Semiconducting properties of barium titanate and iron substituted barium titanate

Single crystals of barium titanate and members of the series BaTi_1?xFe_xO_3?xF_x have been grown from a potassium fluoride flux. These crystals were made conductive by heating in a sealed evacuated silica tube in the presence of freshly ground titanium. Electrical, optical and magnetic measurements were performed in order to characterize these crystals. Optical measurements indicated a decrease in the band edge from 3.2(1) eV for barium titanate to 2.8(1) eV for Bati_1?xFe_xO_3?xF_x(x = 0.02, 0.05, 0.07, 0.10). The photoelectrolytic behavior of reduced barium titanate was strongly quenched upon the substitution of iron and fluorine.     

Effect of copper substitution on the microstructure and ferroelectric properties of barium titanate

Abstracts are not published in this journal This revised version was published online in November 2006 with corrections to the Cover Date.     

Preparation of barium titanate by homogeneous precipitation

The barium titanyl oxalate, which was the precursor of barium titanate, was prepared by homogeneous precipitation using the diethyl oxalate as a precipitating agent. The oxalate dried at 80 °C was the crystalline phase, which was converted to amorphous-like phase after drying at 120 °C. The weight loss of oxalate was 47.3 wt%. The chemical formula of the oxalate could correspond to BaTiO(C₂O₄)₂ · 4H₂O. The barium titanate obtained from the calcination of oxalate at 850 °C was a tetragonal phase with a particle size of 0.2 m.     

Effect of simultaneous substitution of La and Mn on dielectric behavior of barium titanate ceramic

A few compositions in the valence compensated system Ba_1−x La _x Ti_1−x Mn _x O₃ were synthesized by solid-state ceramic method to study the effect of co-doping lanthanum and manganese in equimolar amounts on dielectric behavior of BaTiO₃. Compositions with x ≤ 0.10 have shown solid solution formation. Compositions with x ≤ 0.05 are found to have tetragonal structure at room temperature while composition with x = 0.10 is cubic. Plots of relative dielectric constant, ε_r versus temperature for composition with x = 0.01 show dielectric anomalies around 376 ± 2, 264 ± 2 and 179 ± 2 K which correspond to cubic to tetragonal (T _C–T), tetragonal to orthorhombic (T _T–O) and orthorhombic to rhombohedral (T _O–R) transition, respectively, similar to BaTiO₃. Curie temperature has been found to decrease with increasing concentration of lanthanum and manganese simultaneously in barium titanate. The broadening in the dielectric peak at cubic to tetragonal (T _C–T) transition temperature increases with increasing x. For x = 0.10, only one anomaly at 100 K is observed in its ε_r versus T plots. The observation of this single anomaly may be due to pinching effect of the substitutions on the three phase transitions.     

Preparation of powder barium titanate

Phase-pure BaTiO₃ powder (free of Ba₂TiO₄, BaCO₃, Ba(NO₃)₂, and OH impurities) with an average particle size of about 100 nm is prepared by solid-state reaction between titanium oxyhydroxide and barium hydroxide ground and mixed by sonication in an inert organic liquid.     

Dielectric studies of barium bismuth titanate as a material for application in temperature sensors

Ceramic nanocrystalline samples with composition Ba_1?3aBi_2aTiO₃ were synthesized by sol–gel method, for different values of parameter a (for a = 0.0165, 0.033, 0.050). In order to determine whether barium bismuth titanate is suitable for application in temperature sensors, dielectric properties measurements were conducted on the prepared samples, as a function of both temperature (from room temperature up to 190 °C) and frequency (from 50 kHz to 1 MHz). Real and imaginary parts of dielectric constant were determined using an Impedance Analyzer HP-4194A. Depending on parameter a two different behavior were determined: (1) classical ferroelectric behavior, for the sample with low a value and (2) relaxor behavior for the samples with higher a values. Thus, a typical characteristic of relaxor ferroelectrics with a broad and dispersive dielectric maximum was observed for the samples Ba_0.85Bi_0.1TiO₃ and Ba_0.90Bi_0.066TiO₃. Temperature dependence (for real part of dielectric constant ε_r′) is almost linear, for lower temperatures than peak value (slope +1.3 1/ °C), and higher than this value (slope ?1 1/ °C). The feature of linearity is very important from practical aspects of application of this material in wireless temperature sensors. The temperature coefficient of dielectric constant for the sample with the best linearity (Ba_0.95Bi_0.033TiO₃ at 1 MHz) was found to vary from positive one +3.72 × 10^?3 1/ °C to negative value ?2.85 × 10^?3 1/ °C, in the temperature range 25–190 °C.     

A modified method for barium titanate nanoparticles synthesis

In this research, a modified, cost effective sol-gel procedure applied to synthesize BaTiO₃ nanoparticles. XRD and electron microscopy (SEM and TEM) applied for microstructural characterization of powders. The obtained results showed that the type of precursors, their ratio and the hydrolysis conditions had a great effect on time, temperature and therefore the costs of the synthesis process. By selection, utilization of optimized precursor's type, hydrolysis conditions, fine cubic BaTiO₃ nanoparticles were synthesized at low temperature and in short time span (1 h calcination at 800 °C). The proposed procedure seems to be more preferable for mass production.The result indicated that the polymorphic transformation to tetragonal (ferroelectric characteristic) occurred at 900 °C, which might be an indication of being nanosized.     

