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.     

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.     

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。     

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.     

Modified giant dielectric properties of samarium doped CaCu3Ti4O12 ceramics

Effects of Sm³⁺ substitution on the microstructure and dielectric properties of CaCu₃Ti₄O₁₂ ceramics were investigated. The grain size of CaCu₃Ti₄O₁₂ ceramics was greatly decreased by doping with Sm³⁺, resulting from the ability of Sm³⁺ to inhibit the grain growth rate. This result can cause a decrease in the dielectric constant (?′) and loss tangent (tan δ) of CaCu₃Ti₄O₁₂ ceramics. Interestingly, high dielectric permittivity (?′ ～ 10,863) and low loss tangent (tan δ ～ 0.043 at 20 °C and 1 kHz) were observed in the Ca_0.925Sm_0.05Cu₃Ti₄O₁₂ ceramic. Nonlinear electrical properties of CaCu₃Ti₄O₁₂ ceramics were modified by doping with Sm³⁺. The dielectric relaxation behavior of Sm-doped CaCu₃Ti₄O₁₂ ceramics can be well ascribed based on the internal barrier layer capacitor model of Schottky barriers at the grain boundaries.     

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.     

Microstructure and dielectric properties of Ca1–3/2xBixCu3Ti4O12 (x = 0, 0.05, 0.10, 0.15 and 0.20) ceramics

Influence of bismuth substitution on calcium site in CaCu₃Ti₄O₁₂ has been investigated. Compositions of Ca_1-3/2xBi_xCu₃Ti₄O₁₂ (x = 0, 0.05, 0.10, 0.15 and 0.20) were fabricated by solid-state sintering method. Crystal structure is remained cubic. X-ray diffraction indicates the presence of secondary phase of CuO in CCTO ceramics. Bismuth doping restrains the formation of CuO phase apparently. The grain size of CaCu₃Ti₄O₁₂ ceramics was greatly decreased by Bi³⁺ doping, resulting from the ability of bismuth to inhibit the grain growth. The dielectric and electric properties of CCTO ceramics were found to be influenced by bismuth doping. The fitting results of the complex impedance spectra showed an increase of the resistance of grain and grain boundary by bismuth substitution. Ca_0.70Bi_0.20Cu₃Ti₄O₁₂ showed the highest dielectric constant in the low frequency range. A modest composition such as Ca_0.85Bi_0.10Cu₃Ti₄O₁₂ expressed the optimized dielectric properties of higher dielectric constant (1.3 × 10⁴) and lower dielectric loss (0.06) than pure CCTO. The low and high temperature dielectric loss spectra demonstrate the interfacial polarization of the initial and secondary oxygen ionization, relating with the grain and grain boundary (the electrode contact for Ca_0.70Bi_0.20Cu₃Ti₄O₁₂) respectively.     

Effect of yttrium doping on the dielectric properties of CaCu3Ti4O12 thin film produced by chemical solution deposition

Pure and yttrium substituted CaCu₃Ti_4 − xY_xO_{12 − x / 2} (x = 0, 0.02, 0.1) thin films were prepared on boron doped silica substrate employing chemical solution deposition, spin coating and rapid thermal annealing. The phase and microstructure of the sintered films were examined using X-ray diffraction and scanning electron microscopy. Dielectric properties of the films were measured at room temperature using electrochemical impedance spectroscopy. Highly ordered polycrystalline CCTO thin film with bimodal grain size distribution was achieved at a sintering temperature of 800 °C. Yttrium doping was found to have beneficial effects on the dielectric properties of CCTO thin film. Dielectric parameters obtained for a CaCu₃Ti_4 − xY_xO_{12 − x / 2} (x = 0.02) film at 1 KHz were k ∼ 2700 and tan δ ∼ 0.07.     

Improved dielectric properties of CaCu3Ti4O12 thin films on oxide bottom electrode of La0.5Sr0.5CoO3

We report on the effect of La_0.5Sr_0.5CoO₃ (LSCO) bottom electrode to the dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) thin films grown on Ir/Ti/SiO₂/Si substrates. Compared with the films grown directly on Ir/Ti/SiO₂/Si substrates, the dielectric constant has been increased greatly about 100%, and the dielectric loss decreased to lower than 0.2 in the frequency range of 1-100 kHz. The origin has been discussed in details based on the analysis of the X-ray diffraction and impedance spectra measurements. Results of the impedance spectra suggest that the absence of undesired interfacial layer between Ir/CCTO thin films might be one of the major reasons of the improvement of the dielectric properties when the LSCO was introduced as the bottom electrode.     

