Electrical Conductivity of Y2O3 as a Function of Oxygen Partial Pressure in Wet and Dry Atmospheres

The electrical conductivity of polycrystalline Y₂O₃ has been studied as a function of the partial pressure of oxygen (10^–14 to 10⁵ Pa) at 900° to 1500°C in atmospheres saturated with water vapor at 12°C or dried with P₂O₅. Yttria is a p -conductor at high oxygen activities. The p -conductivity increases with increasing P _O2 and decreases with increasing P_H2O. At low oxygen activities the oxide is a mixed ionic/electronic conductor. The ionic conductivity is approximately independent of P _O2 and increases with increasing P _H2O. In the Y₂O₃ samples, excesses of lower-valent cation impurities (in the 10 to 100 mol-ppm range) are the dominating negatively charged defects, and in the presence of water vapor they are compensated by interstitial protons. At high P _H2O levels additional protons are probably compensated by interstitial oxygen ions. At high temperatures (±1100°C) and for high P _O2 and low P _H2O, the protons are no longer dominant, and the lower-valent cations are mainly compensated by electron holes. The electrical conductivity exhibits hysteresis-like effects which are interpreted in terms of segregation/desegregation of impurities at grain boundaries. The mobility of electron holes in yttria at 1500°C is estimated to be of the order of magnitude of 0.05 cm². s^–1. V^–1     

Microstructure and Dielectric Properties of Textured SrTiO3 Thin Films

We investigate the relationship between microstructure and dielectric properties of textured SrTiO₃ thin films deposited by radio-frequency magnetron sputtering on epitaxial Pt electrodes on sapphire substrates. The microstructures of Pt electrodes and SrTiO₃ films are studied by transmission electron microscopy, atomic force microscopy, and X-ray diffraction. SrTiO₃ films grown on as-deposited and annealed Pt electrodes, respectively, consist of a mixture of (111)- and (110)-oriented grains. Temperature-dependent dielectric measurements show that differences in texture and microstructure are reflected in the Curie–Weiss behavior of the SrTiO₃ films. Phenomenological models that account for the effects of thermal mismatch strain on the dielectric behavior are developed for different film textures. The models predict that at a given temperature, paraelectric (111)-oriented films of SrTiO₃ on tensile substrates will have a higher Curie–Weiss temperature and a greater dielectric constant than (110)-oriented films or bulk SrTiO₃. The experimental dielectric behavior is compared with the predictions from theory, and different contributions, such as interfacial layers, film stress, and microstructure, to the Curie–Weiss behavior are discussed.     

Control of Microstructure and Orientation in Solution-Deposited BaTiO3 and SrTiO3 Thin Films

Columnar and highly oriented (100) BaTiO₃ and SrTiO₃ thin films were prepared by a chelate-type chemical solution deposition (CSD) process by manipulation of film deposition conditions and seeded growth techniques. Randomly oriented columnar films were prepared on platinum-coated Si substrates by a multilayering process in which nucleation of the perovskite phase was restricted to the substrate or underlying layers by control of layer thickness. The columnar films displayed improvements in dielectric constant and dielectric loss compared to the fine-grain equiaxed films that typically result from CSD methods. Highly oriented BaTiO₃ and SrTiO₃ thin films were fabricated on LaAlO₃ by a seeded growth process that appeared to follow a standard "two-step" growth mechanism that has been previously reported. The film transformation process involved the bulk nucleation of BaTiO₃ throughout the film, followed by the consumption of this matrix by an epitaxial overgrowth process originating at the seed layer. Both BaTiO₃ and PbTiO₃ seed layers were effective in promoting the growth of highly oriented (100) BaTiO₃ films. Based on the various processing factors that can influence thin film microstructure, the decomposition pathway involving the formation of BaCO₃ and TiO₂ appeared to dictate thin film microstructural evolution.     

