Low temperature preparation of CaCu3Ti4O12 ceramics with high permittivity and low dielectric loss

Low temperature preparation of CaCu₃Ti₄O₁₂ ceramics with large permittivity is of practical interest for cofired multilayer ceramic capacitors. Although CaCu₃Ti₄O₁₂ ceramics have been prepared at low temperatures as previously reported, they have rather low permittivity. This work demonstrates that CaCu₃Ti₄O₁₂ ceramics can not only be prepared at low temperatures, but they also have large permittivity. Herein, CaCu₃Ti₄O₁₂ ceramics were prepared by the solid state reaction method using B₂O₃ as the doping substance. It has been shown that B₂O₃ dopant can considerably lower the calcination and sintering temperatures to 870 °C and 920 °C, respectively. The relative permittivity of the low temperature prepared CaCu₃Ti_4−xB_xO₁₂ ceramics is about 5 times larger than the previously reported results in the literature. Furthermore, the dielectric loss of the CaCu₃Ti_4−xB_xO₁₂ ceramics is found to be as low as 0.03. This work provides a beneficial base for the future commercial applications of CaCu₃Ti₄O₁₂ ceramics with large permittivity for the cofired multilayer ceramic capacitors.     

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.     

High permittivity and low dielectric loss of the (Ca0.9Sr0.1)1-xLa2x/3Cu3Ti4O12 ceramics

In this work, we have systematically studied the effects of La³⁺/Sr²⁺ dopants on the crystal structure, microstructure, dielectric response and electrical properties of (Ca_0.9Sr_0.1)_1-xLa_2x/3Cu₃Ti₄O₁₂ (x = 0, 0.025, 0.05 and 0.075) ceramics. XRD results show that the lattice parameter increases with the increase in the La³⁺ content. SEM micrographs illustrate that a small amount added of La³⁺ can reduce the grain size of CCTO during sintering. With increasing La³⁺ content, the grains grow larger. Dielectric measurements indicated that all doped samples synthesized by the solid-state reaction exhibit giant dielectric constants ε'>10⁴ over a large frequency range (10 Hz to 1 MHz) and at any temperature below 600 K. In particular, the ceramic with x = 0.05 exhibits a colossal dielectric permittivity ～5.49 × 10⁴; which increases by about 50% compared to that of the undoped ceramic. In addition, the doped ceramic also presents a low dielectric loss ～ 0.08 at 20 °C and 0.6 kHz. The giant dielectric properties of these samples can be explained by the (IBLC) model.     

Optimize the dielectric properties of CaCu3Ti4O12 ceramics by adjusting the conductivities of grains and grain boundaries

Reduction of dielectric loss for CCTO ceramics is a prerequisite for their applications. Considering internal barrier layer capacitance effect, improving the capacitance and grain boundary resistance is an effective way to reduce dielectric loss. Therefore, more conductive Ti³⁺ and Cu⁺ ions were introduced to grains by adding carbon to ceramic bodies, improving the permittivity of CCTO ceramics. Annealing was performed to increase the grain boundary resistance. The dielectric loss of the CCTO ceramics thus prepared, which maintain a giant permittivity, is significantly reduced. Specifically, the CCTO ceramic with carbon addition, which was sintered at 1080 °C for 8 h and air annealed at 950 °C for 2 h, exhibits a giant permittivity of about 2.50(5)×10⁴ and a low dielectric loss of less than 0.050(2) from below 20 Hz to 50 kHz at room temperature. Meanwhile, its dielectric loss at 1–10 kHz is less than 0.050(2) from below room temperature to about 100 °C.     

Grain boundary engineering that induces ultrahigh permittivity and decreased dielectric loss in CdCu3Ti4O12 ceramics

Dielectric materials with ultrahigh permittivity are attracting attention due to the increasing demand for these types of materials for microelectronics and energy storage applications. In this work, we successfully synthesized Zn-doped CdCu₃Ti₄O₁₂ (CdCTO) ceramics with low dielectric loss and large permittivity via an ordinary mixed-oxide technique. Remarkably, at a Zn doping level of 0.10, a CdCu_2.9Zn_0.1Ti₄O₁₂ ceramic exhibited both decreased dielectric loss tangent of ~0.058 and large dielectric permittivity > 4.0 × 10⁴, as well as a good frequency stability over a wide frequency range from 40 Hz to 10⁶ Hz. The high dielectric performance was attributed to the enhanced grain boundary resistance and internal barrier layer capacitor (IBLC) effect due to the fine and uniform grains that formed upon Zn doping. The findings reported in this work provide valuable insights into how to simultaneously realize a low dielectric loss and high permittivity in CdCTO and other related dielectric ceramics.     

