Hydrothermal Preparation and Characterization of Ultra-Fine BaTiO3 Powders from Amorphous Peroxo-Hydroxide Precursor

Ultra-fine BaTiO₃ powders were hydrothermally prepared by using Ba Ti-peroxo-hydroxide precursor. Amorphous Ba Ti-peroxo-hydroxide precursor were prepared by coprecipitation of Ba(NO₃)₂ and TiCl₄ aqueous solution adding in NH₄OH aqueous solution. The phase-pure BaTiO₃ powders with a cubic perovskite structure were synthesized at temperature as low as 110_C and in the pH range of 10–12. This processing method provides a simple low temperature route for producing BaTiO₃ nanoparticles. Under a TEM image and a SAD pattern analysis, it is evident that BaTiO₃ powders had spherical shape and single crystal nature. The BaTiO₃ ceramic sintered at 1200_C for 1 h had 97% of theoretical density and a relatively high dielectric constant ( _r = 3500).     

Microwave Dielectric Properties of Ferroelectric BaTiO3 Thin Film

The dielectric properties of c-axis epitaxial BaTiO₃ thin film on LaAlO₃ are investigated at frequencies of 0.5–30 GHz. For the measurements, interdigital capacitors with the Au/Ti electrode configurations of five fingers pairs that are 15 m wide and spaced 2 m apart are prepared by photolithography and lift-off patterning. Finger length varies from 20 to 80 m. The capacitance of epitaxial BaTiO₃ films exhibited no frequency dependence up to 10 GHz with the exception of slightly upward tendency of capacitance in BaTiO₃ film with a finger length of 80 m due to the self resonant frequency at 20 GHz. The Q-factors of the capacitors, defined as Q = 1/CR, are decreased up to 10 GHz with increased frequency. At 10 GHz, the BaTiO₃ film has a tunability [defined as k(V) = [C(0)–C(V)]C(0)] of 1.5% at 15 V, a loss tangent of 0.2 at room temperature. The small tunability can be interpreted as a result of in-plane compressive stress of BaTiO₃ film exhibiting large dielectric anisotropy. For the improvement of tunability and dielectric loss in the interdigital BaTiO₃ capacitor, the tetragonality (c/a) of epitaxial BaTiO₃ film and design of interdigital capacitor should be modified.     

Crystal Growth and Dielectric Properties of New Ferroelectric Barium Titanate: BaTi2O5

Single crystals of the ferroelectric BaTi₂O₅ and BaTiO₃ were prepared from a solution of 33-mol% BaO and 67-mol% TiO₂ by a rapid cooling method. The dielectric constant () and dielectric loss tangent (tan) were measured in a wide temperature range of 10–860 K and in a frequency range of 0.1–3,000 kHz. The along the b-axis of the BaTi₂O₅ crystal, prepared in air, shows a sharp dielectric anomaly reaching 30,000 at the ferroelectric Curie temperature of T_C = 752 K. By contrast, the crystal prepared in a reducing atmosphere shows a diffuse phase transition near T_C = 703 K. The values of and tan are compared between these three crystals consisting of two kinds of BaTi₂O₅ and one BaTiO₃.     

P-Type Partial Conductivity of Donor(La)-Doped BaTiO3

P-type partial conductivity has been determined on donor (La _Ba )-doped BaTiO₃ in full thermodynamic equilibrium state at a fixed temperature of 1200°C: For the nominal compositions of Ba_0.99La_0.01Ti_0.9975O₃, Ba_0.99La_0.01TiO₃ and Ba_0.985La_0.01TiO₃, the p-type conductivity is found to vary with oxygen activity as _p = (_m/2)(a _{O 2}/a _{O 2}*)^+1/4 with _m 0.01 S cm^–1 and a _{O 2}* 32, 120, 310, respectively, in the a _{O 2} region where conventionally the electronic conductivity varies as a_{O 2} ^–1/4 and hence, the doped donors are believed to be compensated by cation vacancies (say, [La_Ba ] 4[VPrime;_Ti]). This experimental fact supports that in the vicinity of the stoichiometric composition of the system which falls approximately at a _{O 2} = a _{O 2}*, while cation vacancy concentration is fixed by the donor concentration, oxygen vacancy concentration in the minority is also essentially fixed, thus, keeping the activity of TiO₂ (or BaO) fixed. It is consequently suggested that donor-doped BaTiO₃ contains a second phase even in its stoichiometric regime.     

