Grain-Boundary Migration and Dielectric Properties of Semiconducting SrTiO3 in the SrTiO3-BaTiO3-CaTiO3 System

Chemically induced grain-boundary migration and its effects on the interface and dielectric properties of semiconducting SrTiO₃ have been investigated. Strontium titanate specimens that had been doped with 0.2 mol% of Nb₂O₅ were sintered in 5H₂/95N₂. The sintered specimens were diffusion annealed at 1400°C in 5H₂/95N₂ with BaTiO₃ or 0.5BaTiO₃-0.5CaTiO₃ (mole fraction) packing powder. The grain boundaries of the annealed specimens were oxidized in air. In the case of BaTiO₃ packing, grain-boundary migration occurred with the diffusion of BaTiO₃ along the grain boundary. The effective dielectric constant of the specimen decreased gradually as the temperature increased but showed two peaks, possibly because of barium enrichment at the grain boundary and an oxidized Sr(Ba)TiO₃ layer. In the case of 0.5BaTiO₃-0.5CaTiO₃ packing, although barium and calcium were present at the grain boundary of the specimen, no boundary migration occurred, as in a previous investigation. With the diffusion of barium and calcium, the resistivity of the specimen increased and the variation of the effective dielectric constant with temperature was much reduced, in comparison to those without solute diffusion. These enhanced properties were attributed to the solute enrichment and the formation of a thin diffusional Sr(Ba,Ca)TiO₃ layer at the grain boundary.     

Effect of Ba6Ti17O40/BaTiO3 Interface Structure on {111} Twin Formation and Abnormal Grain Growth in BaTiO3

A structural transition of Ba₆Ti₁₇O₄₀/BaTiO₃ interfaces from faceted to rough was induced by reducing oxygen partial pressure in the atmosphere. As the oxygen partial pressure decreased, the number densities of {111} twins and abnormal grain decreased. TEM observation showed that the twin formation was governed only by the faceting of the interface. Experimental evidence of {111} twin-assisted abnormal growth of faceted BaTiO₃ grains was also obtained.     

Dependence of Grain Growth and Grain-Boundary Structure on the Ba/Ti Ratio in BaTiO3

The grain-growth behavior and grain-boundary structure in titanium-excess BaTiO₃ depend on the amount of excess titanium at 1250° and 1300°3C. With excess titanium, abnormal grain growth (AGG) occurs and the grain boundaries are mostly flat or faceted with hill-and-valley shapes. With 0.5 at.% excess titanium, the large grains have flat {111} faces forming singular grain boundaries parallel to {111} double twins. With excess-titanium content between 0.1 and 0.3 at.%, the abnormal grains appear to have polyhedral shapes with {100} faces. These flat or faceted grain boundaries are expected to have singular structures, and hence AGG can occur by the step growth mechanism. When the excess-titanium content is decreased to 0, the grain boundaries become curved, indicating a rough atomic structure, and normal grain growth occurs.     

Grain Growth Control and Dopant Distribution in ZnO-Doped BaTiO3

ZnO additions to BaTiO₃ have been studied in order to determine the role of this dopant on sintering and microstructure development. As a consequence of a better initial dopant distribution, samples doped with 0.1 wt% zinc stearate show homogeneous fine-grained microstructure, while a doping level of 0.5 wt% solid ZnO is necessary to reach the same effect. When solid ZnO is used as the dopant precursor, ZnO is redistributed among the BaTiO₃ particles during heating. Since no liquid formation has been detected for temperatures below 1400°C in the system BaTiO₃-ZnO, it is proposed that dopant redistribution takes place by vapor-phase transport and grain boundary diffusion. Shrinkage and porosimetry measurements have shown that grain growth is inhibited during the first step of sintering for the doped samples. STEM-EDX analysis revealed that solid solubility of ZnO into the BaTiO₃ lattice is very low, being strongly segregated at the grain boundaries. Grain growth control is attributed to a decrease in grain boundary mobility due to solute drag. Because of its effectiveness in controlling grain growth, ZnO appears to be an attractive additive for BaTiO₃ dielectrics.     

Grain Boundary Migration in Cubic Zirconia–Yttria Induced by Addition of Magnesia at Varying Concentrations

When partially sintered cubic ZrO₂–10 mol% Y₂O₃ specimens are heat-treated at 1500°C with powder mixtures of MgO and ZrO₂–10Y₂O₃ at varying ratios, the grain boundaries migrate, leaving behind new solid solutions enriched with MgO but depleted of Y₂O₃. With increasing MgO content in the solute source powder, the average migration velocity increases, and the MgO content increases and the Y₂O₃ content decreases slightly in these new solid solutions. With increasing MgO content in the solute source, the grain boundaries tend to be corrugated and faceted. Migration reversal is also observed at the corrugated boundaries. These variations of the grain boundary migration behavior with the MgO content in the solute source are consistent with the diffusional coherency strain energy as the driving force for the migration.     

