非化学计量比巨介电CaCu_3Ti_4O_(12)陶瓷研究

采用固相反应法制备了不同化学计量比的CaCu3Ti4O12(简称CCTO)陶瓷。当Ca、Cu、Ti的原子摩尔比为1.08∶3.00∶4.44时,获得了相对介电常数在1kHz下高达4×105(1kHz)的巨介电CCTO陶瓷,其介电常数比标准化学计量比CCTO陶瓷高约一个数量级。结合XRD、SEM、EDX等分析表征结果,对巨介电常数的物理机理进行了探讨。     

High performance CaCu3Ti4O12/cyanate ester composites with excellent dielectric properties and thermal resistance

High performance composites based on CaCu₃Ti₄O₁₂ (CCTO) and cyanate ester (CE) were successfully developed with desirable dielectric properties (high dielectric constant and low dissipation factor), outstanding thermal resistance and decreased curing temperature for embedded capacitors. CCTO was treated by γ-aminopropyl triethoxy silane, coded as CCTO(KH550), to investigate the interfacial effects on properties of composites. The addition of CCTO or CCTO(KH550) can significantly reduce the whole curing temperature of CE, while CCTO exhibits a higher catalytic capability than CCTO(KH550). Compared with cured CE resin, two kinds of composites exhibit greatly improved thermal resistance and real permittivity, meanwhile the dissipation factor is still very low. Because the interfacial polarization leads to the dependence of dielectric properties on the frequency and temperature, the improvement of interfacial adhesion for composites is beneficial to reduce the variation of dielectric properties with temperature and frequency, and thus improve the reliability of dielectric materials in applications.     

Low-temperature synthesis of CaCu3Ti4O12 powders, ceramics and thin films via an organic solution

The giant-dielectric-constant material CaCu₃Ti₄O₁₂ (CCTO) was synthesized via an organic solution containing stoichiometric amounts of the metal cations, which is done at lower temperature and shorter reaction time than the conventional solid-state reaction. A stable solution was prepared by dissolving calcium nitrate, copper nitrate, and tetrabutyl titanate in grain alcohol. CCTO powders, ceramics and thin films were synthesized via the solution. The phases, microstructures, and dielectric properties of samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and dielectric spectroscopy. XRD results identify both samples as single phase CCTO. The CCTO ceramics has a low-frequency permittivity of 3.5 × 10⁴. The CCTO thin films has a low-frequency permittivity of 3.1 × 10⁴. Both the CCTO ceramics and CCTO thin films exhibit two dielectric relaxations at room temperature. The low leakage current density of CCTO thin films shows that it is suitable for memory device applications.     

Oleic acid assisted synthesis of CaCu3Ti4O12 powders and ceramics by sol–gel process

The CaCu₃Ti₄O₁₂ (CCTO) powders were prepared via a sol–gel method using oleic acid (OA) as surfactant. The obtained samples were characterized by thermogravimetric/differential scanning calorimeter Fourier transform-infrared spectroscopy, X-ray diffraction (XRD) and scanning electron microscope, the relative density and the dielectric properties of the ceramics were also investigated. The XRD patterns confirm the formation of CCTO crystal phase and no new peaks appeared whether the dispersant was added or not. The dispersibility of the CCTO powders is improved by adding OA as surfactant. The CCTO prepared without surfactant contains particles of various sizes ranging from 200 to 250 nm whereas the CCTO prepared with OA shows uniform particle size about 120–150 nm. The CCTO ceramics prepared with OA has higher dielectric constant (199484) and lower dielectric loss (0.0977) at 25 °C (10 kHz).     

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.     

Comparative dielectric studies of nanostructured BaTiO3, CaCu3Ti4O12 and 0.5BaTiO3⋅ 0.5CaCu3Ti4O12 nano-composites synthesized by modified sol–gel and solid state methods

