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.     

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.     

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.     

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.     

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.     

Chemical stability of CaCu3Ti4O12 thin films grown by MOCVD on different substrates

Calcium copper titanate, CaCu₃Ti₄O₁₂ (CCTO), thin films have been fabricated by Metal Organic Chemical Vapor Deposition on silicon substrates buffered with two different low-k interlayers, namely SiO₂ and Si₃N₄. Depositions have been carried out from a molten mixture consisting of the Ca(hfa)₂ • tetraglyme, Ti(tmhd)₂(O-iPr)₂, and Cu(tmhd)₂ [Hhfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; tetraglyme = 2,5,8,11,14-pentaoxapentadecane; Htmhd = 2,2,6,6-tetramethyl-3,5-heptandione; O-iPr = iso-propoxide] precursors. The chemical stability of CCTO films on both the SiO₂ and Si₃N₄ low-k layers has been investigated by transmission electron microscopy in the perspective of their implementation in capacitor devices.     

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.     

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.     

The effect of Ca-rich on the electric properties of Ca1+xCu3−xTi4O12 polycrystalline system

Ca_1+xCu_3−xTi₄O₁₂ (x = 0, 0.25, 0.5, 1) ceramics were prepared using the conventional solid-state reaction method. The XRD patterns show that Ca_1+xCu_3−xTi₄O₁₂ compounds are comprised of CaCu₃Ti₄O₁₂ (CCTO) and CaTiO₃ (CTO) phases compared with the traditional CCTO and the content of CTO phase increases with the increase of x. The micrographs demonstrate that the sample for x = 0 has larger grain size 8-10 μm. However, for the samples (x = 0.25, 0.5, 1), the mean grain size decreases markedly with the increase of CTO phase. The measurement for electric properties indicates that the permittivity values decrease with the increase of Ca atoms, but the breakdown electric field E_b and the nonlinear coefficient α values have a behavior reverse to it. The nonlinear coefficient α reaches 28 for x = 1, yet it is only 11.4 for x = 0 in the current range of 1-10 mA. This can be ascribed to the reduction of grain size and the changes in the electric conductivity of main grains and grain boundary with increasing Ca/Cu ratio. Imbalances between Ca and Cu atoms with Ca in excess can favor the non-ohmic properties in detriment to the dielectric property and a suitable Ca/Cu ratio can be selected to adjust the permittivity and I-V nonlinearity, according to different desired device applications.     

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.     

Anisotropic grain growth of Bi4Ti3O12 in molten salt fluxes

Bismuth titanate (Bi₄Ti₃O₁₂) platelets were obtained by the molten salt synthesis method in NaCl-KCl and Na₂SO₄-K₂SO₄ fluxes, using an amorphous Bi₄Ti₃O₁₂ precursor and a mechanically mixed Bi₂O₃-TiO₂ mixture as the starting materials. It was found that the synthesizing temperature, salt species and starting materials could significantly affect the crystallization habit and morphology of Bi₄Ti₃O₁₂ platelets. Under the same processing conditions (i.e. in Na₂SO₄-K₂SO₄ flux at 1000 °C), the Bi₄Ti₃O₁₂ platelets synthesized from the Bi₂O₃-TiO₂ mixture generally showed a smaller particle size than those synthesized using the amorphous Bi₄Ti₃O₁₂ precursor. The Bi₄Ti₃O₁₂ platelets prepared in the chloride flux were faceted along either (0 0 1) or (1 1 2) planes, while those prepared in the sulfate flux were solely (0 0 1) faceted. The former system also had smaller particle size than the latter. Furthermore, the salt content and the addition of plate-like Bi₄Ti₃O₁₂ seeds in the amorphous Bi₄Ti₃O₁₂ precursor showed a strong influence on the particle size of the synthesized Bi₄Ti₃O₁₂ platelets. The particle size of Bi₄Ti₃O₁₂ platelets prepared in the sulfate flux decreased as the mole ratio of the sulfate salts to Bi₄Ti₃O₁₂ was increased from 7.9 to 23.7. And the addition of 10 wt.% plate-like Bi₄Ti₃O₁₂ seeds into the amorphous Bi₄Ti₃O₁₂ precursor led to a significant increase in the particle size of the resulting Bi₄Ti₃O₁₂ platelets.     

Crystal structure and ferroelectric properties of Ca(Cu3−xMx)Ti4O12 (M = Fe and Ni) ceramics

M-substituted Ca(Cu_3−xM_x)Ti₄O₁₂ (CCMTO) ceramics, where M = Fe and Ni, were synthesized and the influence of M substitutions for Cu on the crystal structure and ferroelectric properties of CCMTO ceramics were investigated in this study. From the variations in the lattice parameters of CCMTO ceramics, the solubility limit of Ni substitution for Cu in CaCu_3−xNi_xTi₄O₁₂ (CCNTO) ceramics was x = 0.2, whereas that of CaCu_3−xFe_xTi₄O₁₂ (CCFTO) ceramics was x = 0.05. The crystal structural analysis of CCMTO ceramics revealed that the single phase of CCMTO ceramics belongs to the I23 non-centrosymmetric space group of I23; as a result, the P_r and E_c values of CCFTO ceramics at x = 0.05 were 1.8 μC/cm² and 40 kV/cm, respectively. The ferroelectric behavior of CCMTO ceramics by the M substitutions for Cu may be related to the displacement of a Ti⁴⁺ cation in the TiO₆ octahedra and tilting of the Ti–O–Ti angle because of the non-centrosymmetric space group.     