Mn-doped BaTiO3: Electrical Transport Properties in Equilibrium State

The electrical conductivity and thermoelectric power of Mn-doped BaTiO₃ (1 mole%) and undoped BaTiO₃ have been measured as functions of oxygen partial pressure (in the range of 10^-16 to 1 atm) and temperatures (in the range of 900 to 1200°C), and compared with each other to differentiate the effect of the Mn-addition. It is found that the isothermal conductivity of Mn-doped BaTiO₃ varies with increasing Po₂ as to to , unlike previously reported. This behavior is well explained by the shift of the ionization equilibrium, . The corresponding equilibrium constant, K_A, is determined from the Po₂ values demarcating those three different Po₂ regions as =3.19×10²² exp(–1.69 eV/kT). Basic parameters involving carrier density and mobility, and defect structure of Mn-doped BaTiO₃ are discussed in comparison with those of undoped BaTiO₃.     

Copper Compatible Barium Titanate Thin Films for Embedded Passives

Barium titanate thin films have been prepared by chemical solution deposition on 18 m thick, industry standard copper foils in the absence of chemical barrier layers. The final embodiment exhibits randomly oriented BaTiO₃ grains with diameters between 0.1 and 0.3 m, and an equiaxed morphology. The average film thickness is 0.6 m and the microstructure is free from secondary or interfacial phases. The BaTiO₃ films are sintered in a high temperature reductive atmosphere such that copper oxidation is avoided. Subsequent lower-temperature, higher oxygen pressure anneals are used to minimize oxygen point defects. Permittivities of 2500 are observed at zero bias and room temperature, with permittivities greater than 3000 at the coercive field. Loss tangents under 1.5% are demonstrated at high fields. The BaTiO₃ phase exhibits pronounced ferroelectric switching and coercive field values near 10 kV/cm. Temperature dependent measurements indicate a ferroelectric transition near 100C with very diffuse character. Combining the approaches of the multilayer capacitor industry with traditional solution processed thin films has allowed pure barium titanate to be integrated with copper. The high sintering temperature—as compared to typical film processing—provides for large grained films and properties consistent with well-prepared ceramics. Integrating BaTiO₃ films on copper foil represents an important step towards high capacitance density embedded passive components and elimination of economic constraints imparted by traditional noble metallization.     

Thermoelectricity of BaTiO3+δ

Thermoelectricity of mixed ionic electronic conductor BaTiO₃₊ is thermodynamically analyzed, and measured across the mixed n/p regime of both undoped and 1.8 m/o A1-doped BaTiO₃ at elevated temperatures. There can be 4 different measurement conditions with respect to the nonstoichiometry () redistribution and types of atmosphere gases used to control the surrounding oxygen potential, which lead to differences in information content of the thermopower. Experimental thermopower isotherms are exhaustively analyzed to find that the ionic contribution is evident in the mixed n/p regime and that the heats of transport of electrons and holes are about the same as their migration enthalpies.     

BaTiO3−δ: Defect Structure, Electrical Conductivity, Chemical Diffusivity, Thermoelectric Power, and Oxygen Nonstoichiometry

Electrical conductivity, thermoelectric power, and chemical diffusivity are the most typical, charge-and-mass transport properties of a mixed ionic electronic conductor oxide which are essentially governed by its defect structure, and the oxygen nonstoichiometry is a direct measure of its overall defect concentration. For the system of BaTiO_3–, the total electrical conductivity has been the most extensively and systematically studied as a function of oxygen partial pressure at elevated temperatures. The other properties have also been studied, but much less extensively and systematically. The electrical conductivity and thermopower were occasionally measured together on the same specimens so that mutual compatibility or consistency might be secured. But, the rest were all determined separately on the specimens of differing quality, consequently lacking in mutual consistency. It, thus, has remained hard to evaluate the canonical, defect-chemical parameters which are consistent with each and every of these defect structure-sensitive properties that were observed. Very recently the authors have determined the total conductivity, chemical diffusivity and thermoelectric power altogether on the same specimens of BaTiO_3–, and the nonstoichiometry on the same-quality specimens at temperatures of 1073 T/K 1373 over wide enough a range of oxygen partial pressure (normally, 10^–16 Po₂/atm 1) that encloses an electron/hole/ion mixed regime. In this article, we will compile all the literature data on these defect-structure-sensitive properties and extract from the authors' own, without using any ad hoc assumptions regarding, e.g., the electronic carrier mobilities and effective density of states, the basic defect-chemical parameters including defect-equilibrium constants, carrier mobilities and densities, and electronic heats of transport, which are the most consistent with the properties observed. Compared to the conventional picture of the defect structure of undoped BaTiO₃, thus, some new insights into the defect chemical nature of BaTiO_3– are provided.     