Effect of Grain Size on Diffusion-Induced Grain-Boundary Migration in Ba(Zn1/3Nb2/3)O3 Ceramics

Diffusion-induced grain-boundary migration (DIGM) in Ba(Zn_1/3Nb_2/3)O₃ (BZN) ceramics was investigated with small (3.0 μm) and large (31. 4 μm) grain size specimens. The specimens were embedded in Nb₂O₅ or ZnO powders and then heat-treated at 1250° and 1310°C, respectively. The grain boundaries of the small grain size specimens were immobile, while those of the large grain size specimens migrated away from their centers of curvature. From the observed difference in migration behavior depending on grain size, the magnitude of the driving force for the DIGM was estimated.     

Discontinuous Dissolution of a Liquid Phase in Ba(Ni1/3Nb2/3)O3 Ceramics

Discontinuous dissolution of a liquid phase accompanied by diffusion-induced grain-boundary migration (DIGM) in Ba(Ni_1/3Nb_2/3)O₃ (BNN) ceramics has been studied. When the liquid-phase-sintered BNN specimens are heat-treated at low temperatures, the liquid phase formed during sintering is dissolved discontinuously and during the reaction grain boundaries migrate. As the heat-treatment temperature is lowered, the degree of grain boundary migration and dissolution of the liquid phase increase. These results are qualitatively consistent with the coherency strain energy model proposed for the driving force for DIGM.     

Effect of PO2 on Bulk and Grain Boundary Resistance of n-Type BaTiO3 at Cryogenic Temperatures

Complex impedance analysis at cryogenic temperatures has revealed that the bulk and grain boundary properties of BaTiO₃ polycrystals are very sensitive to the oxygen partial pressure during sintering. Polycrystals sintered at P _O2 as low as 10⁻¹⁵ atm were already electrically heterogeneous. The activation energy of the bulk conductivity in the rhombohedral phase was found to be close to that of the reduced undoped single crystal (i.e., 0.093 eV). The activation energy of the grain boundary conductivity increases with the temperature of the postsinter oxidation treatment from 0.064 to 0.113 eV. Analysis of polycrystalline BaTiO₃ sintered in reducing atmosphere and then annealed at P _O2= 0.2 atm has shown that the onset of the PTCR effect occurs at much higher temperatures than expected in the framework of the oxygen chemisorption model. The EPR intensity of barium and titanium vacancies increases after oxidation at T > 1000°C. A substantial PTCR effect is achieved only after prolonged annealing of the ceramic in air at temperatures as high as 1200–1250°C. This result suggests that the PTCR effect in polycrystalline BaTiO₃ is associated with interfacial segregation of cation vacancies during oxidation of the grain boundaries.     

Direct Examinations of PTC Action of Single Grain Boundaries in Semiconducting BaTiO3 Ceramics

R-T and I-V characteristics of single grains and grain boundaries in large-grained BaTiO₃ PTC ceramics were studied with a two-probe technique using a micromanipulator and fine Al wire. The PTC originates in the grain boundary only and behaves differently in each boundary. Even below T_c , the ceramic resistance depends almost entirely on the boundary. I-V characteristics in the boundary follow Ohm's law and conduction by a space-charge-limited current with a trap, using different applied voltages. The PTC anomaly relates to activation of the trap in the boundary, not to barrier height. A band model in the intergranular layer, with dielectric BaTiO₃ and the trap, is proposed.     

Orientation and Grain Boundary Microstructure of Alumina in Al/Al2O3 Composites Produced by Reactive Metal Penetration

The orientation and grain boundary microstructure of alumina in reactive metal penetration Al/Al₂O₃ composites are studied using orientation imaging microscopy and the results are compared with those of sintered polycrystalline Al₂O₃. The interconnected Al₂O₃ in the composite material is separated by Σ3 boundaries (twins) with a 60° rotation around the [0001] direction. A high frequency (∼100%) of Σ3 coincidence boundaries in composite alumina is remarkable since only ∼12% of boundaries in a sintered polycrystalline Al₂O₃ are of special nature. The coincidence boundaries in the in situ alumina grow in a coherent and faceted manner.     