High-resolution FIB-TEM-STEM structural characterization of grain boundaries in the high dielectric constant perovskite CaCu3Ti4O12

In this work, the grain boundaries composition of the polycrystalline CaCu₃Ti₄O₁₂ (CCTO) was investigated. A Focused Ion Beam (FIB)/lift-out technique was used to prepare site-specific thin samples of the grain boundaries interface of CCTO ceramics. Scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray spectrometry (EDXS) and Electron Energy Loss Spectroscopy (EELS) systems were used to characterize the composition and nanostructure of the grain and grain boundaries region. It is known that during conventional sintering, discontinuous grain growth occurs and a Cu-rich phase appears at grain boundaries. This Cu-rich phase may affect the final dielectric properties of CCTO but its structure and chemical composition remained unknown. For the first time, this high-resolution FIB-TEM-STEM study of CCTO interfacial region highlights the composition of the phases segregated at grain boundaries namely CuO, Cu₂O and the metastable phase Cu₃TiO_4.     

Origin of high dielectric performance in fine grain-sized CaCu3Ti4O12 materials

We report on high dielectric constant (8.3 × 10³, 10⁴ Hz), low dielectric loss (0.029, 10⁴ Hz) as well as fine grain size (∼840 nm) achieved in pure CaCu₃Ti₄O₁₂ (CCTO) ceramics through a combination of sol–gel method, spark plasma sintering and annealing process. By adjusting the sintering temperature and annealing conditions, the composition variations, valence states and microstructures of CCTO ceramics are systematically studied, which provide direct clues in understanding the origin of their excellent dielectric response. Through the studies on the dielectric, impedance, modulus and conductivity properties of CCTO ceramics, a modified brick-layer model based on two interfacial polarizations originating from sub-grain boundary and grain boundary barriers is proposed to explain their dielectric behaviors. The high dielectric constant of CCTO ceramics is mainly dominated by the sub-grain contribution; and the reduced dielectric loss is attributed to the decreases of electrical conductivity and relaxation loss.     

Low dielectric loss,colossal permittivity,and high breakdown electric field in Al-doped Y2/3Cu3Ti4O12 ceramics

The miniaturization and high capacitance of electronic components are driving the development of high-performance electronic ceramic materials. In this work, we design a new strategy to achieve satisfactory dielectric properties with low loss, colossal permittivity, and a high breakdown electric field (E_b) in Al-doped Y_2/3Cu₃Ti₄O₁₂ (YCTO) ceramics prepared by a solid-phase synthesis method. The dielectric loss decreased with Al doping in the YCTO. The dielectric constant and the E_b were improved upon Al doping. With Al doping levels of 0.03 and 0.05, Y_2/3Al_0.03Cu_2.97Ti₄O₁₂ and Y_2/3Al_0.05Cu_2.95Ti₄O₁₂ ceramics displayed, respectively, a suppressed loss tangent of about 0.028 and 0.031, a high dielectric constant of approximately 9540 and 11792, and an E_b of approximately 4.32 and 4.54 kV/cm. The improved dielectric properties of the produced ceramics were closely linked to enhanced grain boundaries resistance. This study explores the physical mechanism behind the high performance of the YCTO-based ceramics, and also provides theoretical support for the application of devices comprising YCTO and related materials.     