Electrical Properties of 6H-BaTi0.95M0.05O3−δ Ceramics where M = Mn, Fe, Co and Ni

Hexagonal BaTiO₃ materials have been stabilised at room temperature according to the formula BaTi_0.95M_0.05 O_3– where M = Mn, Fe, Co and Ni. Dense ceramics (> 96% of the theoretical X-ray density) were sintered at 1450C in flowing O₂ gas from calcined powders prepared by the mixed oxide route at 1300C. All samples were single-phase and the bulk conductivity, _b, measured by Impedance Spectroscopy and Q.f measured by microwave dielectric resonance methods showed a strong dependence on the type of dopant. _b at 300C was 10^–7, 10^–5.5, 10^–5.5 and 10^–4 Scm^–1 for M = Mn, Fe, Ni and Co, respectively and Q.f at 5 GHz was 7790, 6670, 2442 and 1291 GHz, for M = Mn, Fe, Ni and Co, respectively. The correlation between _b and Q.f is attributed to the presence of oxygen vacancies and/or mixed valency of the dopant ions.     

Copper Cofire X7R Dielectrics and Multilayer Capacitors Based on Zinc Borate Fluxed Barium Titanate Ceramic

Copper cofired dielectrics may give new opportunities for high temperature capacitors. To demonstrate feasibility, BaTiO₃ has been formulated into X7R dielectrics with copper inner electrodes. This requires the development of a formulation that permits sintering at temperatures below 1000°C, and then firing in a reducing environment in atmospheres pO₂ 10^–8 atms. ZnO—B₂O₃ chemistries were explored with additional dopants to modify densification and the temperature coefficient of capacitance of the BaTiO₃ dielectric anomaly. X7R characteristics with relative dielectric permittivities 2750 and tan 0.01 at 1 kHz were obtained at room temperature. Multilayer capacitors were fabricated in 3.2 mm × 1.6 mm size multilayers with an acrylic binder system and oxidation resistive copper inner electrodes.     

Selective Gas Detection of SnO2-TiO2 Gas Sensors

The composite, consisting of two materials with different sensing temperatures, may show the selectivity for a particular gas. In this study, the microstructural and compositional effects on the electrical conductivity and the CO and the H₂ gas sensing properties of SnO₂-TiO₂ composites were examined. SnO₂-TiO₂ composites in entire (0–100 mol%) composition range were fabricated in the form of porous pellet by sintering at 800C for 3 h. The effects of CuO-coating (or doping) on the electrical conductivity and the sensing properties to 200 ppm CO and H₂ gases were examined.With CuO-coating, SnO₂-TiO₂ composites showed the increased sensitivity to CO gas and a large difference in the sensing temperatures between CO and H₂ gases. As a result, CuO-coated SnO₂-TiO₂ composites showed the selectivity for CO gas between 100C and 190C and the selectivity for H₂ gas between 280C and 380C.     

Nanocrystalline Alkaline Earth Titanates and Their Conductivity Characteristics Under Changing Oxygen Ambients

This work presents the first systematic study of conductivity characteristics of alkaline earth titanates in the form of polycrystalline and heteroepitaxial thin films as well as nanocrystalline ceramics as a function of temperature (between 600_C and 1000_C) and continuously adjustable oxygen partial pressures ranging from 10^{– 20} bar to 1 bar. Compared to the well-known log,-log, pO₂ profiles of single crystals, the conductivity behavior of CSD-prepared, polycrystalline SrTiO₃ thin films with a feature size of about 50 nm differs radically. The most prominent characteristics are a sharp drop under reducing conditions followed by a broad plateau region. Tailored investigations on heteroepitaxial as well as polycrystalline thin films grown by PLD and especially by studies on nanocrystalline BaTiO₃ ceramics with a mean grain size of 100 nm allowed an unambiguous assignment of the described effects to the nanocrystalline morphology of the samples.     

