Sol-gel derived CaCu3Ti4O12 ceramics: Synthesis, characterization and electrical properties

The giant dielectric constant material CaCu₃Ti₄O₁₂ (CCTO) has been synthesized by sol-gel method, for the first time, using nitrate and alkoxide precursor. The electrical properties of CCTO ceramics, showing an enormously large dielectric constant ? ∼ 60,000 (100 Hz at RT), were investigated in the temperature range from 298 to 358 K at 0, 5, 10, 20, and 40 V dc. The phases, microstructures, and impedance properties of final samples were characterized by X-ray diffraction, scanning electron microscopy, and precision impedance analyzer. The dielectric permittivity of CCTO synthesized by sol-gel method is at least three times of magnitude larger than that synthesized by other low-temperature method and solid-state reaction method. Furthermore, the results support the internal barrier layer capacitor (IBLC) model of Schottky barriers at grain boundaries between semiconducting grains.     

Dielectric properties of Poly(vinylidene fluoride)/CaCu3Ti4O12 composites

The possibility of obtaining relatively high dielectric constant polymer–ceramic composite by incorporating the giant dielectric constant material, CaCu₃Ti₄O₁₂ (CCTO) in a Poly(vinylidene fluoride) (PVDF) polymer matrix by melt mixing and hot pressing process was demonstrated. The structure, morphology and dielectric properties of the composites were characterized using X-ray diffraction, Thermal analysis, scanning electron microscope, and impedance analyzer. The effective dielectric constant (ε_eff) of the composite increased with increase in the volume fraction of CCTO at all the frequencies (100 Hz–1 MHz) under study. The dielectric loss did not show any variation up to 40% loading of CCTO, but showed an increasing trend beyond 40%. The room temperature dielectric constant as high as 95 at 100 Hz has been realized for the composite with 55 vol.% of CCTO, which has increased to about 190 at 150 °C. Theoretical models like Maxwell’s, Clausius–Mossotti, Effective medium theory, logarithmic law and Yamada were employed to rationalize the dielectric behaviour of the composite and discussed.     

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.     

Microstructural evolution and dielectric properties of Cu-deficient and Cu-excess CaCu3Ti4O12 ceramics

The microstructural evolution and dielectric properties of CaCu_3−xTi₄O_12−x (3 − x = 2.8-3.05) ceramics were investigated. Normal grain growth behavior was observed at Cu/Ca ≤ 2.9, while abnormal grain growth was observed at Cu/Ca ≥ 2.95. A CuO-rich intergranular liquid phase at Cu/Ca ≥ 2.95 and angular grain morphology were the main reasons for abnormal grain growth. However, the abundant intergranular liquid at Cu/Ca = 3.05 significantly affected the relative dielectric permittivity and dielectric loss. The CuO composition is the key parameter that determines the microstructure and dielectric properties of CCTO ceramics.     

Dielectric and optical properties of CaCu3Ti4O12 thin films containing Ag nanoparticles

Simple sol-gel techniques are used to prepare thin films of a high dielectric constant perovskite CaCu₃Ti₄O₁₂, containing different amounts of metallic silver nanoparticles. The formations of the silver nanoparticles are verified by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and optical absorption studies. The dielectric properties are found to be significantly affected by the presence of the silver nanoparticles. A maximum in the dielectric constant is observed at an intermediate metal particle concentration. This is explained in terms of the polarization at the particle-dielectric interface and the internal barrier layer capacitor effect. The optical absorption spectrum is compared with Mie theory in electrodynamics for the optical absorption of small particles to extract the particle size of the silver particle. Non-uniform distributions of Ag particles through the thickness of the thin films are reported.     

Effect of grain size and Cu-rich phase on the electric properties of CaCu3Ti4O12 ceramics