BaTiO₃ (BTO), CaCu₃Ti₄O₁₂ (CCTO) and 0.5BaTiO₃·0.5CaCu₃Ti₄O₁₂ (BTO–CCTO), as a new nano-composite ceramic, were successfully designed and fabricated by a semi-wet gel route and a modified solid state method. The dielectric properties of the BTO–CCTO ceramic were compared to those of the BTO and CCTO ceramics at lower sintering temperatures and durations. The X-ray diffraction analysis revealed that the BTO and CCTO ceramics form a single crystalline phase and the average crystalline sizes calculated from X-ray diffraction data were in the range of 40–65 nm. The particle sizes of the BTO, CCTO, and BTO–CCTO ceramics obtained from transmission electron microscopy images were in the ranges of 40–65 nm, 80–110 nm, and 70–95 nm, respectively. The phase composition and microstructure were studied by X-ray diffraction and scanning electron microscopy. The energy dispersive X-ray results demonstrated the purity and stoichiometry of the BTO–CCTO nano-composite. The grain sizes of the BTO, CCTO and BTO–CCTO ceramics were found to be in the ranges of 500 nm–1 μm, 4–24 μm, and 250 nm–4 μm, respectively. The AC conductivity as a function of frequency confirmed the semiconducting nature of all of the ceramics and obeyed the Jonscher's power law. The impedance spectrum measurement result showed that the CCTO ceramic possessed an exceptional grain boundary resistance, which supports the internal barrier layer capacitance (IBLC) mechanism present in this ceramic and is responsible for the high ε_r values.     

巨介电常数陶瓷CaCu3Ti4O12的研究进展

CaCu_3Ti_4O_(12)(CCTO)陶瓷具有高介电常数和高热稳定性,这使得CCTO可能在高密度信息储存、高介电电容器、大规模集成电路等领域获得广泛使用。系统地介绍了CCTO高介电常数起源的内禀机制和外禀机制,详细归纳了元素掺杂对CCTO介电特性的影响,阐述了巨介电常数与本征点缺陷的内在关联,肯定了晶粒电导赝极化理论,指出了CCTO巨介电常数陶瓷研究的重点在于:基于外禀机制的IBLC模型,通过晶胞掺杂或晶界掺杂改变晶粒或者晶界的电导,进而调控CCTO的介电损耗,使CCTO保持较高介电常数的前提下,在很宽的频率范围内使介电损耗正切值降低到0.1以下。     

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.     

Elastic modulus and hardness of CaTiO3, CaCu3Ti4O12 and CaTiO3/CaCu3Ti4O12 mixture

Three ceramic systems, CaTiO₃ (CTO), CaCu₃Ti₄O₁₂ (CCTO) and intermediate nonstoichiometric CaTiO₃/CaCu₃Ti₄O₁₂ mixtures (CTO.CCTO), were investigated and characterized. The ceramics were sintered at 1100 °C for 180 min. The surface morphology and structures were investigated by XRD and SEM. Elastic modulus and hardness of the surfaces were studied by instrumented indentation. It was observed that CCTO presented the higher mechanical properties (E = 256 GPa, hardness = 10.6 GPa), while CTO/CCTO mixture showed intermediate properties between CTO and CCTO.     

Structural and electrical study of CaCu3Ti4O12 (CCTO) obtained in a new ceramic procedure

In this study, the CaCu₃Ti₄O₁₂ (CCTO) ceramic phase was synthesized by microwave heating in a much shorter time compared with conventional ceramic methods. The results indicate that the microwave processing is a promising method for preparing CCTO ceramics. CCTO was prepared using a domestic microwave oven operated at 2.45 GHz with 800 W. The XRD, infrared and Raman scattering spectroscopy was used in the structural studies of the samples. After few minutes of microwaves irradiation the formation of CCTO was confirmed by the X-ray powder diffraction. Electrical measurements was performed and shows that the dielectric permittivity of the samples are in the order of 10⁶.     

Very low loss tangent and giant dielectric properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics prepared by the sol–gel process

The pure phase of CaCu₃Ti₄O₁₂ (CCTO) powder can be successfully synthesized by the sol–gel process. CCTO ceramic samples were synthesized at different sintering temperatures of 1015 and 1050?°C and sintering times of 8 and 10 h. X-ray diffraction results indicated a pure phase for all ceramic samples. Rietveld refinements were adopted for the calculation of lattice constants. Scanning electron microscopy micrographs revealed the effect of sintering conditions on the microstructural evolution of ceramic samples. X-ray absorption near edge spectroscopy was performed to determine the oxidation state of Cu and Ti ions in ceramic samples. The dielectric and non-linear current voltage properties of CCTO ceramic samples were systematically investigated. Interestingly, very low loss tangent (tanδ?<?0.017 at 30?°C and 1 kHz) and giant dielectric constant (ε′?～?10,942) with temperature coefficients less than ±15% in a wide temperature range of ?60 to 125?°C were obtained in the CCTO ceramic sample sintered at 1015?°C for 10 h (CCTO1-10). This suggests a potential use for CCTO1-10 sample in capacitor applications. All CCTO ceramic samples display non-linear characteristic with non-linear coefficient (α) and breakdown field (E _b ) values in the range of 5.69–11.02 and 1415–4294, respectively.     

