Formation of Potential Barrier Related to Grain-Boundary Character in Semiconducting Barium Titanate

Resistance–temperature ( R – T ) characteristics were measured directly at single-grain boundaries in 0.1-mol%-niobium-doped barium titanate bicrystals that had been fabricated from polycrystalline sinters, to determine a geometrical grain-boundary character dependence of the positive temperature coefficient of resistivity (PTCR) effect. Both random boundaries and low-Σ boundaries exhibit a similar grain-boundary character dependence of the PTCR effect through a simple geometrical analysis, using the coincidence of reciprocal lattice points. Differences of the R – T characteristics in individual boundaries have been explained in terms of the formation of a potential barrier that is associated with the oxidation of grain boundaries during cooling, after sintering or annealing. The grain-boundary character is likely to affect the diffusivity of O²⁻ ions and, hence, is crucial to the formation of the potential barrier.     

Positive Temperature Coefficient of Resistivity Effect in Highly Donor–Doped Barium Titanate

BaTiO₃ ceramics doped with different La concentrations (0–12 mol%) were prepared by sintering under the reducing conditions of a nitrogen atmosphere containing 1% hydrogen. The critical donor concentration that causes blocking of the exaggerated grain growth was observed to be ∼10 mol% La. The samples, which were semiconducting after sintering under reducing conditions, were subsequently reoxidized by annealing in air to induce the positive temperature coefficient of resistivity (PTCR) effect. After reoxidation at 1150°C a noticeable PTCR effect was observed in the samples doped with La concentrations as high as 2.5 mol%. The room-temperature resistivity after reoxidation was found to increase with increasing donor concentration due to an increase in the thickness of the insulating layers at the grain boundaries. TEM analysis showed that reoxidation of the samples caused precipitation of the Ti-rich compound Ba₆Ti₁₇O₄₀ inside the doped BaTiO₃-matrix grains.     

Grain-Boundary Chemistry of Barium Titanate and Strontium Titanate: II, Origin of Electrical Barriers in Positive-Temperature-Coefficient Thermistors

Scanning transmission electron microscopy (STEM) of positive-temperature-coefficient (PTC) BaTiO₃ thermistors shows that the grain-boundary oxygen content in as-received (oxidatively cooled) materials is slightly enriched compared to quenched samples, and the acceptor-rich space-charge present at high temperatures is retained upon cooling. The defect density of the space charge is approximately equal to the acceptor state density at PTC boundaries determined by electrical measurements. Accordingly, it is proposed that the electrical barrier forms when acceptor defects already segregated in the ionic space charge at high temperature become active interface states when compensating donor defects in the grain-boundary core are oxidized. These acceptor defects appear to be primarily barium vacancies, but need not form upon cooling in the manner proposed by Daniels and Wernicke. Acceptor solutes when present can also contribute to barrier formation through space-charge segregation; the increase in interface state density upon addition of Mn is consistent with the magnitude of the expected segregation.     

Positive Temperature Coefficient of Resistivity Effect in Undoped, Atmospherically Reduced Barium Titanate

A sharp positive temperature coefficient of resistivity effect for undoped, fluorinated BaTiO_3−x samples was observed. The qualitative agreement between the behavior of BaTiO_3−x and La-doped BaTiO₃, with respect to the trap density at the boundaries, suggests that in the absence of counterdopants such as Mn, the main origin of surface acceptor states is chemisorbed gases. Impedance analysis indicates that, under the conditions of the present work, fluorine seems not to diffuse in significant amounts into the lattice. The treatment of the fluorinated samples in inert/reducing atmospheres did not markedly decrease the resistivity jump, suggesting that fluorine might be chemisorbed more strongly than oxygen. The composition of two different liquid phases, produced by excess titania and silica additions, did not have an important effect on the resulting properties.     