Electrical Conductivity and Defect Structure of Y2O3 as a Function of Water Vapor Pressure

The electrical conductivity of several sintered yttria ceramics with different levels of lower valent cation impurities was studied as a function of the partial pressure of water vapor (3 to 1600 Pa) at 500° to 1300°C in oxygen or air. At the higher temperatures yttria is a P -type conductor, but at the lowest temperatures and highest water vapor pressures, an ionic contribution becomes significant. The p -type conductivity decreases with increasing water vapor pressure. This is interpreted in terms of a model involving dissolution of hydrogen as interstitial protons and which counterbalance the effective charges of the lower valent impurities. At the higher water vapor pressures and lower impurity levels excess protons are probably compensated by interstitial hydroxide or oxygen ions. Indications of grain boundary segregation of impurities are reported.     

Core-Shell Structure Formation in Nb2O5-Doped SrTiO3 by Oxygen Partial Pressure Change

A core-shell structure was observed in SrTiO₃ doped with 1.2 mol% of Nb₂O₅, after sintering in a reducing atmosphere (5H₂-95N₂) and then in an oxidizing atmosphere (air). In undoped and Al₂O₃-doped SrTiO₃ specimens, no core-shell structure formed after the same sintering treatments as those for SrTiO₃ doped with 1.2 mol% of Nb₂O₅. The measured chemical compositions of the core and shell regions of 1.2-mol%-Nb₂O₅-doped SrTiO₃ grains showed that the Sr/(Ti + Nb) ratio of the shell regions grown in air was ~1% less than that of core regions grown in 5H₂-95N₂, which was in good agreement with a value predicted by available defect equations. Therefore, the observed core-shell structure is thought to result from the formation of strontium vacancies in an oxidizing atmosphere.     

Direct-Current Conductivity of Y2O3 as a Function of Water Vapor Pressure

The dc conductivity of a sintered sample of Y₂O₃ containing an excess of lower-valent metal (Ml) impurities has been measured at 600° to 1100°C in air as a function of the water vapor pressure (0.4 to 3000 Pa). The logarithm of the p -type conductivity vs log P _H2o has a slope of – 1/2 in certain regions of F _H2o and temperature. This reflects a defect situation where interstitial protons from water vapor balance the excess of lower-valent cation impurities: [H_˙] = [M1_']. The activation energy for the p -type conductivity under these conditions is evaluated and interpreted in terms of the enthalpy needed to dissolve interstitial protons in yttria.     

Crystallographic Domain Structure of an Epitaxial (Pr0.7Ca0.3)MnO3 Thin Film Grown on a SrTiO3 Single Crystal Substrate

We characterized the structure of the crystallographic domain of a (Pr_0.7Ca_0.3)MnO₃ (PCMO ( x =0.3)) thin film epitaxially grown on a (001)SrTiO₃ (STO) single-crystal substrate. We found that the domain structure exhibited an atomically smooth coherent interface with the STO substrate with no misfit dislocations. The crystallographic relationships between the domains and the substrate in their planes were interpreted to be PCMO ( x =0.3)[110][001]//STO[100][010] and PCMO ( x =0.3)[001][1-10]//STO[100][010]. The domain structure of PCMO ( x =0.3)[110][1-10]//STO[100][010] has less possibility of having the larger anisotropic strain energy found in a monoclinically distorted pseudo-cubic perovskite unit cell of PCMO ( x =0.3). This epitaxial growth structure is totally different from the previously reported PCMO ( x =0.5) epitaxial thin-film structure on STO substrate. Our observations suggested that an x value change strongly influences the structure of epitaxial PCMO thin films.     

Electrical Conductivity of Heat-Treated SnO2 Films

Variations in electrical conduction which were caused by heat treatment of SnO₂ films vapor-deposited on glass were studied. In the range 20° to 230°C, the relative importance of semiconduction processes attributed to 3 types of donors (probably O vacancies, interstitial Sn ions, and Cl ions) was determined as a function of heat treatment. A decrease in conductivity at constant temperature above 230°C was ascribed to grain growth of the SnO₂ crystals deposited initially.     

Reaction Rates of BaTiO3 and SrTiO3

The temperature dependence of the reaction rates in a 50(BaTiO₃)-50(SrTiO₃) ceramic mixture (wt%) was studied by high-temperature X-ray diffraction. The data were fitted to two theoretical models and times for complete reactions and activation energy were calculated. Use of the results in electronic material applications is discussed.     

