Effects of Excess Bi2O3 on the Ferroelectric Behavior of Nd-Doped Bi4Ti3O12 Thin Films

Effects of excess Bi₂O₃ content on formation of (Bi_3.15Nd_0.85)Ti₃O₁₂ (BNT) films deposited by RF sputtering were investigated. The microstructures and electrical properties of BNT thin films are strongly dependent on the excess Bi₂O₃ content and post-sputtering annealing temperature, as examined by XRD, SEM, and P – E hysteresis loops. A small amount of excess bismuth improves the crystallinity and therefore polarization of BNT films, while too much excess bismuth leads to a reduction in polarization and an increase in coercive field. P – E loops of well-established squareness were observed for the BNT films derived from a moderate amount of Bi₂O₃ excess (5 mol%), where a remanent polarization 2P _r of 25.2 μC/cm² and 2E _c of 161.5 kV/cm were shown. A similar change in dielectric constant with increasing excess Bi₂O₃ content was also observed, with the highest dielectric constant of 304.1 being measured for the BNT film derived from 5 mol% excess Bi₂O₃.     

Extended Defects in ZnO Ceramics Containing Bi4Ti3O12 Additive

Extended defects in ZnO ceramics containing, 6 wt% Bi₄Ti₃O₁₂ were studied by analytical electron microscopy. Apart from basal plane condensation stacking faults, which are also present in as-received ZnO, extended defects related to the presence of Bi₄Ti₃O₁₂ were observed. In samples sintered at 900°C they lie in the basal or in the prismatic     planes and they quite often form closed loops, whereas they form serpentine-shaped boundaries in samples sintered at 1200°C. Evidence is given that they are inversion boundaries. Their TEM image characteristics, as well as the unambiguous presence of Ti at the boundaries, suggest that they are formed due to the presence of 2-D coherent precipitates of Ti-rich (possibly Zn₂TiO₄-type spinel) phase.     

Bi4Ti3O12 Ceramics from Powders Prepared by Alternative Routes: Wet No-Coprecipitation Chemistry and Mechanochemical Activation

The processing of ferroelectric Bi₄Ti₃O₁₂ ceramics from powders prepared by wet no-coprecipitation chemistry (WNCC) and mechanochemical activation (MCA) has been investigated. Dense ceramics were obtained at sintering temperatures as low as 900°C. Exaggerated grain growth was observed for samples from WNCC, but not for those from MCA. Dielectric properties are discussed in relation to the type and concentration of defects, which is smaller for ceramic samples from WNCC. The activation energy of the dielectric relaxation for ceramics from MCA suggests that additional V _O^•• are present at the pseudoperovskite [Bi₂Ti₃O₁₀]²⁻ block in this case.     

Factors Affecting the Electrical Conductivity of Donor-Doped Bi4Ti3O12 Piezoelectric Ceramics

High-temperature piezoelectric ceramics based on W⁶⁺-doped Bi₄Ti₃O₁₂ (W-BIT) were prepared by both the conventional mixing oxides and the chemical coprecipitation methods. Sintering was carried out between 800° and 1150°C in air. A rapid densification, >99% of the theoretical density (rho_th) at 900°C/2 h, took place in the chemically prepared W⁶⁺-doped Bi₄Ti₃O₁₂ ceramics, whereas conventionally prepared BIT-based materials achieved a lower maximum density, ∼94% of rho_th, at higher temperature (1050°C). The microstructure study revealed a platelike morphology in both materials. Platelike grains were larger in the conventionally prepared W-BIT-based materials. The sintering behavior could be related both to the agglomeration state of the calcined powders and to the enlargement of the platelets at high temperature. The W⁶⁺-doped BIT materials showed an electrical conductivity value 2-3 orders of magnitude lower than undoped samples. The electrical conductivity increased exponentially with the aspect ratio of the platelike grains. The addition of excess TiO₂ produced a further decrease of the electrical conductivity.     

Control of Functional Microstructure in WO3-Doped Bi4Ti3O12 Ceramics

Bi₄Ti₃O₁₂ (BIT) coprecipitated powders sinter in the presence of a transitory liquid phase, which strongly enhances the diffusion of matter and also the anisotropic growth of BIT grains. However, by coating the surface of BIT particles with WO₃ the aspect ratio of the platelets can be controlled. This, in addition to the donor effect of tungsten, finally leads to a decrease of the electrical conductivity of these ferroelectric ceramics.     

