CaCu3Ti4O12多孔陶瓷的介电性能

采用固相烧结法在较低温度(＜1000℃)制备了CaCu3 Ti4 O12 (CCTO)多孔陶瓷.研究了淀粉对CCTO陶瓷的气孔率、显微结构、介电性能的影响.随淀粉含量的增加,CCTO陶瓷的气孔率从32.4％大幅度上升到淀粉含量为5％和10％时的41.3％和48.6％;阻抗明显增大,介电常数和介电损耗明显降低.通过这些结构和性能的变化,分析讨论了CCTO的巨介电机理.     

溶胶-凝胶一步烧结法合成巨介电常数材料CaCu3Ti4O12

通过溶胶-凝胶法合成了巨介电常数材料类钙钛矿型钛酸铜钙(CaCu3Ti4O12,CCTO)先驱物,采用一步烧结法得到纯度较高的CCTO材料。利用X射线衍射、扫描电子显微镜、介电性能测试和阻抗谱测试对样品进行了结构、微观形貌、介电-频率、阻抗谱等分析表征,并讨论了CCTO的微观电导机理和晶粒晶界的性质,计算了晶界活化能。结果表明,此法制备的CCTO样品具有较好的结晶质量、较高的纯度以及优良的介电性能。     

富含CuO的CaCu_3Ti_4O_(12)陶瓷显微结构和介电性能的研究

CaCu3Ti4O12陶瓷具有巨介电性,有助于电容器、存储器等电子器件向高性能化和尺寸微型化的进一步发展。研究了富含CuO对CaCu3Ti4O12陶瓷的显微结构和介电性能的影响,结果表明:富含CuO可促进CaCu3Ti4O12陶瓷晶粒的长大和提高均匀性,富含CuO有利于增加CaCu3Ti4O12陶瓷的介电性能的稳定性,且介电性能的稳定性跟陶瓷晶粒的均匀性有着一定的关系。     

Dielectric properties of Sm-doped CaCu3Ti4O12 ceramics

The effects of Sm substitution on structure, dielectric properties and conductivity of CaCu₃Ti₄O₁₂ ceramics were investigated. Ca_1?xSm_xCu₃Ti₄O₁₂ (x=0.0%, 0.5%, 1.0%) ceramics were synthesized by the solid-state reaction method. Single phase crystal of the ceramics with space group Im3 was obtained. With increasing Sm content, the dielectric loss of Ca_1?xSm_xCu₃Ti₄O₁₂ ceramics improved but the dielectric constant also decreased significantly, with both the low- and high-temperature dielectric relaxations suppressed.     

CaCu3-xMnxTi4O12陶瓷的介电性能研究

本文利用固态反应法制备了CaCu3-xMnxTi4O12(x=0,0.2,0.4,0.6,0.8,1.0)陶瓷,并分析探讨了MnO添加量对其介电性能的影响。研究结果表明,MnO的添加有助于CaCu3Ti4O12相生成,且在高MnO添加的情况下所得陶瓷晶粒尺寸较小。MnO的添加对CaCu3Ti4O12的介电性能有非常不好的影响,少量的添加就会导致其介电常数由10000多降至只有数百。在1000Hz前MnO的添加会使陶瓷的介电损耗大幅上升,这表明MnO添加有降低电阻的效果。     

固态反应法制备CaCu3-xMgxTi4O12陶瓷的介电性能研究

利用固态反应法制备了CaCu3-xMgxTi4O12(x=0,0.2,0.4,0.6,0.8,1.0)陶瓷,并分析探讨了MgO添加量对其介电性能的影响.研究结果表明,添加MgO后陶瓷晶粒有变小的现象,且MgO的添加摩尔比为0.6时其介电常数最佳,但介电常数随频率增加下降也较快;MgO添的加摩尔比为0.2和0.4时虽然介电常数增加较少,但随频率变化幅度却较小.在频率＜1 000 Hz时添加MgO会使陶瓷使的介电损耗大幅上升,这表明添加MgO有降低电阻的效果.     

Dielectric properties of CaCu3Ti4O12 based multiphased ceramics

A “soft chemistry” method, the coprecipitation, has been used to synthesize the perovskite CaCu₃Ti₄O₁₂ (CCT). Three main types of materials were obtained for both powders and sintered ceramics: a monophased consisting of the pure CCT phase, a biphased (CCT + CaTiO₃), and a three-phased (CCT + CaTiO₃ + copper oxide (CuO or Cu₂O)). These ceramics, sintered at low temperature, 1050 °C, present original dielectric properties. The relative permittivity determined in the temperature range (−150 < T < 250 °C) is significantly higher than the one reported in the literature. Internal barrier layer capacitor is the probable mechanism to explain the particular behaviour. Moreover, the presence of a copper oxide phase beside the perovksite CCT plays an important role for enhancing the dielectric properties.     