Positive Temperature Coefficient of Resistance Effect in Heavily Niobium-Doped Barium Titanate by the Growth of the Double-Twinned Seeds

Positive temperature coefficient of resistivity (PTCR) was attained in heavily niobium-doped BaTiO₃ through the addition of BaTiO₃ seed particles. The seed particles containing a double twin grew during heat treatment, and a uniform microstructure composed of large, coarse grains was obtained. The incorporation of niobium into the grain via grain growth probably caused the semiconducting and PTCR character of the niobium-doped BaTiO₃.     

A Novel Method for the Uniform Incorporation of Grain-Boundary Layer Modifiers in Positive Temperature Coefficient of Resistivity Barium Titanate

The presently developed two-stage process involves diping the prefired porous disks of n -BaTiO₃ in nonaqueous solutions containing Al-buty rate, Ti-isopropoxide, and tetraethyl silicate and subsequent sintering. This leads to uniform distribution of the grain-boundary layer (GBL) modifiers (Al₂O₃+ TiO₂+ SiO₂) and better control of the grain size as well as the positive temperature coefficient of resistivity characteristics. The technique is particularly suited for GBL modifiers in low concentrations (< 1%).     

Positive Temperature Coefficient of Electrical Resistivity below 150 K in Barium Strontium Titanate

The resistivity of Ba_{(1– y )(1– x )}Sr _y (1– x )La _x TiO₃ceramics with x = 0.0025 and y = 0.25, 0.5, 0.75, and 0.9 was measured between 50 and 400 K. A resistivity anomaly corresponding to the positive temperature coefficient of electrical resistivity (PTCR) effect was observed for all compositions. The onset temperature decreased from 320 K ( y = 0.25) to 70 K ( y = 0.9). The extent of the PTCR effect was significantly enhanced for the strontium-rich composition and reached ∼8 orders of magnitude for y = 0.9. These results strongly suggested the possibility to fabricate PTCR devices based on (Sr,Ba)TiO₃ ceramics for application at cryogenic temperatures.     

Effects of Excess Barium Ions on Aqueous Barium Titanate Tape Properties

The effects of excess free barium ions in aqueous barium titanate slip on the resulting BaTiO₃ tape properties were investigated in terms of the slip behavior, green/sintered tape density and morphology, and dielectric properties. The excess free barium ions expressed by means of the Ba/Ti ratio adversely affected most tape properties. Increase in the slip viscosity, green porosity, and agglomeration along with a decrease in mechanical properties and green/sintered density were found with the increase in the Ba/Ti ratio. However, dielectric permittivity was increased with increase in the Ba/Ti ratio. An effort was made to correlate these phenomena with Ba²⁺ leaching in water for realistic multilayer ceramic capacitor applications.     

Preparation of Semiconducting Barium Titanate by Excimer Laser Irradiation

A drastic drop of the electrical resistivity was observed on a ferroelectric insulator BaTiO₃ surface, after KrFlaser irradiation in air at atmospheric pressure. The temperature dependence of the resistivity was employed to demonstrate semiconducting behavior. Such behavior was seen when the resistance was measured in nitrogen. When measured in air, the semiconducting layer was oxidized and the insulating behavior restored.     

Electrical Properties of PTCR Barium Titanate

When properly doped, barium titanate ceramics display positive temperature coefficient resistance (PTCR) behavior. This has been proved to be a Schottky barrier type of grain-boundary effect. However there has not yet been a complete point-to-point comparison between the experimental data and theory for the entire set of the material nonlinear dielectric properties. In this study, a methodology has been developed which allows the study of the depletion layer dielectric properties while the PTCR effect is being investigated. An equivalent dielectric constant, the value of which is to be determined from this experiment, is treated as an average of the dielectric properties of the depletion layer and is used to analyze the grain-boundary resistance and capacitance data based on a simple double-depletion-layer model. The theoretical relationship between this equivalent dielectric constant and the material dielectric properties is also explored in this study.     