{111} Twin Formation and Abnormal Grain Growth in Barium Strontium Titanate

Two series of experiments were performed to study the experimental conditions for the formation of {111} twins and related microstructures in barium strontium titanate ((Ba, Sr)TiO₃). In the first series, the phase equilibria in the BaTiO₃–SrTiO₃–TiO₂ system were determined. XRD and WDS analysis, done in the BaTiO₃-rich region, of 45(Ba,Sr)TiO₃–10TiO₂ samples annealed at 1250°C for 200 h in air showed that (Ba,Sr)TiO₃ was in equilibrium with Ba₆Ti₁₇O₄₀ (B₆T₁₇) and Ba₄Ti₁₃O₃₀ phases with strontium solubility (Sr/(Ba + Sr)) of ∼0.02 and 0.20, respectively. In the second series the microstructures of samples consisting of a mixture of (Ba,Sr)TiO₃ and 2.0 mol% TiO₂, were observed after sintering at 1250°C for 100 h in air. {111} twins formed only in the samples with faceted B₆T₁₇ second phase particles, similar to the case of BaTiO₃. In these samples, abnormal grain growth occurred in the presence of the {111} twins. In contrast, no {111} twins formed and no abnormal grain growth occurred in the samples containing second phase particles other than B₆T₁₇. With an increased substitution of strontium for barium, the aspect ratio of abnormal grains containing {111} twin lamellae was reduced. This result was attributed to a reduction in the relative stability of the {111} planes with the strontium substitution.     

Grain Boundary Evolution in Hot-Pressed ABC-SiC

Silicon carbide with aluminum, boron, and carbon additions (ABC-SiC) was hot-pressed to full density. The samples were examined by transmission electron microscopy (TEM), with an emphasis on high-resolution electron microscopy (HREM). Amorphous grain boundary interlayers, typically less than 2 nm wide, were formed between SiC grains. Heat-treating the ABC-SiC at temperatures as low as 1100°C in Ar crystallized the grain boundary interlayers completely without significantly changing the dominant chemical constituents. Chemical microanalyses demonstrated Al and O enrichment for all examined grain boundaries in both as-prepared and annealed samples. Quantitative EDS analyses revealed Al₂OC- and Al₂O₃-related species (with Si, C, B, or S substitutions) as two of the most likely grain boundary interlayer materials, both before and after heat treatment. Al₂O₃, and (Al_{1− x} Si _x )₂OC with a 2H-type wurtzite structure, were identified as grain boundary films by HREM images. The structural evolution in the grain boundary phases during the hot pressing and postannealing is discussed.     

Effect of Sintering Atmosphere on Grain Boundary Segregation and Grain Growth in Niobium-Doped SrTiO3

To investigate the donor segregation in grain boundary regions and its effect on grain growth in SrTiO₃, SrTiO₃ powder compacts were doped with Nb₂O₅ and sintered in air or in hydrogen. The Nb-doped SrTiO₃ sintered in air did not show any detectable Nb segregation at the grain boundary region while an appreciable segregation was observed in the space-charge region of the sample sintered in H₂. The observed donor segregation in H₂ suggests a negative grain boundary charge and compensating positive space charge, which are the opposite to those in air. The negative grain boundary core was attributed to the segregation of inherently present acceptor impurities and the trapping of electrons at grain boundaries. In the H₂-sintered sample, where the added Nb ions were segregated in the space-charge region, the grain growth was suppressed. This result may indicate that the grain growth suppression in H₂ is due to the Nb solute drag of the boundary motion and the reduction in Ti vacancies.     

Grain Boundary Oxidation in PTCR Barium Titanate Thermistors

The phenomenon of grain boundary oxidation in PTCR BaTiO₃ thermistors is discussed. In particular, the energy spectra of the surface states were calculated for different samples, and these were related to the nominal composition, the impurity content of the base BaTiO₃ powder used, and the prevalent atmospheric conditions during cooling and/or annealing. It is proposed that the interaction of manganese with oxygen creates deep-lying traps, and, in general, some proof is offered that the majority of the surface states are due to different oxidizing chemisorbed gases. It is believed that the ability of a particular sample to adsorb such gases in adequate amounts, and thus exhibit an appreciable PTCR effect, is related to the presence of acceptor-type dopants perferentially segregated onto the grain surfaces. Notably, the role of 3 d transition metal cations in this process is discussed in some detail.     