Oxygen Partial Pressure and Grain Growth in Donor-Doped BaTiO3

The grain growth of donor-doped BaTiO₃ at different oxygen partial pressures was studied. Results showed that the oxygen pressure had a pronounced influence on the grain growth and related effects. A model for the grain size anomaly during sintering of donor-doped BaTiO₃ in the presence of a TiO₂-rich liquid phase is proposed.     

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.     

Oxygen Activity Dependence of the Electrical Conductivity of Li-Doped Cr2O3

The electrical conductivity of Li-doped Cr₂O₃ was investigated as a function of PO₂, temperature, and dopant content. Results show that the electrical conductivity remains almost unchanged with decreasing P O₂ in the high-P O₂ region but decreases rapidly at low P O₂. A second phase was found in samples which contained more than 0.85 mol% Li. The results are explained by a model in which the concentration of charge carriers is dependent on the acceptor dopant and oxygen vacancy concentration.     

Multiferroic BiFeO3 Thin Films Buffered by a SrRuO3 Layer

Multiferroic BiFeO₃ thin films of huge polarization have been successfully realized by using SrRuO₃ as a buffer layer on a Pt/TiO₂/SiO₂/Si substrate. They consist of a single perovskite phase and are nearly randomly orientated, where the SrRuO₃ buffer layer lowers the crystallization temperature and improves the crystallinity of BiFeO₃. With increasing deposition temperature during magnetron sputtering, they undergo an apparent grain growth and reduction in surface roughness. The multiferroic thin films deposited on the SrRuO₃-buffered Pt/TiO₂/SiO₂/Si substrate at higher temperatures show much improved polarization and reduced coercive field, together with a lowered leakage current. A huge remnant polarization (2 P _r) of 150 μC/cm² and a coercive field (2 E _c) of 780 kV/cm were measured for the BiFeO₃ film deposited at 650°C.     

Distribution of Grain Boundaries in SrTiO3 as a Function of Five Macroscopic Parameters

Measurements of the grain boundary population as a function of misorientation and boundary plane orientation show that the distribution is inversely correlated to the sum of the energies of the surfaces comprising each boundary. The observed correlation suggests that the difference between the energy of a high-angle grain boundary and the two component surfaces is relatively constant as a function of misorientation. Two exceptions to this correlation were identified: low-misorientation-angle boundaries and the coherent twin boundary, where the (111) planes in the adjoining crystals are parallel to each other, but rotated by 60° around the [111] axis. In these cases, the high degree of coincidence across this interface probably lowers the boundary energy with respect to that of the component surfaces. For all other boundaries, the anisotropy of the population is accurately predicted by the surface energy anisotropy, and in general, boundaries display a preference for {100} orientations, the planes of minimum surface energy.     

Preparation and Characterization of Alkoxy-Derived SrZrO3 and SrTiO3

High-purity strontium, zirconium, and titanium alkoxides were synthesized and characterized as precursors for complex oxides. Simultaneous hydrolytic decomposition either of strontium and zirconium alkoxides or of strontium and titanium alkoxides was used to obtain nearly stoichiometric, ideally mixed SrZrO₃ or SrTiO₃ powders of high surface activity. As-prepared helium-dried SrTiO₃ is crystalline before calcination. An ultraviolet radiation technique demonstrates the nucleation and growth of SrZrO₃ crystallites in the calcination temperature range to 350°C. The experimental results are supported by ir, TGA, and X-ray diffraction data. The high degree of control over purity, mixing uniformity, and crystallite size demonstrates the value of the alkoxide precursor approach for the solution of reproducibility problems encountered in the synthesis of electrical-quality ceramics.     

Recrystallization of Oxygen Ion Implanted Ba0.7Sr0.3TiO3 Thin Films

The crystallization behavior of chemical-solution-deposited and amorphous Ba_0.7Sr_0.3TiO₃ (BST) thin films was analyzed with respect to the evolution of the structural and dielectric properties of the films as a function of the annealing temperature. The amorphous films were produced by oxygen ion implantation into crystalline BST thin films. In the amorphous thin films, the crystallization to the perovskite phase occurred at T = 550°C, whereas the as-deposited CSD films showed the first crystalline XRD-reflex only after annealing at T = 650°C. Here a carbon-rich intermediate phase delayed the crystallization process to higher temperatures.     

