti4O1 2 外延薄膜及其介电性质 .CaCu3Ti4O1 2 相对介电常数ε′在 10 0— 3 0 0K温度范围内基本保持恒定 ,稳定性好 .基于跳跃电导模型 ,对CaCu3Ti4O1 2薄膜介电电导的频率依赖关系作了合理解释     

Dc-bias-field-induced dielectric relaxation and ac conduction in CaCu3Ti4O12 ceramics

The dielectric relaxation and ac conduction of CaCu₃Ti₄O₁₂ (CCTO) ceramics were investigated at different temperatures under a dc bias. The dc bias gives rise to space charge accumulation, i.e. an electrode response, resulting in the significant increase of dielectric permittivity and dielectric loss tangent. Two Debye-like relaxations, arising from electrode and grain boundary responses, are present at low frequency with an increase of the dc bias. The electrode and grain boundary relaxations are distinguished according to the impedance spectroscopy and the frequency-dependent ac conductivity. The relaxation times of electrode and grain boundary relaxation are 0.955 ms and 0.026 ms, respectively, with a dc bias of 10 V at 328 K.     

Enhanced dielectric and nonohmic properties of SrTiO3-modified CaCu3Ti4O12 ceramics

Dielectric and nonohmic properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics can be modified by addition of SrTiO₃ (STO) in different molar proportions which were fabricated by a modified sol-gel method. XRD results indicated that all modified ceramics showed mixed phase consisting of both CCTO and STO. SEM images and grain size distribution probability also presented the change of microstructure with the addition of STO. The dielectric loss of the CCTO/0.4STO ceramics sintered at 1000 °C can be lower than 0.02 in a wide frequency (1 kHz–10 kHz), especially at 1 kHz, the dielectric loss of this sample is as low as 0.012. Furthermore, excellent nonlinear I–V electrical characteristic (high breakdown voltage to 54.15 kV/cm for CCTO/0.4STO sintered at 1000 °C) was observed as well. All the results indicated that the addition of STO does improve the dielectric properties and nonohmic characteristics of CCTO ceramics dramatically.     

Morphology and microstructure of all-epitaxial ferroelectric tri-layered (Bi,La)4Ti3O12/Pb(Zr0.4Ti0.6)O3/ (Bi,La)4Ti3O12 thin films on SrTiO3(011)

The morphology and microstructure of all-epitaxial (Bi,La)₄Ti₃O₁₂/Pb(Zr_0.4Ti_0.6)O₃/(Bi,La)₄Ti₃O₁₂ (BLT/PZT/BLT) tri-layered ferroelectric films, grown on (011)-oriented SrTiO₃ (STO) substrates by pulsed laser deposition, are investigated by transmission electron microscopy (TEM). X-ray diffraction and electron diffraction patterns demonstrate that the epitaxial relationship between BLT, PZT and STO can be described as ; . Cross-sectional TEM images show that the growth rate of BLT is nearly two times that for PZT at the same growth conditions, and 90° ferroelectric domain boundaries lying on {110} planes are observed in the PZT layer. The 90° ferroelectric domains in the PZT layer extend up to 600 nm in length. Long domains penetrate into the neighboring columnar grain through the columnar grain boundary, whereas others are nucleating at the columnar grain boundaries. The roughness of the PZT/BLT interfaces appears to depend on the viewing direction, i.e., it is different for different azimuthal directions. Planar TEM investigations show that the grains in the top BLT layer have a rod-like morphology, preferentially growing along the [110]_BLT direction. The grain width is rather constant at about 90 nm, whereas the length of the grains varies from 150 to 625 nm. These morphological details point to the important role the crystal anisotropy of BLT plays for the growth and structure of the tri-layered films. PACS 81.15-z; 68.37.Lp; 77.84.-s     

Electrical parameters of Schottky contacts in CaCu3Ti4O12 thin film capacitors

CaCu₃T_i4O₁₂ (CCTO) thin films were grown by pulsed laser deposition on Pt and La_0.9Sr_1.1NiO₄ (LSNO) bottom electrodes. The electrical characteristics of the CCTO/Pt and CCTO/LSNO Schottky junctions have been analyzed by impedance spectroscopy, capacitance–voltage (C–V) and current–voltage (I–V) measurements as a function of frequency (40 Hz–1 MHz) and temperature (300–475 K). Similar results were obtained for the two Schottky diodes. The conduction mechanism through the Schottky junctions was described using a thermionic emission model and the electrical parameters were determined. The strong deviation from the ideal I–V characteristics and the increase in capacitance at low frequency for ?0.5 V bias are in agreement with the presence of traps near the interfaces. Results point toward the important effect of defects generated at the interface by deposition of CCTO.     

添加Nb对CaCu3Ti4O12陶瓷介电性能的影响

采用固相反应法制备了CaCu3Ti4-xNbxO12(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40 Hz-110 MHz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10 kHz范围内出现的德拜弛豫行为外,室温下在40 Hz-10 kHz低频率范围内还存在一个新的德拜弛豫峰,低于该弛豫特征频率时介电常数达106以上,该峰的特征频率随着Nb含量的增大向高频方向移动.根据阻抗谱中观察到的三个半圆弧,采用阻挡层电容模型,利用含有三个RC的等效电路对上述实验现象作了合理解释.     

Valence degeneracy in CaCu3Cr4O12

The synthesis of CaCu₃Cr₄O₁₂ has been accomplished at a pressure of 60 kbar. Analysis of single crystal X-ray diffraction data demonstrates that this compound is isostructural with CaCu₃Ti₄O₁₂. The electrical resistivity data for CaCu₃Cr₄O₁₂ show metallic behavior, and the magnetic susceptibility indicates delocalized electrons for both Cr and Cu. The Cu–O and Cr–O bond distances give fractional valences of Cu^2.45 and Cr^3.66, thus indicating both Cu and Cr 3d states at the Fermi level.     

Effects of PVA organic binder on electric properties of CaCu3Ti4O12 ceramics

CaCu₃Ti₄O₁₂ ceramics with incorporation of polyvinyl alcohol (PVA) are prepared from the powder synthesized by a solid state reaction. Their electric and dielectric properties are investigated in this study. It is found that adding PVA can dramatically reduce the dielectric loss of CCTO in the low frequency region, and stabilize the dependence of dielectric constant on the measuring frequency. The minimum dielectric loss of 0.045 is obtained from the sample with 8 wt% PVA. The nonlinear coefficient (α) and breakdown electric field (E_b) increase with an increase of PVA binder.