Thermal Behavior of BaTiO3 Particles Synthesized by Plasma Chemical Vapor Deposition

The thermal behavior of nanoparticles BaTiO₃, prepared by a radio-frequency plasma chemical vapor deposition (RF-plasma CVD) method, was characterized by various analysis methods. The BaCO₃ phase was included in the powder as byproducts, which is also observed in hydrothermal BaTiO₃ powder. The BaCO₃ phase decomposed and disappeared by annealing at 873 K for 30 min. H₂O, N₂, CO₂ and H₂, were detected by a thermal desorption spectra measurement from BaTiO₃ powder. The annealed powder became well-crystallized particles without grain growth, although as-prepared powder included polycrystalline particles. We successfully observed in-situ grain growth for BaTiO₃ nanoparticles by thermal transmission electron microscope. At the initial step of normal grain growth, very fine particles with 40–60 nm diameters started to merge into the larger grains around 1083 K. The migration rate was measured by video images and a grain boundary diffusion coefficient D_gb was calculated.     

Discontinuous Dissolution of Iron Aluminate Spinel in the Al2O3–Fe2O3 System

When sintered 85Al₂O₃–15Fe₂O₃ (in wt%) specimens consisting of corundum grains and spinel particles were annealed at temperature where only a corundum phase was stable, phase transformation of spinel into metastable FeAIO₃ and subsequently complete dissolution of the metastable phase occurred together with the migration of grain boundaries at the surface of the specimens. Since the grain boundary migration was induced by grain boundary diffusion of Fe₂O₃ from the transforming and dissolving particles, the boundary migration by temperature decrease corresponds to a discontinuous dissolution of the spinel particles and a chemically induced grain boundary migration by temperature change. Inside the specimens, however, the transformation—dissolution and the grain boundary migration were suppressed because of unavailable accommodation of the volume expansion due to the transformation.     

Grain Orientation Dependence of the PTCR Effect in Niobium-Doped Barium Titanate

The positive temperature coefficient of resistivity (PTCR) effect is directly measured in single grain boundaries in 0.1-mol%-Nb-doped BaTiO₃ with 1 mm coarse grains. The PTCR effect largely depends on grain boundary structure. Random grain boundaries exhibit the PTCR effect as in polycrystalline samples, but the PTCR effect does not appear in highly coherent boundaries such as small-angle boundaries, twin boundaries, and coincidence site lattice (CSL) boundaries with low Σ values. For Σ= 3 boundaries, the resistance increase above the Curie temperature is a function of deviation angle. A small PTCR effect is observed in Σ= 3 boundaries with a deviation angle of about 9° in contrast with ideal Σ= 3 boundaries and boundaries with a deviation of about 4°.     

Grain Boundary Defect Chemistry of Acceptor-Doped Titanates: Space Charge Layer Width

The grain boundary space charge depletion layers in acceptor-doped SrTiO₃ and BaTiO₃ ceramics were investigated by impedance spectroscopy in the time and frequency domain. Based on the layer width and its dependence on the acceptor concentration, the temperature, and the oxygen partial pressure during annealing, a suggestion for a refined Schottky model is proposed. The local distribution of the donor-type grain boundary states causing the depletion layer and the resulting band bending are discussed.     

Structure–Property Relationship in BT-Based Dielectrics for Ni-MLCC: Modification of Grain Boundary

Structure–property relationship in BaTiO₃ (BT)-based dielectrics for multi-layer ceramic capacitors with nickel internal electrode was investigated using samples having various HoO_3/2 concentrations by measuring temperature characteristics of capacitance, voltage–current characteristics, lifetime at highly accelerated life test, high-resolution analytical electron microscope, and frequency response at elevated temperature and ultra-low frequency. It was concluded that the addition of Ho affected the shell and grain boundary (GB) characteristics. Incorporation of Ho into BT perovskite lattice and the change in GB characteristics along with the doped concentration of HoO_3/2 were discussed to better understand the role of doped Ho₂O₃.     

Effects of Grain Growth on the Distribution of Nb in BaTiO3 Ceramics

Measurements of Nb diffusion into large- and small-grained BaTiO₃ disks show a high ratio of grain boundary to bulk diffusivity. Well defined X-ray diffraction lines are found in Nb-doped BaTiO₃ only when significant grain growth occurs during sintering. When grain growth of a 0.65 μm grain size powder is limited at ∼1 μm, excess line broadening results. This is attributed to the simultaneous presence of Nb-free and Nb-rich regions. Because of its low bulk diffusivity little Nb penetrates into the original BaTiO₃ grain cores, and a solid solution forms only in the regions of recrystallization. When grain growth is limited, the "sintering reaction" results in a non-homogeneous system; when appreciable grain growth occurs, most of the original grain cores are eliminated and an essentially uniform system is obtained.