Nd/V Co-Doped Bi4Ti3O12 Powder Prepared By Molten Salt Synthesis

Powders of Nd/V-doped Bi₄Ti₃O₁₂ with a composition Bi_3.74Nd_0.26Ti_2.98V_0.02O_12.01 (BNTV), prepared by the molten salt synthesis, using chlorides as the fluxes, were successfully obtained. The influences of the molar ratio of KCl to NaCl, temperature, and soak time on the formation and morphology of BNTV were investigated. The results indicated that Na⁺ can enter the lattice of Bi₄Ti₃O₁₂ (BIT), leading to a decrease in the cell dimensions of BIT phase. The grain size and morphology of BNTV powders were considerably affected by the molar ratio of KCl to NaCl in the fluxes, in which the platelets showed the morphology of a rectangle and no regular shape in KCl and NaCl fluxes, respectively. The grain size of BNTV increased with increasing amount of NaCl in the fluxes, but the thickness decreased. The platelets prepared in the NaCl flux were faceted along (0 0 1) plane.     

Preferred Orientation of Bi4Ti3O12 Thick Film

The preferred orientation of thick films prepared by paste printing is rarely observed because of their bulky polycrystalline nature. We found that a Bi₄Ti₃O₁₂ thick film with a thickness of ca. 20 μm showed c -axis-preferred orientation. Initially, the texture of the screen-printed film was found to have a random orientation, which was attributed to the equiaxed particle shape of the raw powder synthesized by the co-precipitation method. During subsequent heating, c -axis orientation emerged in which the degree of orientation was proportional to the film density. Analysis of the orientation distribution revealed that the progress of texturing was attributed to the film deformation, indicating that anisotropic shrinkage and morphological changes in particles during heating influenced the preferred orientation.     

Ferroelectric Thin Films of Bismuth-Containing Layered Perovskites: Part I, Bi4Ti3O12

Ferroelectric thin films of bismuth-containing layered perovskite Bi₄Ti₃O₁₂ have been fabricated by a metalorganic decomposition (MOD) method. Crack-free and crystalline films of ∼5000 Å thickness have been deposited on Pt/Ti/SiO₂/Si substrates. Different heat treatments have been studied to investigate the nucleation and growth of perovskite Bi₄Ti₃O₁₂ crystallites. If the same composition and final annealing temperature are used, films with different orientations are obtained by different heating schedules. These films show a large anisotropy in ferroelectric properties. Theoretical considerations are presented to suggest that nucleation control is responsible for texture and grain-size evolution. Moreover, the origin of the ferroelectric anisotropy is rooted in the two-dimensional nature of layered polarization.     

Preparation of Grain-Oriented Sr0.5Ba0.5Nb2O6 Ferroelectric Ceramics by Magnetic Alignment

The properties of polycrystalline ceramics are strongly influenced by their crystallographic texture. In this study, highly grain-oriented tungsten bronze structure ferroelectric ceramics, Sr_0.5Ba_0.5Nb₂O₆, were successfully fabricated by magnetic alignment and gelcasting techniques using only the conventional solid-state-synthesized starting powder. Spherical Sr_0.5Ba_0.5Nb₂O₆ particles were aligned according to their anisotropic magnetic property in 40 vol% slurry in a 10 T magnetic field, and then in situ locked by polymerization via a gelcasting technique for 30 min. A 〈00 l 〉-axis orientation perpendicular to the magnetic field direction ( B ) was obviously observed in the green compact and sintered sample. The sintered Sr_0.5Ba_0.5Nb₂O₆ sample contained equiaxial grains and reached 98% theoretical density. Compared with the sample with randomly oriented grains, the magnetically aligned sample showed an enhanced with dielectric constant in the ⊥ B direction (1100 versus 750 at room temperature and 4300 versus 2800 at Curie temperature). This new method is readily applicable to other ceramics with tungsten bronze structure, and is expected to facilitate mass preparation of large and dense grain-oriented ceramic materials.     

