Electrical Conduction in Single-Crystal and Polycrystalline Al2O3 at High Temperatures

The electrical conductivity and ion/electron transference numbers in Al₃O₃ were determined in a sample configuration designed to eliminate influences of surface and gas-phase conduction on the bulk behavior. With decreasing O₂ partial pressure over single-crystal Al₂O₃ at 1000° to 1650°C, the conductivity decreased, then remained constant, and finally increased when strongly reducing atmospheres were attained. The intermediate flat region became dominant at the lower temperatures. The emf measurements showed predominantly ionic conduction in the flat region; the electronic conduction state is exhibited in the branches of both ends. In pure O₂ (1 atm) the conductivity above 1400°C was σ≃3×10³ exp (–80 kcal/ RT ) Ω⁻¹ cm⁻¹, which corresponds to electronic conductivity. Below 1400°C, the activation energy was <57 kcal, corresponding to an extrinsic ionic condition. Polycrystalline samples of both undoped hot-pressed Al₂O₃ and MgO-doped Al₂O₃ showed significantly higher conductivity because of additional electronic conduction in the grain boundaries. The gas-phase conduction above 1200°C increased drastically with decreasing O₂ partial pressure (below 10⁻¹⁰ atm).     

Electrical Conductivity of Epitaxial SrTiO3 Thin Films as a Function of Oxygen Partial Pressure and Temperature

SrTiO₃ (100) epitaxial films with thicknesses of 3, 1 μm, and 250 nm were prepared on MgO (100) substrates by pulsed-laser deposition. The electrical conductivities of the thin films were systematically investigated as a function of temperature and ambient oxygen partial pressure. This was made possible by using a specially designed measurement setup, allowing the reliable determination of resistances of up to 25 GΩ in the temperature range of 600°–1000°C under continuously adjustable oxygen partial pressures ranging from 10⁻²⁰ to 1 bar. The capabilities of the measurement setup were tested thoroughly by measuring a SrTiO₃ single crystal. The well-known characteristics, e.g., the decline of the conductivity with a slope of –1/4 under reducing conditions and the opposite +1/4 behavior in oxidizing atmospheres, are found in the log(σ)–log( p O₂) profiles of the epitaxial films. However, the p -type conductivity decreases, and the n -type conductivity increases with decreasing film thickness. This phenomenon is attributed to the charge carrier redistribution in the surface space charge layers. Owing to the high surface-to-volume ratio, the space charge layers play an important role in thin films.     

High-Dielectric-Constant and Low-Loss Microwave Dielectric in the (1−x)Nd(Zn1/2Ti1/2)O3–xSrTiO3 System with a Zero Temperature Coefficient of Resonant Frequency

High-dielectric-constant and low-loss ceramics in the (1− x )Nd(Zn_1/2Ti_1/2)O₃– x SrTiO₃ system have been prepared by the conventional mixed-oxide route and their microwave dielectric properties have been investigated. A two-phase system was confirmed by the X-ray diffraction patterns, the energy-dispersive X-ray spectrometer analysis, and the measured lattice parameters. Addition of SrTiO₃, having a much smaller grain size in comparison with that of Nd(Zn_1/2Ti_1/2)O₃, could effectively hold back abnormal grain growth in the Nd(Zn_1/2Ti_1/2)O₃ matrix. Evaporation of Zn at high temperatures caused an increase in the dielectric loss of the system. The temperature coefficient of resonant frequency increases with increasing SrTiO₃ content and tunes through zero at x =0.52. Specimens with x =0.52 possessed an excellent combination of microwave dielectric properties: ɛ_r∼54.2, Q × f ∼84 000 GHz, and τ_f∼0 ppm/°C. It is proposed as a suitable candidate material for today's 3G passive components and small-sized GPS patch antennas.     

Effects of Palladium Dispersions on Gas-Sensitive Conductivity of Semiconducting Ga2O3 Thin-Film Ceramics

The gas sensitivity of Ga₂O₃ thin-film n -type conductors was investigated at temperatures of 500–1000°C. Palladium dispersions whose particle sizes are dependent on the preceding annealing processes were deposited by a wet-chemical technique onto Ga₂O₃ thin-film ceramics. The palladium clusters and their temperature-dependent growth were detected using scanning electron microscopy micrographs and X-ray photoemission spectroscopy measurements. The effect of the palladium dispersions on the gas-sensitive behavior of the Ga₂O₃ ceramics was investigated in various O₂/H₂ mixtures in the N₂ carrier gas at 700°C. The conductivity of the ceramics treated in this way was dependent on the O₂ partial pressure, as well as on the H₂ partial pressure of the surrounding gas atmosphere. The ceramic conductivity can be described as a function of the O₂:H₂ ratio, in accordance with the relation σ( p O₂/ p H₂/)^−1/3.     

