Effect of yttrium (Y) substitution on the structure and dielectric properties of BaTiO3

As the rate of application of multilayer ceramic capacitors (MLCCs) in small electronic devices increases, the use of the raw material barium titanate (BaTiO₃) with a small particle size and excellent dielectric properties becomes needed. Due to the size effect, small-sized BaTiO₃ generally has a cubic phase structure with a low dielectric constant, which limits its use in MLCCs. We report the preparation of small cubic phase Y-doped BaTiO₃ (BYT) nanoparticles by a hydrothermal method and the preparation of highly dielectric tetragonal phase BYT ceramics based on this method. XRD and Raman analysis showed that the BYT nanoparticles are in substable cubic phases. The particle size of the BYT nanoparticles, measured by TEM, XRD, and BET, was approximately 35 nm. The dielectric properties of the BYT ceramics were tested by an impedance analyzer, and the dielectric constant of the BYT ceramics was 7547 when the Y³⁺ doping amount was 0.5 mol%. In addition, the substitution mechanism of Y³⁺ doping in BaTiO₃ crystals was proposed from XPS and EPR analysis. The results demonstrate for the first time that the 50 nm cubic phase BaTiO₃ powder can meet the needs of next-generation high-capacity MLCCs. This work provides a reference for small cubic phase BaTiO₃ as a dielectric material for high-capacity MLCCs.     

Multi-phase coexistence and temperature-stable dielectric properties in BaTiO3/ZnO composite ceramics

BaTiO₃:100xZnO composite ceramics with different ZnO particle sizes were prepared by using a conventional solid-state method. Phase constitution, microstructure and dielectric properties of BaTiO₃:100xZnO composite ceramics are investigated. Compared to micrometer scaled ZnO particles, nanometer scaled ZnO particles tend to agglomerate at lower ZnO contents in the BaTiO₃:100xZnO composite ceramics. The introduction of ZnO in BaTiO₃ leads to the reduction of grain size, decrease of the tetragonality and shift of phase transition temperature. The optimum composition is BaTiO₃ with 20 wt. % nanometer scaled ZnO particles, which has stable permittivity and low dielectric loss from -100 to 160 °C. The stable dielectric properties are proposed to be beneficiated from the stress induced multi-phase coexistence.     

Improved Energy Storage Properties of Fine‐Crystalline BaTiO3 Ceramics by Coating Powders with Al2O3 and SiO2

The multilayer structure of capacitor demands for fine grain size of dielectric ceramics in devices, because the thinner layer which needs ceramics with fine grain size is helpful in enlarging the capacitance. In this paper, the aqueous chemical coating method was utilized to modify the BaTiO₃ particles. The fine‐crystalline BaTiO₃ ceramics with an average grain size below 200 nm without abnormal grain growth by co‐coating Al₂O₃ and SiO₂ has been prepared. The phase composition, microstructures of coated particles and ceramics, and dielectric properties were investigated. For samples containing 3 wt% of Al₂O₃ and 1 wt% of SiO₂, the energy storage density is 0.725 J/cm³ and the efficiency of the ceramic samples can keep above 80%. The breakdown strength was improved to about 190 kV/cm.     

Percolative BaTiO3–Ni composite nanopowders from alkoxide-mediated synthesis

BaTiO₃–Ni nanopowders have been synthesized via an alkoxide-mediated synthesis route through the hydrolysis and condensation of barium hydroxide octahydrate and titanium (IV) isopropoxide in the presence of submicron sized, spherical Ni particles originating from a commercial Ni paste, that was introduced during the preparation procedure. X-ray diffraction (XRD) patterns indicate that nanocomposite powders of the phases BaTiO₃ and Ni could be successfully prepared and tailor-made composition control was confirmed. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the synthesized BaTiO₃ nanoparticles were aggregates of nanosized primary particles as small as 40 nm in diameter. The average Ni particle size was estimated to be about 200 nm. Dilatometric measurements on green compacts of these powders revealed that the shrinkage of BaTiO₃–Ni composites is retarded compared to both, pure BaTiO₃ and Ni. Thermogravimetric analysis (TGA) shows weight losses due to the decomposition of organic binder from Ni paste, the release of water from the surface and of hydroxyl ions from inside the lattice of the BaTiO₃ nanoparticles. With the addition of nickel, the dielectric constant increased slightly due to the percolation effect.     