Non-Ohmic and dielectric properties of Ba-doped CaCu3Ti4O12 ceramics

The microstructure, dielectric and electrical properties of Ca_1?x Ba _x Cu₃Ti₄O₁₂ (where x = 0, 0.025, and 0.05) ceramics were investigated. Our microstructural analyses revealed that Ba²⁺ doping ions preferentially form in a secondary phase, and are not introduced into the CaCu₃Ti₄O₁₂ lattice. Grain growth rate of CaCu₃Ti₄O₁₂ ceramics was significantly inhibited by the Ba-related secondary phase particles, resulting in a large decrease in their mean grain size. The dielectric permittivity of CaCu₃Ti₄O₁₂ ceramics decreased with increasing Ba content. Their loss tangent decreased after addition of CaCu₃Ti₄O₁₂ with 2.5 mol% of Ba²⁺, and increased with increasing Ba contents to 5.0 mol%. The nonlinear coefficient and breakdown field of the Ca_1?x Ba _x Cu₃Ti₄O₁₂ ceramics were significantly enhanced by adding 2.5 mol% of Ba²⁺, followed by a slight decrease as Ba²⁺ concentration was increased to 5.0 mol%. Using impedance spectroscopy analysis, it was revealed that variations in dielectric and non-Ohmic properties are associated with electrical response of grain boundaries. This supports the internal barrier layer capacitor model.     

Current–voltage nonlinear and dielectric properties of CaCu3Ti4O12 ceramics prepared by a simple thermal decomposition method

In this work, pure-CaCu₃Ti₄O₁₂ was successfully prepared by a simple thermal decomposition method. This can easily be achieved by direct firing of starting raw materials dissolved in an aqueous citric acid solution at 800 °C for 6 h. The results show that sintering conditions have a remarkable influence on the microstructure of the CaCu₃Ti₄O₁₂ ceramics. Interestingly, dense CaCu₃Ti₄O₁₂ ceramic sintered at 1,050 °C for 2 h exhibits a high dielectric constant of ~5.1 × 10³ with low loss tangent of ~0.048 at 30 °C and 1 kHz. The dielectric properties, electrical response of grain boundaries, and related nonlinear current–voltage behavior are found to be associated with the microstructure of CaCu₃Ti₄O₁₂ ceramics.     

Effects of annealing atmosphere on microstructure and ferroelectric properties of praseodymium-doped Bi4Ti3O12 thin films prepared by sol-gel method

Praseodymium-substituted bismuth titanate (Bi_3.2Pr_0.8Ti₃O₁₂, BPTO) thin films were successfully deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by spin coating with a sol-gel technology and rapid thermal annealing. The effects of annealing atmospheres (vacuum, ambient atmosphere and oxygen) on the growth and properties of thin films were investigated. The results show that the intensity of the (117) diffraction peak of Bi_3.2Pr_0.8Ti₃O₁₂ film annealed in oxygen is stronger than those annealed in ambient atmosphere and vacuum. The XRD spectra demonstrated that a highly (117) orientation could be obtained when the Bi_3.2Pr_0.8Ti₃O₁₂ thin film was annealed in an oxygen-sufficient environment. The BPTO thin films annealed in oxygen atmosphere exhibits the maximum remanent polarization (2P_r) of 49 μC/cm² and a low coercive field (2E_c) of 130 kV/cm, fatigue free characteristics up to ≧ 10¹¹ switching cycles. These results indicate that the BPTO thin film is useful in nonvolatile ferroelectric random access memory applications.     

Dielectric enhancement of the trilayered Bi3.15Eu0.85Ti3O12/Bi3.15Nd0.85Ti3O12/Bi3.15Eu0.85Ti3O12 thin film deposited on Pt/Ti/SiO2/Si substrate

The trilayered Bi_3.15Eu_0.85Ti₃O₁₂/Bi_3.15Nd_0.85Ti₃O₁₂/Bi_3.15Eu_0.85Ti₃O₁₂ (BET/BNT/BET) thin film was deposited on Pt/Ti/SiO₂/Si(100) substrates by metal organic decomposition at annealing temperature of 650 °C, and the microstructure, chemical composition, leakage current, dielectric and ferroelectric properties were investigated by field emission scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, semiconductor characterization system, impedance analyzer and ferroelectric tester. The trilayered thin film is of crack-free and dense surface with some discrete cluster distribution, and typical Bi-layered perovskite polycrystalline phase. The dielectric constant ε _r and dissipation factor tanδ are 1,233 and 0.0215 at 100 kHz for the trilayered thin film. Comparing with the pure BET and BNT thin films, the dielectric constant of trilayered thin film is enhanced, which is due to the space charge and the intermediate superlattice. The trilayered thin film shows excellent dielectric properties and can be promisingly used for the high dielectric layer of silicon-based embedded capacitors in package substrate.     