Electrical Properties of Superlattice-Structured Bi4Ti3O12–PbBi4Ti4O15 Single Crystals

Single crystals of superlattice-structured ferroelectrics composed of Bi₄Ti₃O₁₂ and PbBi₄Ti₄O₁₅ were grown and the properties of polarization hysteresis and leakage current along the a -axis were investigated. Oxidation treatment led to a marked increase in leakage current at room temperature, showing that electron hole acts as a detrimental carrier for electrical conduction. A well-developed polarization hysteresis with a remanent polarization of 41 μC/cm² was observed, which is suggested to originate from the peculiar ferroelectric displacement of Bi in the Bi₂O₂ layers.     

Decomposition Reactions in CaCu3Ti4O12 Ceramics

CaCu₃Ti₄O₁₂ (CCTO) ceramics sintered in air at 1115°C for 3 and 24 h have been heat treated in N₂ at 1000°C. Surface layers develop on the outer regions of the ceramics, and a combination of X-ray diffraction and analytical electron microscopy has been used to establish the phase content of the layers. A model to explain the formation of the surface layers is proposed based on decomposition of CCTO into a mixture of CaTiO₃, TiO₂, and Cu₂O. The role of limited decomposition in the development of electrically inhomogeneous CCTO ceramics prepared at elevated temperatures in air is discussed.     

Dielectric and Ferroelectric Properties of Nanocrystalline Bi2Ti2O7 Prepared by a Metallorganic Decomposition Method

Nanopowders of Bi₂Ti₂O₇ were synthesized by a metallorganic decomposition (MOD) technique. Pure Bi₂Ti₂O₇ nanocrystals formed after annealing at 550°C for 5 min. X-ray patterns show that Bi₂₀TiO₃₂ is a metastable phase during Bi₂Ti₂O₇ formation. It was found that there were two peaks in the curves of the dielectric response as a function of temperature for pressed nanocrystalline Bi₂Ti₂O₇ samples. The Curie temperature decreases with decrease of grain size whereas the ferroelectric-ferroelectric phase transition temperature increases. The hysteresis loops observed also suggest that Bi₂Ti₂O₇ might belong to a ferroelectric material.     

Lead-Free SrBi4Ti4O15 and Bi4Ti3O12 Material Fabrication Using the Microwave-Assisted Molten Salt Synthesis Method

In this paper, the microwave-assisted molten salt method (MAMSS) and molten salt method (MSS) were used to synthesize SrBi₄Ti₄O₁₅ (SBT). The phase constitution was determined by powder X-ray diffraction and the microstructure of powder was examined by scanning electron microscopy. In contrast to the conventional MSS method, MAMSS produces more distinct plate-like grains and synthesizes both SBT and Bi₄Ti₃O₁₂ (BTO) at 600°C with a 30-min soaking time. The increase of temperature and soaking time can make the plate-like grains of BTO more distinct.     

Electric and Dielectric Properties of Nb-Doped CaCu3Ti4O12 Ceramics

Pure and Nb-substituted CaCu₃Ti_{4− x} Nb _x O_{12+ x /2} (CCTO, x =0, 0.02, 0.1, 0.2, 0.4) ceramics were prepared by a conventional solid-state sintering, and their electric and dielectric properties were investigated using an impedance analyzer. A single-phase CCTO was obtained up to x =0.2 Nb substitution and the lattice parameter increased with Nb substitution concentration. While the grain size decreased with Nb substitution, the resistivity of the grain boundary decreased. The dielectric constant increased with Nb substitution, and the highest value of ∼420 000 was observed in the x =0.2 Nb-substituted specimen at 10 kHz. The obtained electric and dielectric properties in Nb-substituted CCTO were discussed in terms of the internal barrier layer capacitor model, particularly focusing on a ratio of thickness of the grain boundary region to grain size.     

Grain-Oriented PbNb2O6 Ceramics

Grain-oriented ceramics of ferroelectric lead metaniobate have been prepared by molten salt synthesis of anisotropic crystallites followed by doctor blade casting. The sintered ceramics have an orthorhombic texture with elongated c axis grains parallel to the casting direction. This allows efficient poling in directions perpendicular to the tape.     