Deficient or excessive CuO-TiO2 phase influence on dielectric properties of CaCu3Ti4O12 ceramics

The influence of the CuO–TiO₂ phase (CT) on dielectric properties of the CCTO ceramic was investigated. CaCu_XTi_YO₁₂ (CC_XT_YO) powders were prepared based on the coprecipitated method, where 2.70 ≤ x ≤ 3.30 and 3.25 ≤ y ≤ 4.75. XRD patterns confirmed the presence of CCTO and also the secondary phases as CuO, TiO₂, and CaTiO₃ for each sample and aided in its quantification. Scanning Electron Microscopy (SEM) shows secondary phases evolution in the grain boundaries, and its influence on size and morphology of the grains. Impedance spectroscopy measurements showed that the ceramics with lower amount of CuO and TiO₂ phases (CT/deficient ceramics) exhibited the highest ε′ values (2.1 × 10⁴ at 1 kHz for CC_2.9T_3.75O ceramic). Also, CT/deficient ceramics showed lower tanδ values (0.090 at 1 kHz for CC_2.9T_3.75O ceramic) than ceramics prepared with excessive CuO–TiO₂ phase (0.241 at 1 kHz for CC_3.1T_4.25O ceramics). The deficiency of CuO and TiO₂ phases associated with high percentage of CCTO and CaTiO₃ phases resulted in ceramics with the higher ε′ values.     

Low-temperature synthesis of CdCu3Ti4O12 powders with high dielectric permittivities

The molten salt method was adopted in this work to synthesize CdCu₃Ti₄O₁₂ precursor powders and was found capable of notably reducing the sintering temperature. It was also found that the grain size gradually increases and the grain shape changes from spherical to cubic with increasing proportions of molten salt. The optimal sintering conditions were found to be at approximately 730?°C with the addition of 20% molten salt. After further sintering at 975?°C, the obtained perovskite ceramics exhibited a high dielectric constant at low frequencies.     

Influence of Zn doping on microstructures and dielectric properties in CaCu3Ti4O12 ceramic synthesised by semiwet route

Abstract

A single phase of calcium copper titanate [CaCu₃Ti₄O₁₂ (CCTO)] was produced at lower temperature and shorter calcination time via a novel semiwet route. Undoped CCTO and zinc doped CaCu_3?xZn_xTi₄O₁₂ samples with x?=?0·10, 0·20 and 0·30 were prepared by this method for the first time using solid TiO₂ powder in metal nitrate solutions. The CaCu_3?xZn_xTi₄O₁₂ ceramics were characterised by thermogravimetric/differential thermal analysis, X-ray diffraction, SEM and EDX techniques. The SEM images of the sintered CaCu_3?xZn_xTi₄O₁₂ ceramics showed average grain size in the ranges of 2–6, 8–13, 12–16 and 14–20 μm for x?=?0·00, 0·10, 0·20 and 0·30 respectively. Energy dispersive X-ray spectroscopy studies confirm the purity of parent and Zn doped CCTO ceramics. At room temperature, the dielectric constants of Zn doped CCTO are always higher than pure CCTO. CaCu_3?xZn_xTi₄O₁₂ (x?=?0·20) ceramic has the maximum value of ?_r≈4347 along with the minimum value of tan?δ≈0·14 at 1 kHz.     

Improved dielectric properties in A′‐site nickel‐doped CaCu3Ti4O12 ceramics

The improved dielectric properties and voltage‐current nonlinearity of nickel‐doped CaCu₃Ti₄O₁₂ (CCNTO) ceramics prepared by solid‐state reaction were investigated. The approach of A′‐site Ni doping resulted in improved dielectric properties in the CaCu₃Ti₄O₁₂ (CCTO) system, with a dielectric constant ε′≈1.51×10⁵ and dielectric loss tanδ≈0.051 found for the sample with a Ni doping of 20% (CCNTO20) at room temperature and 1 kHz. The X‐ray photoelectron spectroscopy (XPS) analysis of the CCTO and the specimen with a Ni doping of 25% (CCNTO25) verified the co‐existence of Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺. A steady increase in ε′(f) and a slight increase in α observed upon initial Ni doping were ascribed to a more Cu‐rich phase in the intergranular phase caused by the Ni substitution in the grains. The low‐frequency relaxation leading to a distinct enhancement in ε′(f) beginning with CCNTO25 was confirmed to be a Maxwell‐Wagner‐type relaxation strongly affected by the Ni‐related phase with the formation of a core‐shell structure. The decrease of the dielectric loss was associated with the promoted densification of CCNTO and the increase of Cu vacancies, due to Ni doping on the Cu sites. In addition, the Ni dopant had a certain effect on tuning the current‐voltage characteristics of the CCTO ceramics. The present A′‐site Ni doping experiments demonstrate the extrinsic effect underlying the giant dielectric constant and provides a promising approach for developing practical applications.     