Synthesis of the giant dielectric constant oxide CaCu3Ti4O12 via ethylenediaminetetraacetic acid precursor

CaCu₃Ti₄O₁₂ powders were prepared via EDTA route and single-phase CaCu₃Ti₄O₁₂ was obtained at 800 °C for 2 h. DTA/TG and XRD were used to characterize the precursor and derived oxide powders. The dielectric properties of CaCu₃Ti₄O₁₂ ceramics were presented. Increasing sintering temperature leads to the increase in dielectric constant. CaCu₃Ti₄O₁₂ ceramics sintered at 1090 °C for 3 h exhibited giant dielectric constant of up to 2.1 × 10⁵ at room temperature and 100 Hz, which is significantly higher than those obtained from other chemical methods.     

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.     

V-doping effects on ferroelectric properties of K0.5Bi4.5Ti4O15 thin films

V-doped K_0.5Bi_4.5Ti₄O₁₅ (K_0.5Bi_{4.5 − x/3}Ti_4 − xV_xO₁₅, KBTiV-x, x = 0.00, 0.01, 0.03, and 0.05) thin films were prepared on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. The thin films were annealed by using a rapid thermal annealing process at 750 °C for 3 min in an oxygen atmosphere. Among them, KBTiV-0.03 thin film exhibited the most outstanding electrical properties. The value of remnant polarization (2P_r) was 75 μC/cm² at an applied electric field of 366 kV/cm. The leakage current density of the thin film capacitor was 5.01 × 10⁻⁸ at 100 kV/cm, which is approximately one order of magnitude lower than that of pure K_0.5Bi_4.5Ti₄O₁₅ thin film capacitor. We found that V doping is an effective method for improving the ferroelectric properties of K_0.5Bi_4.5Ti₄O₁₅ thin film.     

Effects of La3+ doping ions on dielectric properties and formation of Schottky barriers at internal interfaces in a Ca2Cu2Ti4O12 composite system

Influences of La³⁺ substitution on the dielectric properties and formation of Schottky barriers at internal interfaces of a Ca₂Cu₂Ti₄O₁₂ (CaTiO₃/CaCu₃Ti₄O₁₂) composite system were investigated. It was found that electrostatic potential barrier height was greatly reduced by doping with La³⁺, leading to a large decrease in the total resistance of internal interfaces between grains. This observation was attributed to the creation of conduction electrons, which were possibly induced by electrical charge compensation of La³⁺ substitution into Ca²⁺ sites. Variations in the dielectric properties of La³⁺-doped CaTiO₃/CaCu₃Ti₄O₁₂ composite ceramics and nonlinear properties can be described based on the electrical responses at the internal interfaces between CaCu₃Ti₄O₁₂–CaCu₃Ti₄O₁₂ grains and CaTiO₃–CaCu₃Ti₄O₁₂ grains. Influence of possible charge compensation due to different levels of La³⁺ dopant on the formation of potential barriers was discussed.     

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.     

Enhancement on effective piezoelectric coefficient of Bi3.25Eu0.75Ti3O12 ferroelectric thin films under moderate annealing temperature

Bi_3.25Eu_0.75Ti₃O₁₂ (BET) thin films were deposited on Pt/Ti/SiO₂/Si(111) substrates by a metal-organic decomposition method. The effects of annealing temperatures 600-800 °C on microstructure, ferroelectric, dielectric and piezoelectric properties of BET thin films were studied in detail. The spontaneous polarization (87.4 × 10^− 6 C/cm² under 300 kV/cm), remnant polarization (65.7 × 10^− 6 C/cm² under 300 kV/cm), the dielectric constant (992.9 at 100 kHz) and the effective piezoelectric coefficient d₃₃ (67.3 pm/V under 260 kV/cm) of BET thin film annealed at 700 °C are better than those of the others. The mechanisms concerning the dependence of the enhancement d₃₃ are discussed according to the phenomenological equation, and the improved piezoelectric performance could make the BET thin film a promising candidate for piezoelectric thin film devices.     

Effect of tantalum substitutions on microstructures and dielectric properties of calcium copper titanate (CaCu3Ti4O12) ceramic

Tantalum (Ta⁵⁺) doped CaCu₃Ti_4−xTa_xO₁₂ (x = 0.05 and 0.10) ceramics were prepared by semi-wet route using solid Ta₂O₅ powder and metal nitrate solutions. Powder X-ray diffraction confirmed the major phase formation of cubic CaCu₃Ti₄O₁₂ ceramic in the doped samples sintered at 900 °C for 6 h. Microstructure has been studied using field-emission scanning electron microscopy. The grain size is in the range of 150 nm to 1 μm for both compositions. Dielectric constant of the samples increases with increasing tantalum concentrations.