Dielectric properties of CaCu3Ti4O12 ceramics with Zn substitution for Cu

Abstract

CaCu_3–xZn_xTi₄O₁₂ (x is from 0 to 1·0) polycrystalline samples were fabricated via a two-step solid state reaction process. The lattice parameter of the monophasic CaCu₃Ti₄O₁₂ phase increased as Zn content increased. Scanning electron microscopy (SEM) images of the CCTO ceramic show bimodal grain size distribution and the grain size decrease largely with the appearance of Zn₂TiO₄ second phase. The dielectric permittivity of pure CCTO ceramic is ～1·5×10⁴ at f?=?100 Hz. The dielectric constant of the sample largely increased with Zn substitution in the frequency range f<10⁴ Hz. The highest dielectric constant was 6·2×10⁴ at f?=?100 Hz with Zn substitution of x?=?0·8. The improved dielectric properties are believed to be related to the presence of a thin grain boundary barrier layer. The resistivity of the grain boundary decreased largely with Zn substitution as evidenced from the impedance plots.     

Dielectric properties of CaCu3Ti4O12 improved by chromium/lanthanum co-doping

The dielectric properties of Cr + La co-doped CaCu₃Ti₄O₁₂ ceramics prepared by a solid-state reaction method were evaluated and compared to Cr-doped, La-doped, and parent CaCu₃Ti₄O₁₂ (CCTO). Their structure and grain size were evaluated by X-ray diffraction and scanning electron microscopy, respectively. No secondary phase was detected based on the XRD analysis. The results show that, the room temperature dielectric loss of the co-doped samples is reduced to 43% compared to CCTO and their dielectric permittivity is higher than the un-doped, Cr-doped, and La-doped samples at frequencies over 325 kHz, 30 kHz, and 12 Hz, respectively. Furthermore, the temperature stability of the co-doped sample is significantly more convenient than that of CCTO, and its dielectric loss is three times lower. The results also indicated that the co-doping method is effective in reducing the dielectric loss, still maintaining the high dielectric permittivity.     

固态反应法制备CaCu3-xMgxTi4O12陶瓷的介电性能研究

利用固态反应法制备了CaCu3-xMgxTi4O12（x=0,0．2,0．4,0．6,0．8,1．0）陶瓷,并分析探讨了MgO添加量对其介电性能的影响。研究结果表明,添加MgO后陶瓷晶粒有变小的现象,且MgO的添加摩尔比为0．6时其介电常数最佳,但介电常数随频率增加下降也较快;MgO添的加摩尔比为0．2和0．4时虽然介电常数增加较少,但随频率变化幅度却较小。在频率〈1000Hz时添加MgO会使陶瓷使的介电损耗大幅上升,这表明添加MgO有降低电阻的效果。     

CaCu3Ti4O12 ceramics from co-precipitation method: Dielectric properties of pellets and thick films

Dielectric properties of CaCu₃Ti₄O₁₂ (CCTO)-based ceramics and thick films (e ～50 μm) prepared from powders synthesized by a soft chemistry method (co-precipitation) are presented and discussed. The characteristics of pellets and thick films are compared.The pellets exhibit high values of the dielectric permittivity (?_r ～1.4 × 10⁵) and relatively small dielectric losses (tan δ ～0.16) at 1 kHz and room temperature. These properties are independent of the nature of the metallization of the electrodes. In addition, the dielectric permittivity decreases when the diameter of the electrodes of the pellets increases, while the losses remain constant. This result, which is strongly related to the nature of the dielectric material in between the electrodes, constitutes a strong indication that the high dielectric permittivity values observed in this material are not related to an interfacial (electrode material) related mechanism but is an internal barrier layer capacitor (IBLC) type.Very high values of the dielectric permittivity of CCTO thick films are measured (?_r ～5 × 10⁴). The differences in dielectric permittivity between thick films and dense pellets may be attributed to the difference in grain size due to different CuO contents, and to the different reactivity of the materials.     