Origin of the temperature stability of dielectric constant in CaCu3Ti4O12

The temperature and dc bias stability of the dielectric constant and loss tangent of CaCu₃Ti₄O₁₂ samples sintered under different oxygen atmospheres are discussed. The results suggest that the metal-oxygen vacancy related defects not only provide the charge carriers for the conduction (defect doping) but also contribute to the huge permittivity in the way of defect dipoles repositioning under charge carrier hopping. The charge localization in a specific copper-oxygen vacancy defect complex is the reason of the huge and stable permittivity and low dielectric loss in the middle temperature range, 90 K-200 K (20 Hz), while the implementation of the large barrier layer height needs a contribution by the titanium oxygen vacancy related trap charges in the grain boundaries, which also lead to a second permittivity stable range in a higher temperature range 200 K–300 K.     

Enhancement of giant dielectric response in Ga-doped CaCu3Ti4O12 ceramics

The influences of Ga³⁺ doping ions on the microstructure, dielectric and electrical properties of CaCu₃Ti₄O₁₂ ceramics were investigated systematically. Addition of Ga³⁺ ions can cause a great increase in the mean grain size of CaCu₃Ti₄O₁₂ ceramics. This is ascribed to the ability of Ga³⁺ doping to enhance grain boundary mobility. Doping CaCu₃Ti₄O₁₂ with 0.25 mol% of Ga³⁺ caused a large increase in its dielectric constant from 5439 to 31,331. The loss tangent decreased from 0.153 to 0.044. The giant dielectric response and dielectric relaxation behavior can be well described by the internal barrier layer capacitor model based on Maxwell?Wagner polarization at grain boundaries. The nonlinear coefficient, breakdown field, and electrostatic potential barrier at grain boundaries decreased with increasing Ga³⁺ content. Our results demonstrated the importance of ceramic microstructure and electrical responses of grain and grain boundaries in controlling the giant dielectric response and dielectric relaxation behavior of CaCu₃Ti₄O₁₂ ceramics.     

Improved dielectric properties and grain boundary response of SrTiO3 doped Y2/3Cu3Ti4O12 ceramics fabricated by Sol-gel process for high-energy-density storage applications

A chemical solution processing method based on sol-gel chemistry (SG) was used to synthesize (1-x)Y_2/3Cu₃Ti₄O₁₂-xSrTiO₃ (x = 0, 0.05, 0.1, 0.15, 0.2, 0.25) ceramics successfully. The 0.85Y_2/3Cu₃Ti₄O₁₂-0.15SrTiO₃ ceramics sintered at 1050 °C for 20 h showed fine-grained microstructure and high dielectric constant (ε′ ≈ 1.7 × 10⁵) at 1 kHz. Furthermore, the 0.85Y_2/3Cu₃Ti₄O₁₂-0.15SrTiO₃ ceramics appeared distinct pseudo-relaxor behavior. Two electrical responses were observed in the combined modulus and impedance plots, indicating the presence of Maxwell-Wagner relaxation. Sr vacancies and additional oxygen vacancies had substantial contribution to the sintering behavior, an increase in grain growth, and relaxation behaviors in grain boundaries. The contributions of semiconducting grains with the nanodomain and insulating grain boundaries (corresponding to high-frequency and low-frequency electrical response, respectively) played important roles in the dielectric properties of (1-x)Y_2/3Cu₃Ti₄O₁₂-xSrTiO₃ ceramics. The occurrence of the polarization mechanism transition from the grain boundary response to the electrode one with temperature change was clearly evidenced in the low frequency range.     

溶胶-凝胶法制备巨介电常数材料CaCu3Ti4O12

通过溶胶-凝胶法制备CaCu3Ti4O12干凝胶,再经700～900℃,6～10h预烧和950～1 100℃,16～20h烧结,成功制备了CaCu3Ti4O12粉体和CaCu3Ti4O12巨介电常数陶瓷材料.用X射线衍射、扫描电镜分别确定了样品的结晶性能和形貌.用阻抗分析仪在10～106Hz范围内测试了陶瓷样品的介电性能.结果表明:粉体的结晶性能与煅烧温度有关,陶瓷介电性能与其晶粒大小有关.相对于传统固相反应合成法制备的粉体和陶瓷,粉体的预烧和陶瓷的烧结温度都有明显降低,烧成温度至少降低100℃.在800℃预烧的CaCu3Ti4O12粉体并在1 100℃温度下烧结制备的陶瓷,其介电常数可达194753.     