Uniform Coating of BaTiO3–Dy2O3–SiO2 Compound Nano Layer on Ni Particles for MLCC Electrode

Uniform coating of nanometer‐scale BaTiO₃–Dy₂O₃–SiO₂ layers on spherical Ni particles are achieved by controlled hydrolysis of tetrabutyl titanate (TBT), hydrothermal reaction with Ba(OH)₂, and co‐precipitation of tetraethylorthosilicate (TEOS) and Dy(NO₃)₃. The composition of the coating layer is similar to rare earth oxide‐silica–doped BaTiO₃, which is the main component of dielectric layer for base metal electrode (BME) multilayer ceramic capacitors (MLCCs). After coating, the shrinkage onset temperature of Ni particles is significantly increased. After sintered to pellets, the electrode has good electrical conductivity. This electrode material has good compatibility with rare earth oxide and silica‐doped BaTiO₃ dielectric materials, and could serve as promising candidate for application in the next generation BME‐MLCCs.     

Simultaneous enhancement of dielectric properties and temperature stability in BaTiO3-based ceramics enabling X8R multilayer ceramic capacitor

Modified BaTiO₃ ceramics that possess high dielectric permittivity and acceptable temperature stability have been widely utilized as multilayer ceramic capacitors (MLCCs) for high-frequency bypass and power filtering in automotive applications. However, since the increasing demand for high-capacity and small-size, high-permittivity materials that can serve as dielectric layers in MLCCs are urgently required. In this work, we design and fabricate a special BaTiO₃-0.03Mg-0.02Y-0.02CaZrO₃ ceramic with a high dielectric permittivity of 3000 and the dielectric variation below ±13% in the temperature range of -55–150°C, fulfilling the requirements of X8R capacitors. To achieve these results, we employed grain size engineering and cation doping, using BaTiO₃ precursors with a particle size of 240 nm to prepare the BaTiO₃-based ceramics with fine grains, while Mg and Y co-doping was used for improving the temperature stability due to dielectric dispersion. Utilizing these high-permittivity BaTiO₃-based materials, we fabricated MLCCs that satisfy the X8R criterion, possessing a high dielectric constant of 2950 and a high breakdown field (410 kV/cm).     

Rapid Formation of Nanocrystalline BaTiO3 and Its Highly Stable Sol

Ultrafine BaTiO₃ nanoparticles and their highly stable sols are prepared by a novel and rapid route. In this method, the formation mechanism that lies between the chemical precipitation and the sol–gel process is proposed. The BaTiO₃ nanocrystal sols are synthesized in as fast as 15 min in an air atmosphere. Dynamic light scattering analysis and the observation of the Tyndall effect confirm the existence of crystalline nanoparticles in these sols. After careful separation, nanocrystalline BaTiO₃ powders with an average particle size as small as 2.8 nm are obtained. These particles have perovskite phase structures as determined by X‐ray diffraction and selected‐area electron‐diffraction analysis. Fourier transform infrared spectroscopy (FT‐IR) and thermal analysis are used to detect the characteristic functional groups of the solvents on the particles to reveal the formation mechanism. Uniform BaTiO₃ nanocrystal films with high dielectric constants, low dielectric losses, and paraelectric behavior are prepared through solvent evaporation of the nanocrystal sols, providing a new low‐temperature route for the fabrication of perovskite thin films.     

Preparation and characterization of polyimide/silica‐barium titanate nanocomposites

The silica‐barium titanate (SiO₂‐BaTiO₃) nanocomposites coated with polyimide had been synthesized successfully by a dispersion polymerization method. The conformation, structure, and size of SiO₂‐BaTiO₃ nanocomposites coated with polyimide were investigated by using FT‐IR, EDAX, XRD,TEM, SEM, and TGA. The results indicate that there is a thin layer polymer of SiO₂‐BaTiO₃ nanocomposites surface, in which the polymer thickness is about 10 nm and the size of them are about 50–60 nm, and the particles are well‐dispersed with even particle size. In addition, the crystal structure of BaTiO₃ is stable in preparing composite process and the chemical bond is formed between the inorganic phase and the polymer matrix. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Size and scaling effects in barium titanate. An overview