The CaCu₃Ti₄O₁₂ ceramics were prepared by the traditional solid-state reaction method under different sintering conditions. The XRD patterns show that crystal structures of the samples are basically single-phase pseudo-cubic, except little second phases of CuO and Cu₂O in the samples sintered in air at 1050 and 1100 °C, respectively, for 12 h. The SEM results indicate that the pellet sintered at 1100 °C for 12 h possess larger grain size and more Cu-rich phases at the grain boundaries than the pellet sintered at 1050 °C for 12 h. It is interesting that the pellet sintered at 1050 °C under the pressure of 5 Gpa for 3 h shows smaller grain size (~1 μm) and no Cu-rich phases due to the higher pressure during the sintering process. The results show that the grain size has a reverse effect on the values of the permittivity and the values of breakdown electric field (E _b) and nonlinear coefficient. The pellet sintered at 1100 °C for 12 h exhibits a higher permittivity, but with a lower breakdown electric field (E _b) and a lower nonlinear coefficient due to larger grain size. The pellet sintered at 1050 °C under the pressure of 5 Gpa for 3 h exhibits a lower permittivity, but with a higher breakdown electric field (E _b) and a higher nonlinear coefficient due to smaller grain size. The Cu-rich phases at grain boundaries can raise the resistance of the grain boundary leading to the lower dielectric loss tangent, which has been supported by the results of impedance spectroscopy analysis.     

Abnormal dielectric behaviors in Mn-doped CaCu3Ti4O12 ceramics and their response mechanism

Mn-doped CaCu₃Ti₄O₁₂ (CCTO) polycrystalline ceramics have been prepared by the conventional solid state sintering. Our results indicate that 10% Mn doping can decrease the dielectric permittivity in CaCu₃Ti₄O₁₂ by about 2 orders of magnitude (from 10⁴ to 10²). The grain and grain boundary activation energies show an obvious increase from 0.054 eV to 0.256 eV, and decrease from 0.724 eV to 0.258 eV with increasing the Mn doping concentration, respectively, which may be caused by the variation of Cu and Ti valence states in the CCTO samples evidenced by the X-ray absorption spectra. The similar grain and grain boundary activation energies result in invalidation of the internal boundary layer capacitance effect for the 10% Mn-doped CCTO sample, and thus result in the dramatic decrease of dielectric permittivity.     

CaCu3Ti4O12陶瓷深陷阱松弛特性研究

研究了固相反应法及共沉淀法制备的CaCu3Ti4O12陶瓷深陷阱松弛特性.测试了CaCu3Ti4O12陶瓷在频率为0.1～107Hz,温度为–100～100℃的范围内的介电频谱及温谱.通过对不同温度下介电频谱的分析,研究了双Schottky势垒结构中深陷阱松弛特性.研究表明:在交流小信号作用下,由于Schottky势垒中深陷阱与Fermi能级的上下关系发生变化,引起深陷阱电子发射和俘获即电子松弛过程,在介电频谱中表现为松弛峰;并且由介电谱的分析结果可得深陷阱能级等微观参数.比较不同试样的深陷阱参数可知:在CaCu3Ti4O12陶瓷中,在导带以下约0.52和0.12 eV的能级处存在由本征缺陷产生的深陷阱.介电温谱与频谱的分析类似,二者可以互为补充.     

Dielectric and Electrical Transport Properties of the Fe3+-doped CaCu3Ti4O12

CaCu(3-x)FexTi4O(12)(x=0, 0.015, 0.03, 0.045, 0.06) ceramics were synthesized by sol-gel method. The electrical conduction and dielectric measurements show that the doping of a very small amount of Fe(3+) ions greatly reduces the low-frequency dielectric constants and leakage, and enhances grain resistivity. For the doped samples, the appearance of the strong low-frequency peaks in the spectra of dielectric loss confirms that the doping of Fe(3+) ions induces the contact-electrode effect on ceramic surface. These great changes of electrical properties may originate from the reduced amount of oxygen vacancies by doping Fe(3+)     

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.     

Synthesis of CaCu3Ti4O12 ceramic via a sol-gel method

The novel nano-ultrafine powders for the preparation of CaCu₃Ti₄O₁₂ ceramic were prepared by the sol-gel method and citrate auto-ignition method. The obtained precursor powders were pressed, sintered at 1000 °C to fabricate microcrystal CaCu₃Ti₄O₁₂ ceramic. The microcrystalline phase of CaCu₃Ti₄O₁₂ was confirmed by X-ray powder diffraction (XRD). The morphology and size of the grains of the powders and ceramics under different heat treatments were observed using scanning electron microscopy (SEM). The relative dielectric constant of the ceramic sintered at 1000 °C was measured with a magnitude of more than 10⁴ at room temperature, which was approaching to those of Pb-containing complex perovskite ceramics, and the loss tangent was less than 0.20 in a broad frequency region. The relative dielectric constant and loss tangent were also compared with that of CaCu₃Ti₄O₁₂ ceramic prepared by other reported methods.     