Oxidation Kinetics of Single-Crystal SrTiO3

The oxidation kinetics were determined for single-crystal SrTiO₃ by measuring the time and temperature dependence of the weight gain of reduced crystals. The oxidation can be described as a diffusion-controlled process. The calculated diffusion coefficients between 850° and 1460°C are represented by D = 0.33 exp (-22.5 ± 5.0 kcal/ RT ) cm²/sec. Directly measured oxygen ion diffusion coefficients in the same temperature interval reported earlier are interpreted as being extrinsic and can be represented by D = 5.2 × 10⁻⁶ exp (-26.1 ± 5.0 kcal/ RT ) cm²/sec, where the activation energy is for mobility only. Assuming that the calculated diffusion coefficients are for vacancy diffusion and the two activation energies are equivalent within experimental error, a vacancy concentration (fraction of vacant lattice sites), [O□], fixed by impurities in the fully oxidized crystal is calculated to be 1.6 × 10⁻⁵ by virtue of the relation between the oxygen self-diffusion coefficient, D_02-, and the oxygen vacancy diffusion coefficient, D_o□ ; D _o2-= [O□] D _o□ where the oxygen ion concentration [O^2-] is taken as unity.     

Microcontact Printed BaTiO3 and LaNiO3 Thin Films for Capacitors

There is an ongoing need to develop new technologies to enable further down-scaling of layer thicknesses in multilayer ceramic devices, for example, in multilayer capacitors (MLC). Microcontact printing of chemical solutions of both the dielectric and electrode layers was explored as an economical means of preparing patterned thin films for MLC without requiring photolithography. For this purpose, methanol/acetic acid-based BaTiO₃ solutions were spun onto polydimethylsiloxane stamps, printed onto substrates, pyrolyzed, and crystallized. LaNiO₃ was used as a prototype electrode that could also be microcontact printed. The line edge roughness produced this way was on the order of a tenth of a micrometer, which should enable very small margins. The printed layer thickness was also very uniform. Microcontact printed capacitors with a single dielectric layer were fabricated and found to have dielectric constants >800 with loss tangents <2%. Alignment between subsequent layers is readily achieved. Multilayer dielectric/electrode stacks could be fabricated without cracking or delaminations. Consequently, microcontact printing appears to be a viable potential means of preparing MLC with layer thicknesses in the range of ≤0.2 μm.     

Sintering of UN as a Function of Temperature and N2 Pressure

The sintering of uranium mononitride (UN) depends on temperature and the N₂ pressure maintained over the nitride during heat treatment. At a given temperature, an N₂ pressure that maintained the UN in the single-phase region slightly above the phase boundary where the reaction UN→U+½N₂(g) occurred was most effective in accelerating the sintering of single-phase UN. For example, specimens sintered at 1600°C under N₂ pressures of either 1140 or 1.7XlO⁻⁴ torr had essentially identical compositions, but the density of the former was 10.78 g/cm³ (75% of theoretical), whereas that of the latter was 12.20 g/cm³ (85% of theoretical). Results were similar at temperatures up to 2100°C. The X-ray lattice constant of UN sintered at reduced N₂ pressures was slightly larger than that of UN sintered in 1140 torr of N₂. The observed constants ranged from 4.88904 to 4.88991 Å; the combined O+C content varied from 400 to 900 ppm.     

Sol–Gel Fabrication of Epitaxial and Oriented TiO2 Thin Films

Thin films of titania have been prepared by spin coating on fused silica, Si(100), and rutile(110), starting with a sol–gel process. The alkoxide solution was chelated with diisopropanolamine, and the resulting precursor solution was hydrolyzed prior to coating. Oriented rutile films were obtained on fused silica and Si(100), while epitaxially oriented film was formed on rutile (110). X-ray diffraction results indicated that the as-deposited films transformed to rutile via anatase with increasing temperature. The phase transformation temperature was found to be dependent on the substrate, and it was in general higher on the substrates than that observed for the gel powder. Microstructural studies revealed that these films consisted of finely dispersed grains of 0.05 to 0.15 μm in size.