Utilization of Multiple-Stage Sintering to Control Ni Electrode Continuity in Ultrathin Ni–BaTiO3 Multilayer Capacitors

Microstructural control in thin-layer multilayer ceramic capacitors (MLCCs) is one of the present-day challenges for maintaining an increase in capacitive volumetric efficiency. The present paper continues a series of investigations aimed at understanding and controlling the microstructural stability of ultrathin Ni electrodes in MLCCs. Here, a kinetic approach based on the control of sintering profiles is used. Ni–BaTiO₃ MLCC chips (0805-type with 300 active layers) are nonisothermally sintered up to 900°–1300°C with different heating rates in the range from 200° to 3000°C/h. In general, the continuity of the Ni electrodes increases with heating rate. However, a strong nonlinear dependence of Ni electrode continuity on sintering temperature is observed. It is concluded that a low-melting interfacial liquid (Ni,Ba,Ti) alloy layer initiates at temperatures between 1000° and 1100°C when the Ni electrodes are under tension. This interfacial liquid phase accelerates a stress-induced diffusion and is the key cause of the severe electrode discontinuities during heating. At higher temperatures (above 1100°C), where compressive stresses are active, the interfacial liquid alloy layer facilitates some recovery of the Ni electrode microstructure. The formation of the interfacial liquid alloy layer can be kinetically controlled using fast-heating rates, which improves the Ni electrode continuity.     

Defects of Base Metal Electrode Layers in Multi-Layer Ceramic Capacitor

An ultra-thin Ni-based metal used as the electrode layer in multilayer ceramic capacitor determines the dielectric performance of the capacitor. The warpage and the continuity of the inner electrode layers, and a dihedral angle between BaTiO₃ layers and metal electrodes of two ceramic capacitors (X7R and X5R) were characterized by optical microscopy and scanning/transmission electron microscopes. The results show that the warpage of the chips is closely related to the discontinuity of the inner electrode. The discontinuity takes place mainly because of Rayleigh instability of the Ni layer, but is less induced by the tensile stress from sintering.     

Dielectric Properties and Reliability of Zn0.95Mg0.05TiO3+0.25TiO2 MLCCs with Different Pd/Ag Ratios of Electrodes

In order to study the micromechanism of silver migration that influences the dielectric properties and reliability of Zn_0.95Mg_0.05TiO₃+0.25TiO₂ (ZMT") with 1 wt% 3ZnO–B₂O₃ multilayer ceramic capacitors (MLCCs), various silver (Ag)–palladium (Pd) ratios of conductors were used as inner electrodes. It was found that the electrical resistance of a MLCC sample with pure Ag as inner electrodes was degraded drastically to compared with the Ag/Pd inner electrodes at measuring temperatures ranging from 25°C to 175°C. It may be explained that the pure Ag migrates easily into the dielectric layer along the grain boundary during co-firing. The ZMT" MLCCs exhibited increasing dielectric constant and insulation resistance considerably with increasing sintering temperature. Moreover, the results also indicate that Ag diffusion changes the dielectric properties and decreases the breakdown voltage. A ZMT" MLCC with a high Ag content in the inner electrode exhibits poor reliability, and the effect of Ag⁺ migration is markedly enhanced when the activation energy of the ZMT" dielectric is considerably lowered due to the excessive formation of oxygen vacancies and the semiconducting Zn₂TiO₄ phase when Ag⁺ substitutes for Zn²⁺ during co-firing.     

Microcontact Printed BaTiO3 and LaNiO3 Thin Films for Capacitors

There is an ongoing need to develop new technologies to enable further down-scaling of layer thicknesses in multilayer ceramic devices, for example, in multilayer capacitors (MLC). Microcontact printing of chemical solutions of both the dielectric and electrode layers was explored as an economical means of preparing patterned thin films for MLC without requiring photolithography. For this purpose, methanol/acetic acid-based BaTiO₃ solutions were spun onto polydimethylsiloxane stamps, printed onto substrates, pyrolyzed, and crystallized. LaNiO₃ was used as a prototype electrode that could also be microcontact printed. The line edge roughness produced this way was on the order of a tenth of a micrometer, which should enable very small margins. The printed layer thickness was also very uniform. Microcontact printed capacitors with a single dielectric layer were fabricated and found to have dielectric constants >800 with loss tangents <2%. Alignment between subsequent layers is readily achieved. Multilayer dielectric/electrode stacks could be fabricated without cracking or delaminations. Consequently, microcontact printing appears to be a viable potential means of preparing MLC with layer thicknesses in the range of ≤0.2 μm.     