Ferroelectric perovskites such as BaTiO₃ and Pb(Zr,Ti)O₃ are well-suited for a variety of applications including piezoelectric transducers and actuators, multilayer ceramic capacitors, thermistors with positive temperature coefficient, ultrasonic and electro-optical devices. Ferroelectricity arises from the long-range ordering of elemental dipoles which determines the appearance of a macroscopic polarization and a spontaneous lattice strain. The confinement of a ferroelectric system in a small volume produces a perturbation of the polar order because of the high fraction of surface atoms and ferroelectricity vanishes when the size of the material is reduced below a critical dimension. This critical size is of a few nanometres in the case of epitaxial thin films and of 10−20 nm for nanoparticles and nanoceramics. The change in properties with decreasing physical dimensions is usually referred to as size effect. Thin films and ceramics are particularly prone to show size effects. A progressive variation of dielectric, elastic and piezoelectric properties of ferroelectric ceramics is already observed when the grain size is reduced below ≈10 μm, i.e. at a length scale much larger than the critical size. In this case it is more appropriate to refer to scaling effects as they are not related to material confinement.The aim of this contribution is to review the current understanding of size and scaling effects in perovskite ferroelectric ceramics and, in particular, in BaTiO₃. After a short survey on the intrinsic limits of ferroelectricity and on the impact of particle/grain size on phase transitions, the role of interfaces such as ferroelectric/ferroelastic domain walls and grain boundaries in scaling of dielectric and piezoelectric properties will be discussed in detail. Multiple mechanisms combine to produce the observed scaling effects and the maximization of the dielectric constant and piezoelectric properties exhibited by BaTiO₃ ceramics for an intermediate grain size of ≈1 μm. The broad dispersion of experimental data is determined by spurious effects related to synthesis, processing and variation of Ba/Ti ratio. Furthermore, we will consider these size effects, and other properties in relation to the downsizing the modern multilayer BaTiO₃ based capacitors.     

Toward green three‐phase composites with enhanced dielectric permittivity

This work aims to investigate the dielectric potential of microcrystalline cellulose, a green biosourced material, as a third constituent in the three‐phase composites based on ethylene vinyl acetate‐vinyl ester of versatic acid (EVA‐VeoVa) terpolymer and BaTiO₃. For that, new green three‐phase composites were prepared using an economic and green process, with simple implementation at room temperature and using water as a solvent. Compared with the binary composite EVA‐VeoVa/BaTiO₃, the three‐phase composite EVA‐VeoVa/BaTiO₃/microcrystalline cellulose showed an improvement of the BaTiO₃ particles dispersion, enhanced relative permittivity, and reduced dielectric loss, which explains the significance of this study. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46147.     

Enhancement on electric responses of BaTiO3 particles with polymer‐coating

To enhance electric response by polymer coating, BaTiO₃/polymer shell–core composite particles were prepared by emulsion polymerization with polyimide, chitosan, polystyrene, polyacrylic acid, and polyacrylamide. Their micro structure was characterized by transmission electron microscopy, Fourier transform infrared, and automatic X‐ray diffraction, their properties were investigated using optical contact angle and dielectric constant, and their electric responses were studied indirectly by dynamic viscoelasticity analyzer. The results showed that BaTiO₃ cores remained in cubic, the surface hydrophilic of the particles changed as follows: BaTiO₃ > BaTiO₃/PI > BaTiO₃/PAM > BaTiO₃/Chitosan > BaTiO₃/PAA > BaTiO₃/PS, and the dielectric constants of the particles varied with the order of that BaTiO₃ > BaTiO₃/PI > BaTiO₃/PAM > BaTiO₃/Chitosan > BaTiO₃/PAA > BaTiO₃/PS. Eventually, the particles' electric response activities exhibited the order of BaTiO₃/PI > BaTiO₃/PAM > BaTiO₃/Chitosan > BaTiO₃/PAA > BaTiO₃/PS > BaTiO₃. Furthermore, the electric response of the particles showed a chief dependence on polymer‐coating, surface hydrophilic, and dielectric constant. As a result, BaTiO₃ particles' electric response was much enhanced by polymer‐coating, and their compatibility to aqueous continuous phase was ameliorated. For the BaTiO₃/polymer particles, fine surface hydrophile and high dielectric constant dominated the strong response to electric field. Ultimately, BaTiO₃/PI and BaTiO₃/PAM particles possessed the strongest electric response in the five composite particles. The conclusion suggests an effective approach to prepare excellent hydrous electrorheological elastomers. POLYM. COMPOS., 34:897–903, 2013. © 2013 Society of Plastics Engineers     

Stability of Aqueous Barium Titanate Suspensions for MLCC Inkjet Printing

BaTiO₃‐based materials are currently used for the fabrication of multilayer ceramic capacitors (MLCC) because of their high dielectric properties. The inkjet printing (IJP) process can be used to fabricate MLCC of complex configurations by integrating internal electrodes and dielectric layers in a single step using a multi printing‐head system. Stabilized aqueous suspensions of BaTiO₃‐based powders are required to obtain dielectric inks adapted to IJP. This study investigates the influence of BaTiO₃ powder hydrolysis in water on the surface chemistry and stability in relationship with the milling step used to adjust the powder grain size to IJP. Optimum parameters for a good stability of BaTiO₃ suspensions are identified. The selected dispersant is a polyacrylate (PAA) for which the content is adjusted to minimize the sedimentation rates as required by IJP. Moreover, the addition of ethylene glycol is shown to be necessary to avoid the formation of a gel structure which could result from the interaction of borates ions leached from the surface of BaTiO₃ with the PAA dispersant. A mechanism of gel formation is proposed.     