Influence of Fabrication Parameters on the Phase Formation and Dielectric Properties of CaCu3Ti4O12 Ceramics

The giant dielectric permittivity materials CaCu 3 Ti 4 O 12(CCTO) were synthesized by conventional solid-state reaction techniques.X-ray diffraction and Raman scattering for the powder indicate that the powder calcined at 950 C for 12 h has been completely transformed into the purer CCTO phase.Furthermore,the morphology and size of the grains of the ceramics sintered at 1090 C in the dwell time range from 0 to 26 h were observed by scanning electron microscopy(SEM).Dielectric properties of the polycrystalline CCTO ceramics were characterized in a broad frequency range(100 Hz-1 MHz) and at a temperature ranged from 300 to 500 K.The longer sintering time may lead to more defect structures and the enhanced conductivity,also leads to substantial improvements in permittivity.Grain size and density differences were not large enough to account for the enhancement in dielectric permittivity.Based on the observations,it is believed that the primary factor affecting dielectric behavior is the development of internal defects.The CCTO ceramics sintered at 1090 C for 15 h exhibit lower dielectric loss(～0.05) near room temperature,and the dielectric relaxation behavior above 1 kHz was observed to follow the Arrhenius law.The activation energy(E a) of 0.65 eV indicates that the doubly ionized oxygen vacancies in the grain boundaries are responsible for the dielectric relaxation of the CCTO ceramics.     

第一性原理对CaTiO3和CaCu3Ti4O12的对比研究

通过Ca替换CaCu_3Ti_4O_(12)晶胞中的所有Cu,建立了包含TiO6八面体扭转的CaTiO3;通过Cu替换CaTiO32×2×2超胞中3/4的Ca,建立了不包含CuO_4正方形的CaCu_3Ti_4O_(12)。采用Materials Studio软件的CASTEP模块,对比了上述晶体和标准晶体成键状况、能带结构、态密度及介电函数,分析了TiO6八面体扭转和CuO_4正方形的影响,发现了Cu-O键或CuO_4正方形对CaCu_3Ti_4O_(12)光频介电常数的关键性作用。研究结果提供了通过内禀机制优化CaCu_3Ti_4O_(12)材料介电性能的新途径。     

溶胶-凝胶法制备CaCu_3Ti_4O_(12)粉体及其电性能

利用溶胶-凝胶法制备CaCu3Ti4O12粉体,采用差热分析、X射线衍射、扫描电子显微镜等技术进行表征,并探讨CaCu3Ti4O12粉体的烧结特性及电性能。结果表明,干凝胶经750℃低温煅烧可获得粒径分布较窄、平均粒径为80～100 nm的CaCu3Ti4O12粉体。CaCu3Ti4O12陶瓷在1 000℃时实现致密烧结,比固相反应法制备的粉体烧结温度降低100～200℃,具有较宽的烧结温区。溶胶-凝胶法制备的陶瓷经1 050℃烧结2 h,获得优良的电性能,相对介电常数为20 190,介电损耗为0.022,非线性系数为4.530。     

Deposition and dielectric properties of CaCu3Ti4O12 thin films deposited on Pt/Ti/SiO2/Si substrates using radio frequency magnetron sputtering

Polycrystalline CaCu₃Ti₄O₁₂ thin films were deposited on Pt(111)/Ti/SiO₂/Si substrates using radio frequency magnetron sputtering. The phase formation and the physical quality of the films were crucially dependent on the substrate temperature and oxygen partial pressure. Good quality films were obtained at a substrate temperature of 650 °C and 4.86 Pa total pressure with 1% O₂. The dielectric constant (∼ 5000 at 1 kHz and 400 K) of these films was comparable to those obtained by the other techniques, eventhough, it was much lower than that of the parent polycrystalline ceramics. For a given temperature of measurements, dielectric relaxation frequency in thin film was found to be much lower than that observed in the bulk. Also, activation energy associated with the dielectric relaxation for the thin film (0.5 eV) was found to be much higher than that observed in the bulk ceramic (0.1 eV). Maxwell-Wagner relaxation model was used to explain the dielectric phenomena observed in CaCu₃Ti₄O₁₂ thin films and bulk ceramics.     