Improvement in the Temperature Stability of a BaTiO3-Based Multilayer Ceramic Capacitor by Constrained Sintering

In this study, a self-constrained BaTiO₃ material system, composed of a low-fire BaTiO₃-based X7R (Δ C / C ±15% within −55° to 125°C) MLCC dielectric and a high-fire, BaTiO₃-based X7R MLCC dielectrics eliminated sintering aid that are laminated on both sides of the BaTiO₃-based X7R MLCC, has been developed. The temperature dependence of capacitance of the BaTiO₃-based X7R MLCC is significantly improved to satisfy X8R requirements over the entire temperature range studied (Δ C / C ±15% within –55° to 150°C) using the self-constrained sintering. The curie temperature of BaTiO₃-based X7R MLCC increases on increasing the thickness of the constraining layers. Compared with the specimen fired by free sintering, a substantial reduction in grain size, leading to a decrease in dielectric constant, was observed in the specimen fired by constrained sintering with the thickness of the constraining layer being 170 μm. The increase in Curie temperature and decrease in grain size of the specimen fired by constrained sintering can be explained in terms of the presence of in-plane tensile stress. The in-plane tensile stress that introduces a friction force between the multilayer matrix and the nonshrinkage constraining layers to suppress the in-plane shrinkage and to inhibit the rate of grain growth was formed during constrained sintering.     

Low-Temperature Sintering Barium Titanate-Based X8R Ceramics with Nd2O3 Dopant and ZnO–B2O3 Flux Agent

To demonstrate that barium titanate-based ceramics could be sintered at a low temperature thus reducing the cost of capacitor production, systematic investigation has been made on the structure and dielectric properties of barium titanate-based X8R ceramics, doped with various Nd₂O₃ content and different ZnO–B₂O₃ solution as the sintering aids. The dielectric ceramic powder with good permittivity and low dielectric loss were obtained at a sintering temperature of 900°C, meeting X8R specifications. Transmission electron microscopy and EDS analysis shows a high concentration of Nd element in the boundary regions, which verifies the beneficial role of Nd in facilitating the formation of core-shell structure. The results also suggest that the developed BaTiO₃-based ceramics may serve as a promising candidate for fabricating cheap multilayer capacitors with pure Ag as inner electrode.     

Preparation of Nano BaTiO3-Based Ceramics for Multilayer Ceramic Capacitor Application by Chemical Coating Method

The base-metal-electrode multilayer ceramic capacitors (BME MLCCs) for future application require much thinner dielectric layers (<1 μm). Therefore, the grain size and uniformity of BME MLCC powders should be effectively controlled. In this paper, the nanosized BME MLCC powders were prepared by chemical coating method. The well-coated BaTiO₃ particles were obtained by adjusting an appropriate pH value. Transmission electron microscopy, energy-dispersive spectroscopy, X-ray photoelectron spectrum were utilized for the study of microstructures and element analysis. The high-performance X7R dielectric ceramics were produced in reducing atmosphere by "two-step" sintering method at a low temperature of 950°C. The dielectric constant at room temperature could reach ∼2400, with low dielectric loss below 1.0% and high insulation resistivity ∼10¹²Ω·cm. The ceramic grains were very homogenous with the average size below 150 nm.     