Fabrication of BaTiO3-PTFE composite film for embedded capacitor employing aerosol deposition

The potential for using aerosol deposition (AD) as an alternative fabrication method to the conventional polymer composite process for embedded capacitors was examined. In order to achieve a high relative dielectric permittivity, BaTiO₃-polytetrafluoroethylene (PTFE) composite thick films were attempted by AD at room temperature. For the high dielectric constant, the BaTiO₃-PTFE composite films grown by AD should satisfied the following two critical conditions: a reduced decrement in ceramic particle size and a relieved distortion of the crystal structure. However, the relative permitivity of the composite films was too low compared with that of the BaTiO₃ films grown by AD. By predicting the dielectric constant in several composite models using the Hashin-Shtrikman bounds theory and 3-dimenstional (3-D) electrostatic simulation, we confirmed that the connectivity between ceramic particles is a highly critical factor for achieving a high dielectric constant in composite films.     

Grain size engineered high-performance nanograined BaTiO3-based ceramics: Experimental and numerical prediction

The ultra-thin multilayer ceramic capacitors (MLCCs) with layer thickness less than 1 μm or even 0.5 μm are in urgent demand due to the rapid development of modern electronic industries. Notably, the dielectric and ferroelectric properties of nanograined BaTiO₃-based ceramics, which are widely used as dielectric materials in MLCCs, are highly related to grain size. In this work, nanograined BaTiO₃-based ceramics with various grain sizes (50-100 nm) were prepared via the chemical coating method. The grain size effect on the dielectric and energy storage properties were systematically investigated. TEM and EDS images demonstrate that the typical core-shell structure is obtained inside ceramic grains even if the grain size is reduced to 50 nm. The fine-grain ceramic displays a lower maximal polarization but a higher breakdown strength, which ascribes to its weaker ferroelectric contribution and higher grain boundary ratio, respectively. As a result, it is confirmed that there exists an optimal grain size around 70 nm where maximum discharge energy density is achieved under the synergy effect of breakdown strength and polarization, which is also verified by a finite element analysis based on a modified hyperbolic tangent model. All these features provide important guidance towards the design of ultra-thin layer MLCCs by optimizing the dielectric properties and energy storage performance while pursuing miniaturization.     

The role of diffusion behavior on the formation and evolution of the core-shell structure in BaTiO3-based ceramics

In this work, the influence of starting particle size and sintering conditions on the microstructures and dielectric properties of BaTiO₃-based ceramics coated with 0.3Bi(Zn_1/2Ti_1/2)O₃-0.7BaTiO₃ were investigated to reveal the core-shell structure by using high resolution transmission electron microscopy technique coupled with energy-dispersive spectrometer analysis. The ion-diffusion behavior plays a critical role in the formation and evolution of the core-shell structure and, therefore, significantly influences the dielectric properties. When using starting powders containing BaTiO₃ particles larger than 100 nm in size and sintering for shorter dwelling times (0.5-2.0 hours), a core-shell structure could be formed and retained owing to the limited diffusion behavior, enabling BaTiO₃-based ceramics to meet the X8R specification for multilayer ceramic capacitors applications at high temperatures. However, when using 80 nm BaTiO₃ nanopowders and further extending the dwelling time to 6.0 hours, more driving energy was provided to prompt ion diffusion, which led to the compositional inhomogeneity becoming homogenized.     

Shrinkage behavior and interfacial diffusion in Ni-based internal electrodes with BaTiO3 additive

The effects of particle size of starting materials and amount of a BaTiO₃ additive on the shrinkage behavior and elemental diffusion in Ni-based internal electrodes have been investigated in order to control the shrinkage of the internal electrode in multilayer ceramic capacitors (MLCCs). Two kinds of Ni and BaTiO₃ powders were used with different particle sizes. Volume shrinkage over the range of 700–1300 °C at 150 °C intervals and linear shrinkage during sintering were measured for starting materials and composites in a reducing atmosphere. The interfaces of Ni/BaTiO₃ composites with 90:10 and 70:30 volume ratios, respectively, were investigated using TEM. Composites with bimodal Ni powder show less shrinkage than those with monomodal Ni powder, showing less shrinkage in monolith Ni of bimodal particle size. The shrinkage behavior is changed during sintering with increasing amounts of BaTiO₃ additives in both Ni-based composites. The particle size of the BaTiO₃ additive affects the shrinkage behavior of composites, without the additional amount affecting the final shrinkage. A reaction layer of about 300 nm wide is observed at the interface between the Ni and BaTiO₃ powders in composites, in which elemental Ni diffuses into the BaTiO₃ without counterdiffusion.     