Lead Titanate Ceramics with Positive Temperature Coefficients of Resistivity

Lead titanate ceramics were successfully made into semiconductors exhibiting anomalous positive temperature coefficients of resistivity (PTCR) about 3 orders of magnitude above the Curie point (480° to 490°C). The PTCR characteristics of the materials prepared were found to be unstable and to show a significant degradation in both room-temperature resistivity and magnitude of the PTCR effect with time. The instability of the PTCR characteristics observed in the present materials is considered to be related to the morphologies of their grain structures.     

Anomalous Grain Growth in Donor-Doped Barium Titanate with Excess Barium Oxide

Grain growth and semiconductivity of donor-doped BaTiO₃ceramics with an excess of BaO and additions of SiO₂or B₂O₃were studied. The microstructures and electrical measurements on sintered samples revealed that their electrical properties are related to the microstructure development of the sintered samples. Samples heated with an excess of BaO developed a normal microstructure during sintering, as a consequence of normal grain growth (NGG), and were yellow and insulating. In contrast, samples with an excess of BaO and an addition of SiO₂or B₂O₃exhibited anomalous grain growth (AGG) and were dark blue and semiconducting after sintering. When some BaTiO₃seed grains were embedded in a sample of donor-doped BaTiO₃with an excess of BaO (without SiO₂or B₂O₃), AGG was observed, i.e., some seed grains grew into large grains and were blue and semiconducting. An explanation is given for why AGG is responsible for the oxygen release and the formation of semiconducting grains in donor-doped BaTiO₃and not NGG.     

Role of Liquid Phase in PTCR Characteristics of (Ba0.7Sr0.3)TiO3 Ceramics

The role of liquid phase in the enhancement of the PTCR (positive temperature coefficient of resistance) effect in (Ba_0.7Sr_0.3)TiO₃ (BST) with the addition of AST (4Al₂O₃· 9SiO₂· 3TiO₂) is investigated in this paper. The AST–BST samples were characterized with optical microscopy, transmission electron microscopy, energy-dispersive spectroscopy, and impedance spectroscopy. Microscopic observations showed that slower cooling might facilitate the precipitation of the (Ba,Sr)TiO₃ phase from the liquid phase on matrix grains since the amount of liquid phase was reduced with a decreasing cooling rate. Impedance spectroscopy indicated that this variation accompanied the change in the intrinsic properties of grain boundaries, which could not be explained by well-known oxidation effects. With the aid of a brick-layer model and high-resolution transmission electron microscopy (HRTEM), it appeared that the change in electrical characteristics of grain boundaries with decreasing cooling rate originated from the precipitation of (Ba,Sr)TiO₃. Finally, the effect of precipitated (Ba,Sr)TiO₃ on the PTCR characteristics is discussed in terms of the acceptor-state density and the polarization state at grain boundaries.     

XPS Analysis of Submicrometer Barium Titanate Powder

A commercial submicrometer BaTiO₃ powder was analyzed using X-ray photoelectron spectroscopy. The analysis revealed the powder surfaces to be covered with a layer of physisorbed H₂O and chemisorbed –OH ions. A BaCO₃ residual not detected with XPS was shown to be present in the powder using X-ray diffraction, suggesting that the carbonate takes the form of discrete particles rather than of a continuous surface layer. A relaxed surface phase detected in previous XPS analyses of bulk BaTiO₃ was also shown to be present. Depth profiling revealed the powder surfaces to be Ti-rich, confirming the presence of a phase, or phases, to stoichiometrically balance the barium carbonate.     