Effect of Oxygen Partial Pressure on the Dielectric Properties and Microstructures of Cofired Base-Metal-Electrode Multilayer Ceramic Capacitors

The dielectric properties, dopant distributions, and microstructures of BaTiO₃-based multilayer ceramic capacitors (MLCCs) sintered in H₂–N₂–H₂O atmospheres with     =10^−7.5 Pa (BMX-7.5) and     =10^−9.5 Pa (BMX-9.5) were studied, and the effects of oxygen partial pressures were analyzed. Dielectric measurements showed that BMX-7.5 had a lower dielectric constant at temperatures above 20°C, but a higher dielectric constant at temperatures below 10°C when compared with BMX-9.5. The coexistence of core–shell and core grains was observed in bright field (BF) transmission electron microscopy images in both types of capacitors. Triple-point and grain boundary phases were observed more frequently in BMX-9.5 than in BMX-7.5, and energy-dispersive X-ray spectrometer point-by-point analysis revealed that these second phases contained high concentrations of dopants such as Si, Y, and Ca. The dopant concentration in the shell regions in BMX-7.5 was higher than that in similar regions in BMX-9.5. Smeared and twisted grain boundaries with fringes observed in both types of MLCCs indicated that the shell regions in both samples were formed either by diffusion of foreign ions into BaTiO₃ or by crystallization of grain boundary and triple-point liquid phases. It was deduced that the partial pressure of oxygen in the sintering atmosphere influenced the microstructures, dopant distributions, and core–shell ratios of the grains in these materials.     

Reversible Weight Change of Acceptor-Doped BaTiO3

The oxygen vacancy concentration of BaTiO₃ doped with acceptors (Cr to Ni) is determined gravimetrically as a function of the O₂ partial pressure during and after annealing at 700° to 1300°C. The oxygen vacancy concentration of these materials is larger than that of undoped and donor-doped BaTiO₃. The oxygen vacancies are doubly ionized and they compensate the acceptors of lower valence. Both the vacancy concentration and the valence of the acceptor dopants depend on the annealing conditions. The electronic energy levels of the acceptors within the BaTiO₃ band gap are derived from the gravimetric measurements. The electrical properties of the acceptor-doped ceramics are favorable for base-metal-electrode multilayer capacitors, which require sintering in reducing atmospheres.     

Effect of Densification Mismatch on Camber Development during Cofiring of Nickel-Based Multilayer Ceramic Capacitors

The development of camber during the cofiring of a two-layered structure of Ni-electrode/BaTiO₃-dielectric as a function of temperature has been investigated. At a given thickness of Ni electrode, less camber and camber rate with increasing thickness of BaTiO₃ dielectric have been observed. This phenomenon is attributed to the densification mismatch between the Ni electrode and the BaTiO₃ dielectric during cofiring. The mathematical analysis of camber development, based on a viscous model, shows significant agreement with experimental observations.     

Equivalent Circuit Model in Grain-Boundary Barrier Layer Capacitors

Electrical properties of BaTiO₃-based capacitors are investigated. A new model is developed to explain the frequency response of the impedance of grain-boundary barrier layer (GBBL) capacitors. This model takes into consideration the dipole polarization effect and provides a simple and effective approach to evaluate the performance of GBBL capacitors with various dopants and sintering in different atmospheres. When sintered in a reducing atmosphere, doped BaTiO₃ exhibits a higher dielectric constant and a relatively stable dieletric constant with respect to the frequency response and temperature dependence. Also, smaller grain resistivity is obtained with addition of both Dy₂O₃ and Nb₂O₅.     

Kinetic Process of Reoxidation of Base Metal Technology BaTiO3-Based Multilayer Capacitors

Base metal technology, mainly using Ni electrodes in multilayer ceramic capacitors (MLCCs), is now well established. This technology requires a so-called reoxidation treatment after sintering the MLCCs in a reducing atmosphere to guarantee a sufficient electrical reliability. Large numbers of electrodes, and production of physically larger components for high-voltage components, are two technological trends that make the control of the reoxidation process rather difficult. The reoxidation process has been studied to determine oxygen diffusion pathways into commercial MLCCs, using ¹⁸O tracer diffusion and finite element calculations. In MLCCs oxygen diffusion mainly occurs along the Ni electrodes. Furthermore, the reoxidation process is mostly controlled by the thermodynamic potential of the Ni/NiO equilibrium in the interior of the capacitor, but it is the short circuit diffusion along the interface of the electrode that controls the kinetics of the oxygen transport into the interior of the capacitor device.     