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.     

Influence of strontium substitution on the dielectric properties of Ca(1 − x)SrxTi0.9Zr0.1O3 solid solutions

A conventional solid-state reaction has been used to synthesize the perovskite Ca_(1 − x)Sr_xTi_(1 − y)Zr_yO₃ (y = 0.1). The aim of this study is focused on the development of new materials with complex perovskite structure and on their dielectric property improvement. The temperature and substitutional ratio effects on the different phase evolutions is investigated by X-ray diffraction (XRD) and scanning electron microscope observations. These ceramics sintered at 1500 °C, present a density higher than 95% and their dielectric properties are significantly affected by the substitution. The CaTiO₃ ceramic present a relative permittivity of 190 and the temperature coefficient of the permittivity of − 1828 ppm/C°. The substitution with zirconium (for x = 0 and y = 0.1: Σ = 145; |Σ = − 917 ppm/C°). Both permittivity and temperature coefficient values decrease; however, an opposite effect is observed when substituting with the strontium. With increasing an x value and maintaining a y value constant (y = 0.1), the dielectric constant increases and the temperature coefficient remains constant. Therefore, the dielectric properties of CaTiO₃ ceramics are improved with the combined substitution.     

Dielectric and non-Ohmic properties of CaCu3Ti4O12 ceramics modified with NiO, SnO2, SiO2, and Al2O3 additives

In order to conciliate dielectric and non-Ohmic properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics, NiO, SnO₂, SiO₂, and Al₂O₃ were added as sintering aids to promote the grain growth of CCTO ceramics. Microstructure, dielectric properties, and non-Ohmic behavior of the CCTO ceramics were investigated. Among them, NiO-modified CCTO exhibits good dielectric and non-Ohmic properties (ε = 69833, tanδ = 0.073, α = 3.66 and E _B = 296.7 V/cm), due to NiO is also one of giant dielectric materials. Therefore, it is suitable for applying semiconductor circuits. The relationship between electrical current density (J) and electrical field (E) demonstrated that Schottky barrier should exist at grain boundaries. Non-linear coefficient α was directly proportional to the height of barrier. Depressing barrier width would improve significantly dielectric permittivity but decrease breakdown voltage.     

The non-ohmic and dielectric behavior evolution of CaCu3Ti4O12 after heat treatments in oxygen-rich atmosphere

CaCu₃Ti₄O₁₂ (CCTO) ceramics pellets were prepared using the solid-state reaction method, and then they were heat-treated at different temperatures in oxygen-rich atmosphere. The effect of heat treatments on the non-ohmic behaviors and dielectric properties were investigated. EDS analysis results indicate that the percent of oxygen at grain boundaries of CCTO ceramics heat-treated in oxygen-rich atmosphere increases markedly with the rise of temperature and approaches saturation state at about 850 °C. The breakdown voltage and nonlinear coefficient also exhibit an increase trend with the rise of temperature. In addition, the calculated results manifest that the height of Schottky potential barrier is closely related to the oxygen content at the grain boundaries. The permittivity and dielectric loss of samples heat-treated present a relatively intense decrease with the rise of temperature. But the permittivity has a behavior just reverse to the non-ohmic characteristics, which can be explained by the Schottky potential barrier theory.     

Ba2Ti9O20-Ba1.85Sm4.1Ti9O24 layered dielectric resonators with adjustable effective dielectric constant

The layered dielectric resonator structures composed of Ba₂Ti₉O₂₀ (BTO) and Ba_1.85Sm_4.1Ti₉O₂₄ (BSTO) ceramic pellets were introduced to design new microwave dielectric materials with adjustable dielectric constant between 50 and 70. Good combination of microwave dielectric properties (?_r,eff = 50 ~ 70, Qf = 11,700-19,100 GHz and τ_f = − 4.3 to − 1.5 ppm/°C) was obtained by the present approach, and such combination could be optimized by adjusting the volume fraction of BSTO and stacking scheme. For practical applications, the BTO and BSTO layers could be bonded by low-loss adhesive, and the effects of the adhesive on the microwave dielectric properties were limited.     

Ferrimagnetic and semiconducting CaCu3Fe2Sb2O12 by first principles

CaCu₃Fe₂Sb₂O₁₂ is mechanically stable, thermodynamically stable at pressures above 18 GPa. Both GGA and GGA + U methods predict that it is a ferrimagnetic semiconductor with Fe³⁺ in high spin state (S = 5/2). The coupling of Fe–Cu is antiferromagnetic, while that of Cu–Cu is ferromagnetic. The calculated total spin moment is 6.17 μ_B.     

Effects of ZnNb2O6 addition on BaTiO3 ceramics for energy storage

BaTiO₃ ceramics were prepared using solid state reaction with addition of ZnNb₂O₆, to investigate the effects of ZnNb₂O₆ addition on structure and properties. The results show that the ZnNb₂O₆ addition lowers sintering temperature, decreases grain size, while introduces second phase (Ba₂Ti₅O₁₂) for x ≥ 7.26 wt%. The dielectric breakdown strength is enhanced with the increasing doping level of ZnNb₂O₆ and reaches a maximum value at x = 7.26 wt%, exhibiting a maximum energy storage capability.