Point Defect Concentrations in Barium Titanate Revisited

An analytic link between the oxygen partial pressure and the concentrations of the point defects for given temperatures and A/B conditions is presented for perovskites. A clear distinction between three different conditions is made. These are the sintering conditions, an intermediate metastable state, and a low-temperature metastable state. The analytical solution for a metastable state resulting from nonequilibrated metal vacancies permits a more accurate and self-consistent approach to calculating the equilibrium constants from conductivity– P (O₂) data. One of the reasons for the higher accuracy is that there is no need to divide the existence regime into subregimes with different approximations to the electroneutrality equation (Brouwer approximation). An excellent fit of the experimental conductivity data to a single function with only two adjustable parameters over all conductivity– P (O₂) space is obtained. The relative importance of frozen-in metal vacancies and foreign acceptors is discussed for BaTiO₃.     

Nanosized Barium Titanate Powder by Mechanical Activation

Mechanical activation, without any additional heat treatment, is used to trigger the formation of a perovskite BaTiO₃ phase in an oxide matrix that consists of BaO and TiO₂ in a nitrogen atmosphere. The resulting BaTiO₃ powder exhibits a well-established nanocrystalline structure, as indicated by phase analysis using X-ray diffractometry. A crystallite size of ∼14 nm is calculated, based on the half-width of the BaTiO₃ (110) peak, using the Scherrer equation, and an average particle size of 20–30 nm is observed using transmission electron microscopy for the activation-derived BaTiO₃ powder.     

Necessary Conditions for the Formation of {111} Twins in Barium Titanate

The experimental conditions for {111} twin formation in BaTiO₃ were investigated. When BaTiO₃ compacts without excess TiO₂ were sintered either in an oxidizing atmosphere (air) or in a reducing atmosphere (95N₂–5H₂), no {111} twins formed within the BaTiO₃ grains and no abnormal grain growth occurred. In contrast, many {111} twins were present within the abnormally grown grains in the excess-TiO₂-containing BaTiO₃ samples sintered in air, while no twins were observed in the excess-TiO₂-containing samples sintered in 95N₂–5H₂. X-ray diffraction analysis showed that excess TiO₂ forms a Ba₆Ti₁₇O₄₀ phase during sintering with the space group A 2/ a in air and a Ba₆Ti₁₇O_{40− x} phase with the space group C in 95N₂–5H₂. It appears therefore that excess TiO₂ and an oxidizing atmosphere are necessary for {111} twin formation in BaTiO₃. These results may also indicate that the interface structure between BaTiO₃ and Ba₆Ti₁₇O₄₀ influences the twin formation.     

Dependence of the Crystal Structure on Particle Size in Barium Titanate

The effect of the sample particle size on the crystal structure and the Curie temperature of BaTiO₃ powder has been investigated in the particle size range 0.1 to 1.0 μm. The transformation from tetragonal to cubic symmetry occurs at a critical particle size of 0.12 μm at room temperature, and the Curie temperature drops below room temperature at the critical particle size.     

Intermediate Phase Development in Phosphorus-Doped Barium Titanate

In the present work, the phase formation and thermal evolution in phosphorus-doped BaTiO₃ have been studied using differential thermal analysis, X-ray diffractometry, scanning electron microscopy coupled with energy-dispersive spectroscopy, transmission electron microscopy, and high-temperature nuclear magnetic resonance. Phosphorus cations that are incorporated from ester phosphate form a surface layer that covers the BaTiO₃ particles. This layer acts as a reactive coating during sintering. Phosphorus-doped BaTiO₃ samples that have been treated at temperatures of 650°–900°C show the presence of crystalline Ba₂TiP₂O₉ and/or Ba₃(PO₄)₂ phases. The appearance of secondary phases is dependent on the cooling rate. Higher temperatures (900°–1200°C) result in the presence of a phosphorus–BaO-rich phase that covers the BaTiO₃ particles. As a consequence, the remaining titanium-rich BaTiO₃ drives the formation of a liquid phase at temperatures >1200°C. In regard to the reported sintering behavior of P⁵⁺-doped BaTiO₃, the formation of a phosphorus–BaO-rich phase that covers the BaTiO₃ particles could be the origin of the improved porosity coalescence and removal that is observed at the earlier stages of sintering.