Microstructure of X7R Type Base-Metal-Electroded BaTiO3 Capacitor Materials Co-Doped with MgO/Y2O3 Additives

Detailed microstructure of MgO/Y₂O₃ co-doped BaTiO₃ materials were examined using transmission electron microscopy (TEM). For the 1250_C-sintered BaTiO₃ samples possessing flat K-T characteristics, which meet the X7R specification, the granular structure is complicated. Most of the grains are very small ( 150 nm) and are highly strained. The small grains contain large proportion of Y₂O₃ species and are paraelectric, whereas the large grains contain Y₂O₃ species unevenly distributed and are of core-shell structure. In contrast, for the 1300C-sintered BaTiO₃ samples, which have K-T properties slightly off the X7R specification, the grains grew larger to around 300 nm. The core-shell structured grains are seldom observed. Apparently, it is the existence of such a non-equilibrium core-shell microstructure, which renders the dielectric properties of the BaTiO₃ materials extremely sensitive to the processing parameters.     

Ca Substituted PbTiO3 Thin Films for Infrared Detectors

Crack free Ca substituted PT thin films have been deposited on ITO coated 7059 glass substrates by sol gel technique and crystallized at 650C. Characterization of these films by X-ray diffraction show that the films exhibit tetragonal structure with perovskite phase. AFM, hysteresis, dielectric relaxation and pyroelectric studies have been carried out. The pyroelectric figures of merit of the films have been calculated. Our investigations show that these films are expected to give high infrared detector performance due to its high pyroelectric coefficient (43 nC/cm²K), high voltage responsivity (2340 Vcm²/J) and detectivity(3 × 10^{– 5} Pa^{– 1/2}) along with small value of dielectric constant (83) and loss tangent (0.04).     

Annealing Effects on Structural and Dielectric Properties of Tunable BZT Thin Films

Ba(Zr, Ti)O₃ thin films have attracted great attention in recent years for their potential use in DRAMs and MCMs due to their high dielectric constant and relatively low leakage current. However, their tunable dielectric properties were rarely investigated and the corresponding potential for tunable microwave applications was seldom reported. In this paper, we present the tunable dielectric behavior of BZT thin films deposited by RF magnetron sputtering from a Ba(Zr_0.3Ti_0.7)O₃ ceramic target on MgO single crystal substrates. The composition, thickness and crystallinity of the thin films were analyzed by Rutherford backscattering (RBS), scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The dielectric constant and loss tangent were measured as a function of electric field (0–7 kV/mm) and temperature (–140 to +160°C) at frequencies up to 1 MHz, using interdigital capacitors (IDC) with Au electrodes on thin films. By optimizing the preparation process, a tunability {defined as = [ (0) – (E_max)]/ (0)} of 76% at E_max = 7 kV/mm and a low loss tangent of 0.0078 can be achieved. In addition, the influence of annealing temperature on the dielectric properties of the thin films is also discussed.     

Structural, Thermal and Electrical Properties of Ce-Doped SrMnO3

The Sr_1-xCe_xMnO_1- system (0 x 0.5) was investigated with respect to its structural, thermal and electrical properties. Although un-doped SrMnO₃ has the perovskite structure above 1400°C, the structure is unstable at room temperature. However, partial substitution of Ce for Sr in SrMnO₃ stabilizes the perovskite structure down to room temperature. Single phase perovskite is obtained for 0.1 x 0.3 in Sr_1-xCe_xMnO_1-, and it remains stable even following heat treatment at 800°C for 100 h. The dependence of the electrical conductivity on temperature was measured from room temperature to 1000°C in air. Ce doping dramatically enhanced the electrical conductivity of SrMnO₃. Sr_0.7Ce_0.3MnO_1- exhibits a higher conductivity (290 S · cm^-1 at 1000°C) than that of La_0.8Sr_0.2MnO₃ (LSM, about 175 S · cm^-1) and remains n-type over the whole range of temperature examined. The thermal expansion coefficients in the system were nearly constant with values ranging between 1.24 × 10^-6 and 1.01 × 10^-6 cm/cm · K for temperatures of 50°C to 1000°C.     