High-Energy Density Capacitors Utilizing 0.7 BaTiO3–0.3 BiScO3 Ceramics

A high, temperature-stable dielectric constant (∼1000 from 0° to 300°C) coupled with a high electrical resistivity (∼10¹²Ω·cm at 250°C) make 0.7 BaTiO₃–0.3 BiScO₃ ceramics an attractive candidate for high-energy density capacitors operating at elevated temperatures. Single dielectric layer capacitors were prepared to confirm the feasibility of BaTiO₃–BiScO₃ for this application. It was found that an energy density of about 6.1 J/cm³ at a field of 73 kV/mm could be achieved at room temperature, which is superior to typical commercial X7R capacitors. Moreover, the high-energy density values were retained to 300°C. This suggests that BaTiO₃–BiScO₃ ceramics have some advantages compared with conventional capacitor materials for high-temperature energy storage, and with further improvements in microstructure and composition, could provide realistic solutions for power electronic capacitors.     

Dielectric Properties of (Pb1–xXx) (Zr0.7Ti0.3)O3 (X = Ca, Sr, Ba) Ceramics

The dielectric properties of (Pb_{1– x} X_x) (Zr_0.7Ti_0.3)O₃ (X = Ca, Sr, Ba) ceramics (abbreviated PXZT) were investigated for applications to multilayer ceramic capacitors (MLCs) with dielectric layers thinner than 10 μm. The dissipation factors for MLCs with 5-μm-thick dielectric layers were estimated from those for 100-μm-thick disk specimens measured at an oscillation voltage of 20 V_rms. Those for PCZT and PSZT were less than 1.0% when the oscillation voltage was 20 V_rms, while those for conventional BaTiO₃-based dielectric ceramics were greater than 2.5% at 20 V_rms. According to polarization–electric field hysteresis measurements, PCZT and PSZT revealed linear and double hysteresis loops, respectively, while PBZT and BaTiO₃ indicated typical ferroelectric hysteresis loops. The differences in the dissipation factors for the dielectric compositions are attributed to hysteresis in the polarization–electric field loops. These results suggest that PCZT and PSZT are promising dielectric ceramics for MLCs with dielectric layers thinner than 10 μm.     

Direct Writing of Dielectric Ceramics and Base Metal Electrodes

Three-dimensional structures were assembled by direct writing of colloidal gel-based inks of electro-ceramic and metal electrode compositions. The ternary mixtures of BaTiO₃, BaZrO₃, and SrTiO₃ were explored via an active mixing nozzle print strategy that allowed for rapid screening of complex oxide ceramics. In a second experiment, Ni and BaTiO₃ inks were developed from commercially available powders in the form of concentrated, aqueous colloidal gels having shear thinning with yield stress rheology. The different surface chemistry of Ni and BaTiO₃ was accommodated by adsorbing a bi-layer of oppositely charged polyelectrolytes on the BaTiO₃ particles. Alternating layers of metal and ceramic were printed to build a multilayer structure. The multilayer Ni–BaTiO₃ structures were sintered in a reducing atmosphere and the capacitance was measured. These two examples illustrate the use of discrete or graded deposition capabilities of direct writing.     

Investigation on the Microstructure and Dielectric Properties of BaTiO3–Nb2O5–Fe2O3 Materials Doped with La2O3

The influence of La₂O₃ doped on the microstructure and dielectric properties, including the phase structure, temperature dependence of permittivity, and the hysteresis loop of BaTiO₃–Nb₂O₅–Fe₂O₃ (BTNF) materials has been investigated in X-ray diffraction, SEM, and LCR analyzer, respectively. Experiments revealed that incorporation of proper content of La₂O₃ basically soluted in the lattice of BaTiO₃ and can control the grain-growth, reduce the dielectric loss of the BTNF materials. The development of microstructure promoted by the additives can result in the improvement of the dielectric constant. When the doping concentration of La₂O₃ was 3.846 wt%, the relative dielectric constant of the sample sintered at 1280°C only for 2 h could reach 4308, and improve the dielectric-temperature characteristics markedly. As a result, a novel Y5P can be achieved in the BTNF ceramics, which is very promising for practical use in Y5P multilayer ceramic capacitors.     