The influence of the segregation of Cu-rich phase on the microstructural and impedance characteristics of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics

The influence of sintering conditions on the microstructural features and impedance characteristics of the giant dielectric constant material CaCu₃Ti₄O₁₂ (CCTO) was investigated. The microstructure and impedance characteristics were found to be strongly dependent on the sintering conditions. Sintering of the CCTO ceramics at elevated temperatures (>1100 °C) for prolonged durations resulted in the segregation of Cu-rich phase, mostly confined to the surface, which was in concomitance with the appearance of the additional semicircle at the low frequency end in Impedance (Z*) plots. The absence of this additional semicircle in the Cu-deficient CCTO ceramics and the appearance of the same in Cu-rich CCTO ceramics that were deliberately fabricated corroborated the above observations. Also, La_2/3Cu₃Ti₄O₁₂ (LCTO), a low dielectric constant member of CCTO family, which consisted of small grains without the segregation of Cu-rich phase at the grain boundary, did not reveal the presence of additional semicircle in the Z*plots.     

稀土氧化物Eu_2O_3掺杂对CaCu_3 Ti_4O_(12)陶瓷微结构及介电特性的影响

以稀土氧化物Eu_2O_3为添加剂,采用固相反应法制备了不同掺杂比例(质量比:x=0,0.2%,0.5%,1%)的CCTO陶瓷样品,利用SEM、XRD、4294A型高精密阻抗分析仪等测试手段对样品的微观结构、介电性能和交流电阻率进行了测试分析.掺杂之后样品的晶格结构并未发生改变,但是样品内部相对晶相含量和晶粒平均尺寸减小,同时掺杂阻碍了样品内部晶界处富铜相的生成;纯CCTO的XRD图谱中分别出现了CuO、TiO_2和CaCO_3杂相,掺杂样品的图谱中并未出现上述杂相;样品的介电性能与相同组分材料内部的相对晶相含量,晶粒平均尺寸和晶界处富铜相有很大关系.Eu_2O_3掺杂提高了样品介电性能的频率和温度稳定性.当掺杂量为0.2%和0.5%时,样品的介电性能得到较好改善效果.样品在低频40Hz和高频3.5MHz的交流电阻率测量结果很好的验证了Eu_2O_3掺杂导致的微结构变化对样品介电性能的影响.     

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.     

Formation behavior of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> from CaTiO<Subscript>3</Subscript>, CuO and TiO<Subscript>2</Subscript>

The formation behavior of CaCu₃Ti₄O₁₂ (CCTO) had been investigated via solid state reaction from CaTiO₃, CuO and TiO₂ powders. In the temperature range from 750 to 1,200 °C, the reaction sequence was traced by XRD, and the microstructure evolution of calcined powders was also investigated by SEM. CCTO began to form owing to the reaction between CaTiO₃, CuO and TiO₂ at around 850 °C, and became the major phase at 1,000 °C. Finally, the single phase CCTO was obtained at 1,150 °C. However, CCTO was decomposed at CaTiO₃, CuO and TiO₂ when the temperature increased to 1,200 °C. In addition, no other intermediate phases occurred in the synthesized process. The formation behaviors indicated that CaTiO₃ prevented the formation and growth of CCTO.     

Deposition and dielectric properties of CaCu3Ti4O12 thin films on Pt/Ti/SiO2/Si substrates using pulsed-laser deposition

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully deposited on Pt/Ti/SiO₂/Si(1 0 0) substrates using pulsed-laser deposition technique. The crystalline structure and the surface morphology of the CCTO thin films were greatly affected by the substrate temperature and oxygen pressure. Thin films with a (2 2 0) preferential orientation were obtained at the substrate temperature above 700 °C and oxygen pressure above 13.3 Pa. The 480-nm thin films deposited under 720 °C and 26.6 Pa have a fairly high dielectric constant of near 2000 at 10 kHz and room temperature. The values of the dielectric constant and loss and their temperature-dependence under different frequency are comparable with those obtained in the epitaxial CCTO films grown on oxide substrates.     