CoAl2O4/Al2O3纳米复合陶瓷的结构与表征

利用溶胶-凝胶方法制备了的CoAl2O4/Al2O3纳米复合陶瓷,并用X-ray分析(XRD)、红外光谱(IR)和扫描电镜分析(SEM)对其结构进行了分析.结果表明,随Al2O3含量增多,CoAl2O4尖晶石相从CoAl2O4/Al2O3凝胶中的析晶温度升高.SEM形貌也说明,随Al2O3含量增多,CoAl2O4/Al2O3陶瓷中形成一定的层状结构.     

Growth of Al2O3 thin film by oxidation of resistively evaporated Al on top of SnO2, and electrical properties of the heterojunction SnO2/Al2O3

Aiming for the investigation of insulating properties of aluminum oxide (Al₂O₃) layers, as well as the combination of this oxide with tin dioxide (SnO₂) for application in transparent field effect transistors, Al thin films are deposited by resistive evaporation on top of SnO₂ thin films deposited by sol–gel dip-coating process. The oxidation of Al films to Al₂O₃ are carried out by thermal annealing at 500 °C in room conditions or oxygen atmosphere. X-ray diffraction data indicate that tetragonal Al₂O₃ is indeed obtained. A simple device and electric circuit is proposed to measure the insulating properties of aluminum oxide and the transport properties of SnO₂ as well. Results indicate a fair insulation when four layers or Al₂O₃ are grown on the tin dioxide film, concomitant with thermal annealing between each layer. The current magnitude through the insulating layer is only 0.2% of the current through the semiconductor film, even though the conductivity of the SnO₂ alone is not very high (the average resistivity is 2 Ω cm), because no doping is used. The presented results are a good indication that this combination may be useful for transparent devices.     

Nano-structure formation of Fe-Pt perpendicular magnetic recording media co-deposited with MgO, Al2O3 and SiO2 additives

Perpendicular magnetic recording media samples were prepared by sputter deposition on sapphire with a layer sequence of MgO seed-layer/Cr under-layer/FeSi soft magnetic under-layer/MgO intermediate layer/FePt-oxide recording layer. The effects of MgO, Al₂O₃ and SiO₂ additives on the morphology and orientation of the FePt layer were investigated by transmission electron microscopy. The samples exhibited (001) orientation of the L1₀ FePt phase with the mutual orientations of sapphire substrate//MgO(100)[001]//Cr(100)[11¯0]//FeSi(100)[11¯0]//MgO(100)[001]//FePt(001)[100]. The morphology of the FePt films varied due to the co-deposited oxides: The FePt layers were continuous and segmented by stacking faults aligned at 54° to the surface. Films with SiO₂ addition, beside the oriented columnar FePt grains, exhibited a fraction of misoriented crystallites due to random repeated nucleation. Al₂O₃ addition resulted in a layered structure, i.e. an initial continuous epitaxial FePt layer covered by a secondary layer of FePt-Al₂O₃ composite. Both components (FePt and MgO) of the MgO-added samples were grown epitaxially on the MgO intermediate layer, so that a nano-composite of intercalated (001) FePt and (001) MgO was formed.The revealed microstructures and formation mechanisms may facilitate the improvement of the structural and magnetic properties of the FePt-oxide composite perpendicular magnetic recording media.     

Machinable Al2O3/BN composite ceramics with strong mechanical properties

Al₂O₃/BN composite ceramics with nano-sized BN dispersions ranging from 0 to 30 vol.% were successfully fabricated by hot-pressing α-Al₂O₃ powders with turbostratic BN (t-BN) coating, which was prepared through chemical processes using boric acid and urea. SEM observations revealed that the nano-sized hexagonal BN (h-BN) particulates were homogeneously dispersed within Al₂O₃ grains as well as at grain boundaries. Vickers hardness of materials decreased with an increase in BN content. The fracture toughness was improved but the fracture strength had a small decrease, in comparison to Al₂O₃ monolithic ceramics. The nanocomposite ceramics with BN content more than 20 vol.% exhibited excellent machinability, which could be drilled using conventional hard metal alloy drills. Drilling rates and normal forces demonstrate the ease of machining of these materials. The preliminary information on the relationship between microstructures and properties are provided. The mechanism of material removal is also discussed.