Uniform Coating of Nanometer-Scale BaTiO3 Layer on Spherical Ni Particles via Hydrothermal Conversion of Ti-Hydroxide

A uniform BaTiO₃ nano layer was coated on spherical Ni particles for multilayer ceramic capacitor applications via a Ti-hydroxide coating using the controlled hydrolysis of a TiCl₄ butanol solution containing (C₂H₅)₂NH (diethylamine, DEA) and its subsequent hydrothermal reaction at various [Ba(OH)₂], residual [DEA], and hydrothermal temperatures. The hydrothermal conversion was successful at [Ba(OH)₂]≥0.065 M (Ba/Ti≥1.3) and T ≥150°C, and the residual DEA in the Ti-hydroxide coating layer not only affected the formation of the BaTiO₃ phase but also resulted in a rough surface morphology. When a minimal amount of DEA was involved in the formation of Ti-hydroxide, a uniform BaTiO₃ coating with a clean surface morphology could be attained, which was confirmed by elemental mapping of the coated powder and the observation of hollow spheres after removing the Ni core. The BaTiO₃ coating was very effective not only in preventing Ni oxidation but also in shifting the starting point of Ni densification to a higher temperature.     

A novel approach to sintering (Ba,Ca)(Ti,Zr)O3 multilayer ceramic capacitors with Ni electrodes

In this study, a novel sintering technique combining rapid heating and constrained sintering was adopted to fire multilayer ceramic capacitors (MLCCs). It was demonstrated that chamber development can be significantly minimized, leading to a small internal residual stress in MLCCs when they were fired by the novel sintering technique instead of free sintering. The magnitude of tensile stress was closely related to the heating rate and the thickness of the constraining layer. The presence of in-plane tensile stress resulted from the constrained sintering in the x–y plane of the MLCCs, which then modified both the densification rate of the dielectric materials and the inner electrode. The thin inner electrode (<1 μm) with high continuity (>98%) and the fine grain size (1.5 μm) with narrow distribution (±0.10 μm) of BCTZ-based MLCC with a concave-free morphology can be attained by using such a rapid constrained sintering technique when BT is used as a constraining layer laminated on both sides of the multilayer BCTZ-based MLCC.     

Effect of Manganese Oxide Additive on the Dielectric Properties of Mixed-Sintering Ceramics

The influence of internal electrode material on the sintering of mixed-sintering ceramics and the effect of MnO₂ additive on improving their dielectric properties were investigated for their application as multilayer ceramic capacitors. The resistivities of mixed-sintering ceramic pellets sintered with Ag-Pd electrode material decreased remarkably because of the expulsion of component elements during sintering. A small amount of MnO₂ additive improved the resistivities. Extended X-ray absorption fine-structure analysis showed that MnO₂ exists in the grain boundaries and compensates for the electrical valence of the expelled elements.     

Electrode–Ceramic Inter-Diffusion of Ba(Ti,Zr)O3-Based Y5V MLCCs with Ni Electrodes

The Ba(Ti,Zr)O₃-based multilayer ceramic capacitors (MLCCs) with Ni electrodes, which meet the Electronic Industry Association Y5V standard (from −30° to 85°C, at a temperature capacitance coefficient between −82% and 22%), have been studied in view of the electrode-ceramic inter-diffusion by several microstructual techniques (scanning electron microscopy/transmission electron microscopy/high-resolution transmission electron microscopy (HRTEM)) with an energy-dispersive X-ray spectrometer (EDS). The EDS analysis shows that the elements' inter-diffusion took place along the metal–dielectric interface and the migration of Ni toward the dielectric layers dominated this process. The incorporation of Ni did not transform the crystal structure but introduced lattice distortions, which were characterized by HRTEM, X-ray diffraction, and EDS. The degree of Ni diffusion in the sample with the thinner dielectric layer was more severe. It was concluded from the results that the Ni diffusion is related to the formation of oxygen vacancies after the annealing process, which should be a noticeable factor in the degradation behavior and reliability of base metal electrode MLCCs. The factors influencing the inter-diffusion are also discussed.