Effect of copper-oxide segregation on the dielectric properties of CaCu3Ti4O12 thin films fabricated by pulsed-laser deposition

We investigated the effects of post-deposition cooling conditions on the surface morphologies and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) thin films grown by pulsed-laser deposition on Pt/TiO₂/SiO₂/Si substrates. CCTO thin films cooled under the typical cooling parameters, i.e., slow cooling (3 °C/min) at high oxygen pressure (66 kPa) showed a severe segregation of nanoparticles near the grain boundaries, which was identified to be copper oxide from electron probe micro analyzer mapping. On the other hand, we could not observe any segregation on the film surface when the samples were cooled fast (∼ 20 °C/min) at relatively low oxygen pressure (100 Pa). The dielectric constant, ε_r, of CCTO thin films deposited at 750 °C with severe surface segregation (ε_r ∼ 750 at 10 kHz) was found to be much lower than that (ε_r ∼ 2000 at 10 kHz) of CCTO thin films with smooth surface. As the copper-oxide segregation becomes more serious, which preferentially occurs at relatively high ambient oxygen pressure and temperature, the degradation in the dielectric properties of CCTO films becomes larger. The variation of dielectric constant of CCTO films with no copper-oxide segregation could be related to the presence of an impurity phase at grain boundaries.     

Electric properties of Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript>(BIT)–CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> (CCTO) composite substrates for high dielectric constant devices

A study of the effect of the presence of BIT (Bi₄Ti₃O₁₂) in the dielectric and optical properties of the CaCu₃Ti₄O₁₂ (CCTO) is presented. The samples were prepared by the solid state procedure. Mechanical alloying followed by the solid state procedure has been used successfully to produce powders of CaCu₃Ti₄O₁₂ (CCTO) and BIT (Bi₄Ti₃O₁₂) to be used in the composites. We also look at the effect of the grain size of the BIT and CCTO in the final properties of the composite. The samples were studied using X-Ray diffraction, scanning electron microscopy (SEM), Raman and infrared spectroscopy. We also did a study of the dielectric function K and dielectric loss of the samples. The role played by the grain size of CCTO and BIT in the dielectric constant and structural properties of the substrates are discussed. For frequencies below 10 MHz the K value presented by the CCTO100 sample is always higher than the K value presented by the BIT100 sample. At 100 Hz the value of K 1900 for the CCTO100 sample and 288 for the BIT100 sample. However for the composite sample one has an unexpected result. The dielectric constant is higher for all the frequencies under study. At 100 Hz the value of the K is around 10.000 for the BIT10 sample. Which is more than one order bigger compared to the CCTO100 value for the same frequency. Therefore, these measurements confirm the potential use of such materials for small high dielectric planar devices. These composites are also attractive for capacitor applications and certainly for microelectronics, microwave devices (cell mobile phones for example), where the miniaturization of the devices is crucial.     

CaCu3Ti4O12 thin film capacitors: Evidence of the presence of a Schottky type barrier at the bottom electrode

This study aims to distinguish between the contributions of bottom and top electrodes to the dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) based parallel plate thin film capacitors. For this purpose, Au, Pt, and La_0.9Sr_1.1NiO₄ as electrode materials were compared. Epitaxial and polycrystalline CCTO films were pulsed laser deposited. The nature of electrodes played a major role in altering the dielectric characteristics of the thin films. Existence of one or two Schottky barriers at either or both of the CCTO/electrode interfaces was observed. A careful comparison of the electrical characteristics allowed us to discriminate between the interfaces hosting the Schottky barrier without assuming the conduction type. In return, this knowledge of the Schottky barrier location allowed us to unambiguously establish the carrier's nature. Results point toward n-type carriers in CCTO thin films, in contradiction with previous reports.     

Properties of calcium copper titanate and barium titanate filled epoxy composites for electronic applications: effect of filler loading and hybrid fillers

Inorganic ceramics such as calcium copper titanate, CaCu₃Ti₄O₁₂ (CCTO) and barium titanate (BaTiO₃) were used as fillers to produce epoxy thin film composites for capacitor application. The effects of filler types and loading range on the dielectric, tensile, morphology, and thermal properties of the epoxy thin film composites were determined. Results showed that epoxy thin film composites with 20 vol% filler loading of CCTO and BaTiO₃ showed good dielectric properties, thermal stability, and thermal conductivity. However, the tensile properties of the CCTO/epoxy thin film composite was reduced as the filler loading increased. On the other hand, the tensile properties of BaTiO₃/epoxy thin film composite improved as the filler loading increased. Hybrid fillers CCTO and BaTiO₃ filled epoxy composites were fabricated and the effect of hybrid fillers on the dielectric properties and morphology of the epoxy thin film composites were investigated. Results indicated that positive hybrid effect in dielectric constant and dielectric loss showed by the hybrid composites.