Microwave synthesis of nano-sized barium titanate

Nano-sized barium titanate powders have been synthesized by microwave processing at 2.45 GHz. Using barium titanyl oxalate (BTO) as a precursor, microwave processing was carried out by heating the precursor to a temperature between 600 °C and 750 °C with different heating rates from 10 °C/min to 20 °C/min without isothermal holding. X-ray diffraction analysis indicates that the decomposed product at 680 °C was pure cubic BaTiO₃. The BET specific surface area of barium titanate powder, after microwave heating to 680 °C, was 14.2 ± 0.5 m²/g, corresponding to an average particle size of 70 nm. This particle size was confirmed by the scanning electron microscopy (SEM). Parallel study shows that the conventional heating in a regular resistance furnace using a similar heating schedule did not result in complete conversion of BTO. This study shows that the microwave processing significantly accelerated the decomposition of barium titanyl oxalate and reduced the temperature of barium titanate nano-powder formation, resulting in nano-sized pure cubic barium titanate powder.     

Microwave-hydrothermal synthesis of tetragonal barium titanate

Tetragonal barium titanate with c/a ratio of 1.0093 and average particle size of 240 nm was synthesized by the microwave-hydrothermal (MH) method at 240 °C in only 12 h. Temperatures above 200 °C were first introduced to the MH process in this study, since the temperature has a critical effect on the formation of tetragonal BaTiO₃, shown by the experiments here. Hydrous titanium oxide and Ba(OH)₂ were used as precursors, without halide anions and alkali-metal cations to avoid contamination. The kinetics of tetragonal phase formation in BaTiO₃ was considerably promoted in the MH processing, in comparison with the conventional hydrothermal (CH) route.     

Ultrathin barium titanate films by polyol thermal decomposition process

We have successfully fabricated barium titanate (BaTiO₃) films on Si (100) and Pt(111)/Ti/SiO₂/Si substrates using the polyol thermal decomposition (PTD) process by spin-coating technique. In PTD process, we confirmed that the crystalline oxycarbonate Ba₂Ti₂O₅CO₃ films were directly formed as a consequence of evaporation of polyol precursor solution prepared simply by mixing metal chlorides and ethylene glycol, and then converting them into crystalline BaTiO₃ films through thermal decomposition at >500 °C. This feature makes it possible to grow densely packed and crack-free BaTiO₃ films as thin as 70 ? per cycle. Although PTD is described here for a complex metal-oxide film of BaTiO₃, other simple and complex metal-oxide thin films with high-dielectric constant materials are also likely to be suitable for deposition with accurate control of film thickness and composition using the polyol precursor solutions.     

Study on barium titanate ceramics prepared by various methods

Barium titanate (BaTiO₃) ceramics have been fabricated using powders prepared by sol-gel, coprecipitation and mixed oxide methods. The powders prepared by sol-gel and coprecipitation have average crystallite diameters of 100 nm and 300 nm, respectively while the diameter of the mixed oxide powder is 1–3 m. When sintered at the same temperature of 1320°C, the three BaTiO₃ ceramics have very different grain size, with the one prepared by the mixed oxide method having the largest grain size of 20 m. The dielectric permitivity increases as the grain size of the ceramic becomes smaller. The room temperature (25°C) dielectric permittivity, pyroelectric and piezoelectric properties of these ceramics have been measured as functions of the poling field. The BaTiO₃ ceramic fabricated from nanosized powder derived from the coprecipitation method is found to have the smallest grain size and better properties than prepared from the sol-gel route, and is thus a good candidate for use in devices that required thick (10 to 20 m) ferroelectric films.     

Effects of barium dissolution on dispersing aqueous barium titanate suspensions

Dissolution of barium ion and its effect on dispersion behavior of aqueous barium titanate suspensions at various pH values have been investigated. The amount of leached barium ion decreases with increasing pH value. The dissolution of barium ion also causes an increase in pH value of suspension, but the change decreases with increasing initial pH value. The iso-electric point (IEP) of leached barium titanate powder increases with increasing leaching pH value and solid loading as well. The dissolution of barium ion enhances the colloidal stability of aqueous barium titanate suspension, in agreement with zeta potential measurement.     

Optimization of barium titanate nanopowder slip for tape casting

Dispersion of barium titanate nano powder of average particle size ∼30 nm in different solvent systems of tape casting (toluene–ethanol, methyl ethyl ketone–ethanol, xylene–ethanol) along with Triton x-100 or phosphate ester as dispersants has been studied using sedimentation experiments. The influence of different parameters such as type of solvent system, dispersant and concentration of dispersant on BaTiO₃ slip dispersion, viscosity and the properties of green tape were studied. The optimal concentration of dispersant was determined from the minimum slip viscosity. Xylene–ethanol with phosphate ester was found to be the best solvent and dispersant system for tape casting. Defect free, denser and smooth green tapes are formed with this system.     

Synthesis of barium titanate nanopowder by a soft chemical process

A simple soft chemical method of synthesizing barium titanate nanopowders and nanorods is described here, where titanium dioxide/titanium isopropoxide was taken as a source of titanium, tartaric acid was taken as a template material, nitric acid as an oxidizing agent. The synthesized powders and rods were characterized by XRD, TG and DTA, SEM and IR spectroscopy. In this process phase pure barium titanate nanopowders and nanorods can be prepared at a temperature of 900 °C and the process is simple and cost-effective.