Optical Waveguiding Properties of (Pb,La)TiO3/Al2O3 Planar Structures

Thin films of lead lanthanum titanate (Pb,La)TiO₃ have been grown by radio-frequency magnetron sputtering on (0001) Al₂O₃ substrates. The structure, the microstructure and the optical properties of the films have been investigated as a function of the postdeposition annealing. Films deposited at low temperatures crystallize to a perovskite phase after the annealing treatment from 500°C to 650°C. X-ray (–2) diffraction studies have shown that films are crystallized with a strong (111) orientation and the best crystalline structure is reported at 600°C. The optical properties were both demonstrated by spectrophotometry and prism coupling. PLT thin films with a transparency of 80% in the wavelength range 300–2000nm have exhibited a refractive index of 2.38 @ 632.8nm representing 97% of the bulk corresponding material. Investigation of optical propagation has been accomplished in a 10mm long planar optical waveguide using a butt-coupling configuration.     

Dielectric Properties and Sintering Characteristics of CaTiO<Subscript>3</Subscript>-(Li<Subscript>1/2</Subscript>Nd<Subscript>1/2</Subscript>)TiO<Subscript>3</Subscript> Ceramics

The dielectric properties and the sintering effect upon microstructure of (1–x) CaTiO₃-x(Li_1/2Nd_1/2)-TiO₃ Ceramics are investigated in this paper. Nd³⁺ and Mg^{2 +} ions co-substitution for Ca^{2 +} on A site improves the sintering characteristic of CaTiO₃ ceramics with forming orthorhombic perovskite structure. The structure of (1 – x) CaTiO₃-x(Li_1/2Nd_1/2)TiO₃ changes from orthorhombic to tetragonal as (Li_1/2Nd_1/2)TiO₃ addition increasing. Limited solubility of (Li_1/2Nd_1/2)TiO₃ in CaTiO₃ forming a part solid solution compound achieves the adjustment of for CaTiO₃ at low sintering temperature. The proper dielectric properties with = 78, tan = 0.0006, = +7 ppm/C are obtained for 0.8Ca_0.67(Nd,Mg)_0.22TiO₃-0.2(Li_1/2Nd_1/2)TiO₃ ceramics.     

Microstructural Control of BaTiO3 Thick Film Fabricated by Utilizing Slide-Off Transfer Printing

Effects of fabrication conditions on the microstructure of thick BaTiO₃ films have been investigated by employing slide-off transfer printing technique. Formation of dense films with good adhesive properties was difficult when screen-printing was employed in preparing the slide-off transfer sheets (BaTiO₃ green films), irrespective of the kind of solvents used for the slurries. On the other hand, relatively dense films could be fabricated from the slide-off transfer sheet prepared by spin-coating of the slurries consisting of fine BaTiO₃ powder (particle size: ca. 0.1 m), printing oil, and 2-propanol, though cracks formed obviously. Co-addition of large BaTiO₃ particles (particle size: ca. 0.5 m) was very effective for reducing the formation of cracks, and homogenous and dense films could be fabricated by controlling the additive amount of the large particles.     

β″-Al2O3 Single-Crystal Films and their Optical Properties

The development of large-area, Na--Al₂O₃ single-crystal films on sapphire substrates via vapor reaction is reported. The films form at the expense of the sapphire which reacts with the alkali-vapors generated from mixed (Na,Li)--Al₂O₃ powders occupying the same space as the sapphire. A number of -Al₂O₃ single-crystal, large area isomorphs have been synthesized via ion exchange and their refraction and luminescence properties are reported. Patterned luminescence has been achieved in Cu⁺-doped single-crystal films using an electrochemical cell with + electrolyte separator between aqueous-solution electrodes. Ag⁺ ions are injected into the -Al₂O₃ electrolyte and Na⁺ expelled. The distribution of luminescent and environment ions is controlled by electrical charge and the chemical potential of the ions in the solution electrodes.