Synthesis of CaAl2xB2O4+3x: Novel microwave dielectric ceramics with low permittivity and low loss

Novel CaAl_2xB₂O_4+3x (x = 0.25, 0.5, 0.75, and 1) ceramics were prepared via solid-state reaction method. The investigation is concentrated on sintering behavior, phase composition and dielectric properties of CaAl_2xB₂O_4+3x ceramics with various ratios of Al₂O₃ content. The optimal sintering temperature and the content of CaAl₂B₂O₇ are highly related to the variation of x value. CaAl_2xB₂O_4+3x ceramics possess excellent microwave dielectric properties: ε_r = 5.8 ± 0.05, Q × f = 63,338 ± 2690 GHz (@13.57 GHz), and τ_f=-29 ± 2 ppm/℃ when sintered at 940 ℃ for x = 0.5. Comparing the properties of CaAl_2xB₂O_4+3x ceramics with reported borate ceramics, the ceramics prepared in this study with low dielectric loss and low sintering temperature have promising prospects in LTCC technology.     

Co-doping effects of A-site Y3+ and B-site Al3+ on the microstructures and dielectric properties of CaCu3Ti4O12 ceramics

Different doping elements have been used to reduce the dielectric losses of CaCu₃Ti₄O₁₂ ceramics, but their dielectric constants usually are undesirably decreased. This work intends to reduce their dielectric losses and simultaneously enhance their dielectric constants by co-doping Y³⁺ as a donor at A site and Al³⁺ as an acceptor at B site for substituting Ca²⁺ and Ti⁴⁺, respectively. Samples with different doping concentrations x = 0, 0.01, 0.02, 0.03, 0.05 and 0.07 have been prepared. It has been shown that their dielectric losses are generally reduced and their dielectric constants are simultaneously enhanced across the frequency range up to 1 MHz. The doped sample with x = 0.05 exhibits the highest dielectric constant, which is well over 10⁴ for frequency up to 1 MHz and is about 20% higher than the undoped sample. Impedance spectra indicate that the doped samples have much higher grain boundary resistance than the undoped one.     

Effect of calcium stoichiometry on the dielectric response of CaCu3Ti4O12 ceramics

Ca_xCu₃Ti₄O₁₂ (x = 0.90, 0.97, 1.0, 1.1 and 1.15) polycrystalline powders with variation in calcium content were prepared via the oxalate precursor route. The structural, morphological and dielectric properties of the ceramics fabricated using these powders were studied using X-ray diffraction, scanning electron microscope along with energy dispersive X-ray analysis, transmission electron microscopy, electron spin resonance (ESR) spectroscopy and impedance analyzer. The X-ray diffraction patterns obtained for the x = 0.97, 1.0 and 1.1 powdered ceramics could be indexed to a body-centered cubic perovskite related structure associated with the space group Im3. The ESR studies confirmed the absence of oxygen vacancies in the ceramics that were prepared using the oxalate precursor route. The dielectric properties of these suggest that the calcium deficient sample (x = 0.97) has a reduced dielectric loss while retaining the high dielectric constant which is of significant industrial relevance.     

Composite screen‐printed thick films for high dielectric constant devices: Bi4Ti3O12–CaCu3Ti4O12 films

In this paper, we did a study of the effect of the presence of BIT (Bi₄Ti₃O₁₂) in the dielectric and optical properties of the CaCu₃Ti₄O₁₂ (CCTO) thick films. The films were prepared by the solid sate 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 film. 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 (D) of the films. The role played by the grain size of CCTO and BIT in the dielectric constant and structural properties of the films are discussed. These measurements confirm the potential use of such materials for small high dielectric planar devices. These films are also attractive for capacitor applications and certainly for microelectronics, microwave devices (mobile phones for example), where the miniaturization of the devices is crucial. POLYM. COMPOS., 28:771–777, 2007. © 2007 Society of Plastics Engineers