Preparation of Bi4Ti3O12 Powders in the Presence of Molten Salt Containing LiCl

The reaction between Bi₂O₃ and TiO₂ in molten LiCl-KCl was examined with special emphasis on the reaction mechanism and the size of Bi₄Ti₃O₁₂ particles. The oxides reacted with LiCl to form an intermediate compound, which changed into Bi₄Ti₃O₁₂ on extended heating. Potassium chloride retarded the reaction between the oxides and LiCl and promoted the change from the intermediate compound to Bi₄Ti₃O₁₂. Bi₄Ti₃O₁₂ particles prepared in the flux were platelike, irrespective of the preparation conditions, but their size depended on reaction temperature and time, the ratio of LiCl to KCl, and the amount of flux.     

Grain Growth-Controlled Giant Permittivity in Soft Chemistry CaCu3Ti4O12 Ceramics

We report a dielectric constant of up to 5.4 × 10⁵ at room temperature and 1 kHz for CaCu₃Ti₄O₁₂ (CCTO) ceramics, derived from multiphase powders (coprecipitation products), made by a "chimie douce" (coprecipitation) method, and then sintered in air. The sintered products are pure-phase CCTO ceramics. The high dielectric constant is achieved by tuning the size of grains and the thickness of grain boundaries. The grain growth is controlled by varying the concentration of excess CuO in the initial powder (calcined coprecipitation products) between 1 and 3.1 wt%. The dielectric constant of pure CCTO ceramics increases with the initial CuO concentration, reaching its maximum at 2.4 wt% of CuO. A further increase of excess CuO in powders results in a permittivity decrease, accompanied by the formation of CuO as a separate phase in the sintered products. The unusual grain growth behavior is attributed to a eutectic reaction between CuO and TiO₂ present in the initial powder.     

Laser Sintering of Bismuth Germanate (Bi4Ge3O12) Ceramics

A solid-state route to synthesize bismuth germanate (Bi₄Ge₃O₁₂, or BGO) ceramics, and the optimum conditions for the laser sintering of these ceramics, were investigated. Special emphasis was placed on the influence of laser power and irradiation time on densification and microstructure evolution. The procedure that was used involved preheating the samples and a laser-irradiation program, which resulted in sintered, crack-free BGO ceramics with good pore shrinkage and a relative density of 95% (±3%).     

Fabrication of Grain-Oriented Bi2WO6 Ceramics

Grain-oriented Bi₂WO₆ ceramics were fabricated by normal sintering techniques. Platelike crystallites were initially synthesized by a fused salt process using an NaCl-KCI melt. When calcined at <800°C, the Bi₂WO₆ crystallites are 3∼5 μ m in size and, at >850°C, =100 μm. After dissolving away the salt matrix, the Bi₂WO₆ particles were mixed with an organic binder and tapecast to align the platelike crystallites. Large particles were easily oriented by tapecasting but the sinterability of the tape was poor. Preferred orientation of small particles was increased by tapecasting and grain growth during sintering further improves the degree of orientation. Sintering above the 950°C phase transition, however, results in discontinuous grain growth and low densities. Optimum conditions for obtaining highly oriented ceramics with high density occur at sintering temperatures of 900°C using fine-grained powders which yield orientation factors of =0.88 and densities of 94% theoretical.     

Structure, Properties, and Impedance Spectroscopy of CaCu3Ti4O12 Ceramics Prepared by Sol–Gel Process

CaCu₃Ti₄O₁₂ (CCTO) ceramics with high dielectric constant (2–4 × 10⁴) and low loss (0.04) were prepared by the sol–gel process and sintered at 1050°C for different times. The sintering time has a sensitive influence on the values of the dielectric constant and nonlinear coefficient. Tailored dielectric constant and nonlinear coefficient can be obtained by selecting a suitable sintering time according to different desired device application. The result of current–voltage characteristics and Cole–Cole plots in a broad temperature range (60–400 K) provide more effective evidence of the high dielectric constant supported by the grain boundary barrier layer (GBBL) capacitors model. Below 150 K, the GBBL capacitors effect weakens and gradually disappears with further decrease of temperature, thus leading the dielectric constant to decrease rapidly. Two values of grain activation energy acting at different temperature for each sample were obtained.