High permittivity nanocomposites fabricated from electrospun polyimide/BaTiO3 hybrid nanofibers

High dielectric permittivity, good mechanical properties, and excellent thermal stability are highly desired for the dielectric materials used in the embedded capacitors and energy‐storage devices. This study reports polyimide (PI)/barium titanate (BaTiO₃) nanocomposites fabricated from electrospun PI/BaTiO₃ hybrid nanofibers. The PI/BaTiO₃ nanocomposites were investigated using Fourier transform infrared spectroscopy, scanning electron microscope, transmission electron microscope, thermal gravimetric analysis, an electromechanical testing machine, a LCR meter and an electric breakdown strength tester. The results showed that BaTiO₃ fillers were uniformly dispersed up to 50 vol% in PI matrix. The dielectric permittivity of the composite (50 vol% BaTiO₃) was 29.66 with a dielectric loss of 0.009 at 1 kHz and room temperature. The dielectric permittivity showed a very small dependence on temperature (up to 150°C) and frequency (100 Hz–100 kHz). The nanocomposites also showed high thermal stability and good mechanical properties. The PI/BaTiO₃ nanocomposites will be a promising candidate for uses in embedded capacitors, especially in high temperature circumstance. POLYM. COMPOS., 37:794–801, 2016. © 2014 Society of Plastics Engineers     

Enhanced dielectric permittivity of BaTiO3/epoxy resin composites by particle alignment

Barium titanate (BaTiO₃)/epoxy resin composites with a novel structure, in which the BaTiO₃ particles were directionally aligned in the epoxy resin matrix, were fabricated using the ice-templating method. The effects of the filler particle alignment and the filler fraction on the dielectric permittivity as well as the dielectric loss of the composites were studied. The results show that the aligning filler particles can significantly improve the dielectric permittivity while maintaining the dielectric loss compared with the traditional composite structure (homogeneously distributed). Due to the feasibility of the enhancement of the dielectric properties of the composites, the particle alignment that is achieved via the ice-templating method can be used in the field of high energy density capacitors.     

The influence of concentration on the formation of BaTiO3 by direct reaction of TiCl4 with Ba(OH)2 in aqueous solution

The formation of fine BaTiO₃ particles by reaction between liquid TiCl₄ and Ba(OH)₂ in aqueous solution at 85 °C and pH⩾13 has been studied for 0.062⩽[Ba²⁺]⩽0.51 mol l⁻¹. The concentration of Ba²⁺ ions has a strong influence on reaction kinetics, particle size and crystallite size. When [Ba²⁺]>≈0.12 mol l⁻¹, the precipitate consists of nanosized (≈30 nm) to submicron (100–300 nm) particles of crystalline BaTiO₃. At lower concentrations, the final product is a mixture of crystalline BaTiO₃ and a Ti-rich amorphous phase even for very long reaction times. A two-steps precipitation mechanism is proposed. Initially, a Ti-rich amorphous precipitate is rapidly produced. Reaction between the amorphous phase and the Ba²⁺ ions left in solution then leads to crystallisation of BaTiO₃. In addition to nucleation and growth of nanocrystals, the final size and morphology of BaTiO₃ particles obtained at low concentration can be determined by aggregation of nanocrystals and heterogeneous nucleation on existing crystal surfaces.     

Characteristics of Ag-doped BaTiO3 nanopowders prepared by spray pyrolysis

Pure and Ag-doped BaTiO₃ nanopowders were prepared by spray pyrolysis. Precursor powders, prepared from a spray solution with citric acid and ethylenediaminetetraacetic acid (EDTA) as chelating agents, had large, hollow particles irrespective of Ag doping. Both pure and Ag-doped powders had partially aggregated particles after post-treatment at 900 °C that could be easily milled to nanoparticles. The mean sizes of the pure and Ag-doped BaTiO₃ particles were 75 and 91 nm, respectively. The Ag-doped particles were mainly of cubic BaTiO₃ crystal structure, with small Ag phases observed. High-density BaTiO₃ pellets were formed by sintering the powders at the low temperature of 1000 °C. The silver was uniformly distributed in a tetragonal BaTiO₃ phase without phase separation in the doped pellet. The dielectric constants of the pellets formed from the pure and Ag-doped BaTiO₃ powders were 1826 and 2400, respectively.