Electrical properties of Co-doped CaCu3Ti4O12

Co-doped CaCu₃Ti₄O₁₂ samples were synthesized by solid-phase reaction. Electrical properties were studied by impedance spectroscopy in wide temperature (25–450 °C) and frequency (10 Hz–10 MHz) intervals. It was shown that the presence of the copper oxide interlayer significantly reduces the value of the dielectric constant. The amount of impurity copper in the CaCu₃Ti_4-хCo_хO_12-δ samples (x = 0.06; 0.12; 0.24) rise with an increase in the cobalt content. The samples are characterized by a granular microstructure, with an average grain size ranging from 2 to 10 μm. The impedance of the samples was simulated at a temperature of 25 °C and in the range of 100–450 °C. It was found that the samples are characterized by low- and high-frequency polarization. The conductivity activation energy varied from 0.94 to 0.87 eV depending on the cobalt content. The CaCu₃Ti_3.94Co_0.06O_12-δ sample are characterized by the best values of the dielectric permittivity and the dielectric loss tangent, ε = 400 and tanδ = 0.2 (at 1 MHz and room temperature), respectively.     

Electrical Conduction and Dielectric Properties of the Rb‐doped CaCu3Ti4O12

Ca_1?xRb_xCu₃Ti₄O₁₂ (x = 0, 0.03, and 0.05) ceramics were synthesized by the sol‐gel method. Their microstructure and electrical properties were investigated. In the Rb‐doped samples, the Cu‐rich and Ti‐poor grain‐boundary layers are formed, and electrical properties are also changed by doping: With the increase in doping concentration, the grain resistivity and the grain‐boundary Schottky potential barrier are changed, the grain‐boundary resistivity is enhanced, and the low‐frequency dielectric constants and loss are reduced. These results were discussed in terms of the internal barrier layer capacitor (IBLC) mechanism, particularly focusing on the electrical properties in grains and the cationic nonstoichiometry at grain boundaries.     

钛酸铜镧粉末及陶瓷的制备、结构及介电性能研究

采用溶胶-凝胶法制备La2/3Cu3Ti4O12(LCTO)粉末和陶瓷,详细研究了溶胶条件对LCTO粉末和陶瓷的显微结构的影响.结果表明溶胶条件在Ti4+浓度为1.0 mol/L,pH=0.3,[H2O]/[Ti4+]=5.6的条件下制备LCTO的粉末分散程度较好,颗粒均匀.当在1100 ℃下烧结保温10 h后制备的LCTO陶瓷显示出较大的晶粒尺寸、高的致密度以及高的晶界电阻(1.95×105Ω· cm).另外,在保持高达(0.92~1.6)×104的巨介电常数同时,介电损耗降低至0.041.模拟计算LCTO陶瓷的晶界电导激活能为0.664 eV和0.893 eV.     

Dielectric behaviour of Hf-doped CaCu3Ti4O12 ceramics obtained by conventional synthesis and reactive sintering

CaCu₃(Ti_4?xHf_x)O₁₂ ceramics (x = 0.04, 0.1 and 0.2) were prepared by conventional synthesis (CS) and through reactive sintering (RS), in which synthesis and sintering of the material take place in one single step. The microstructure and the dielectric properties of Hf-doped CCTO (CCTOHf) have been studied by XRD, FE-SEM, AFM, Raman and impedance spectroscopy (IS) in order to correlate the structure, microstructure and the electrical properties. Samples prepared by reactive sintering show slightly higher dielectric constant than those prepared by conventional synthesis in the same way than the pure CCTO. Dielectric constant and dielectric losses decrease slightly increasing Hf content. For CCTOHf ceramics with x > 0.04 for CS and x > 0.1 for RS, a secondary phase HfTiO₄ appears. As expected, the reactive sintering processing method allows a higher incorporation of Hf in the CCTO lattice than the conventional synthesis one.     

Synthesis of CaCu3Ti4O12 Micron-cubes and rods via high proportion molten salt method

CaCu₃Ti₄O₁₂ (CCTO) particles were produced from a CuO–CaCO₃–TiO₂ peroxo-hydroxide precursor material in NaCl–KCl and Na₂SO₄–K₂SO₄ salt mixtures via the molten-salt synthesis method at different salt-to-precursor mass ratios. Regular-shaped CCTO particles of cubes, rods, and polyhedrons can be obtained at large salt-to-precursor mass ratios of above 50:1. With the extension of sintering time, the particle shape is more regular and the size is larger. Long micro rods with a length of about 53 μm can be obtained at a mass ratio of 125:1 and a long sintering time of 72 h in sulfate salts. The formation mechanisms are also discussed and the results suggest that a large salt-to-precursor mass ratio may provide a sufficient number of Na − K ions to sufficiently modify the particle shape and form regular-shaped cubes and rod-like particles. At the same time, CCTO ceramics synthesized by Na₂SO₄–K₂SO₄ molten-salt method show good dielectric properties, with a dielectric constant higher than 10⁴ and a loss factor less than 0.45 in the range of 20 Hz to 1 MHz.     

Dielectric properties of conventional and microwave sintered Lanthanum doped CaCu3Ti4O12 ceramics for high-frequency applications

The colossal dielectric response of La-doped CaCu₃Ti₄O₁₂ ceramics has been probed at room temperature for a frequency of 1Hz–20 MHz. In this work, the La-doped (CaCu₃Ti₄O₁₂)_x samples for x = 0.1, 0.2, and 0.3 have been sintered at 1100 °C using two different heating modes. SEM and EDS analysis investigated the microstructural chrysalis, grain size distribution, and the inhibitions of Cu-rich phase segregation into grain boundaries by the effect of La³⁺. The presence of main cubic single-phase of CCTO and the diminutive Bragg peak shift due to ion size effect of La³⁺ and Ca²⁺ have been identified by XRD for both conventional (CS) and microwave sintered (MWS) samples. XPS study revealed the effect of La³⁺ on the binding energies of Cu and Ti in CCTO. The dielectric properties namely dielectric constant (?), tan δ, and dielectric relaxation peaks were measured using BDS in which CS and MWS La-doped samples demonstrated (?) ～ >10⁴ and ～ >10³ along with low tan δ for x ≥ 0.1 at medium and high frequency (10⁴–10⁷Hz) than pure CCTO.     

Improved Dielectric and Nonlinear Electrical Properties of Fine‐Grained CaCu3Ti4O12 Ceramics Prepared by a Glycine‐Nitrate Process

Pure CaCu₃Ti₄O₁₂ was successfully prepared by a glycine‐nitrate process using a relatively low calcination temperature and short reaction time of 760°C for 4 h. Fine‐grained CaCu₃Ti₄O₁₂ ceramics with dense microstructure and small grain size were obtained after sintering for 1 h. The nonlinear coefficient of a fine‐grained CaCu₃Ti₄O₁₂ ceramic calculated in the range 1–10 mA/cm² was found to be very high of ~16.39 with high breakdown electric field strength of 1.46 × 10⁴ V/cm. This fine‐grained CaCu₃Ti₄O₁₂ ceramic also exhibited a very low loss tangent of 0.017 at 20°C with temperature stability over the range ?55°C to 85°C. The grain growth rate of the CaCu₃Ti₄O₁₂ ceramics was found to be very fast after increasing the sintering time from 1.5 to 3 h, leading to formation of a coarse‐grained CaCu₃Ti₄O₁₂ ceramic with grain size of about 100–200 μm. The dielectric permittivity of this coarse‐grained ceramic was found to be as high as 1.03 × 10⁵ with a low loss tangent of 0.054.     

Wideband frequency tunability of CaCu3Ti4O12-based dielectric resonator antennas via the addition of glass

In this study, DRAs produced using CaCu₃Ti₄O₁₂ (CCTO) as a high dielectric material (ε_r) was added with BaO–SrO–Nb₂O₅–B₂O₃–SiO₂ (BSNBS) glass for possible tunability in a wideband frequency range. BSNBS glass (0.01-1 wt%) was mixed with CCTO powders (calcined) and compacted at 250 MPa into mixed-powder pellets. All the green body samples were then sintered at 1040°C for 10 hours. The wideband frequency tunability, measured using a network analyzer, showed that the addition of ≤0.05 wt% BSNBS glass decreased the resonance frequency from 9.51 to 9.33 GHz; later, the values increased to 9.89 GHz when BSNBS content was > 0.05 wt%. The ε_r of each sample was around 11-36 when measured at 9.5-11.8 GHz. The radiation pattern of CCTO for each sample that had been set up as a DRA radiated the signal equally or nearly identical to each other. Furthermore, the addition of BSNBS glass produced micrographs with finer grains, improved the density and reduced the porosity of the composite. Therefore, the addition of the BSNBS glass is a successful aid in the wideband frequency tunability of pure CCTO-based ceramics when used as DRAs.     

Extremely Enhanced Nonlinear Current–Voltage Properties of Tb‐Doped CaCu3Ti4O12 Ceramics

Nonlinear current–voltage properties of CaCu₃Ti₄O₁₂ ceramics were extremely enhanced by doping with Tb. Substitution of Tb to CaCu₃Ti₄O₁₂ resulted in a decrease in grain size due to the ability of Tb ions to inhibit grain boundary mobility. The dielectric properties of CaCu₃Ti₄O₁₂ ceramics were degraded after doping with Tb. Surprisingly, the nonlinear electrical properties were strongly enhanced. The best properties with a nonlinear coefficient of ~29.67 and breakdown electric field strength of ~1.52 × 10⁴ V/cm were obtained in the Ca_0.775Tb_0.15Cu₃Ti₄O₁₂ ceramic. These extremely enhanced properties were attributed to modification of grain boundary electrical response due to the effect Tb substitution.