Thermodynamics of CuAlO2 and CuAl2O4 and Phase Equilibria in the System Cu2O-CuO-Al2O3

The standard Gibbs free energies of formation of CuAlO₂ and CuAl₂O₄ were determined in the range 700° to 1100°C, using emf measurements on the galvanic cells (1) Pt,CuO +] Cu₂O/CaO-ZrO₂/O₂,Pt; (2) Pt,Cu +] CuAlO₂+] Al₂O₃/CaO-ZrO₂/ Cu +] Cu₂O,Pt; and (3) Pt,CuAl₂O₄+] CuAlO₂+]Al₂O₃/CaO-ZrO₂/O₂,Pt. The results are compared with published information on the stability of these compounds. The entropy of transformation of CuO from tenorite to the rock-salt structure is evaluated from the present results and from earlier studies on the entropy of formation of spinels from oxides of the rock-salt and corundum structures. The temperatures corresponding to 3-phase equilibria in the system Cu₂O-CuO-Al₂O₃ at specified O₂ pressures calculated from the present results are discussed in reference to available phase diagrams.     

Hole Mobility in Acceptor-Doped, Monocrystalline SrTiO3

The oxidation reaction equilibrium constant and the holes mobility in p -type-semiconducting SrTiO₃ single crystals were determined directly by simultaneous Hall and conductivity measurements between 500° and 1000°C. This information and the SrTiO₃ defect model were used to interpret the electrical measurements taken on this substance which represents a model substance for semiconducting perovskites. Measurements with varying oxygen partial pressures showed that shifts of the crystal defect equilibrium give rise to changes in the carrier concentration with unchanged carrier mobility.     

Electronic Conductivity, Seebeck Coefficient, and Defect Structure of LaFeO3

Electronic conductivity and Seebeck coefficients of LaFeO₃ were measured as a function of temperature (1000° to 1400°C) and P ( O ₂) (10⁵ to 10⁻¹³ Pa). Electronic conduction was found to be n-type in the lower P ( O₂ ) range, and p -type in a higher P(O₂) range. The calculated carrier mobilities suggest a hopping-type conduction mechanism. The carrier concentrations were calculated as a function of P ( O₂ ) and the defect structure was described. It was found that the electrical properties of LaFeO₃ are determined not only by the concentration of oxygen vacancies, but also by the La/Fe ratio.     

Ti-Rich Nonstoichiometric BaTiO3: I, High-Temperature Electrical Conductivity Measurements

Equilibrium electrical conductivity of nonstoichiometric poly-crystalline BaTiO₃ with varying Ba:Ti ratios was investigated at temperatures between 800° and 1200°C and P o₂ from 10⁻²² to I atm. A transition from p -type to n -type conductivity was observed. Although the electrical conductivity of different specimens varied slightly, these differences did not appear to be a function of the Ba:Ti ratio in the region investigated. An intrinsic band-gap energy of ∼3.1 eV was calculated from the temperature dependence of the minimum conductivity. The O₂ partial pressure dependence of the isothermal n -type conductivity cannot be described by simple defect models incorporating only singly or doubly ionized O vacancies. Likewise, simple defect models incorporating cation vacancies are not consistent with the observed pressure dependence of the p -type conductivity. More complex defect models which correspond to the observed behavior over the entire range of temperature and P o₂ will be discussed in a subsequent paper.     

Reverse Micellar Route to Nanocrystalline Titanates (SrTiO3, Sr2TiO4, and PbTiO3): Structural Aspects and Dielectric Properties

Nanoparticles of strontium titanates (SrTiO₃, Sr₂TiO₄) and lead titanate (PbTiO₃) have been obtained using reverse micelles as nanoreactors. Powder X-ray diffraction studies of the powders after calcining at 800°C show monophasic SrTiO₃, Sr₂TiO₄, and PbTiO₃. X-ray line broadening studies and transmission electron microscopic studies show spherical grains of 30–40 nm size for strontium titanates, while PbTiO₃ is obtained in the form of nanorods. The dielectric constant of SrTiO₃ and Sr₂TiO₄ is found to be 90 and 30, respectively, (at 100 kHz) for samples sintered at 1000°C. PbTiO₃ shows a dielectric constant of 160 (at 100 kHz) after sintering at 900°C. The dielectric constant of Sr₂TiO₄ (with temperature) is highly stable. The temperature variation studies of the dielectric constant of PbTiO₃ show a ferroelectric phase transition at 490°C (1 kHz). The T _c varies with frequency and is found to decrease to 470°C at 100 kHz.     

Effect of Oxide Defect Structure on the Electrical Properties of ZrO2

The defect structure of monoclinic ZrO₂ was studied by measuring the transfer numbers and electrical conductivity as functions of O₂ pressure and temperature. The data suggest a defect structure of doubly ionized oxygen vacancies at low pressures, i.e. <10⁻¹⁹ atm, and singly ionized oxygen interstitials at pressures >10⁻⁹ atm. Zirconia is primarily an ionic conductor below #700°C and an electronic conductor at 700° to 1000°C for 10⁻²²≤P_o2≤1 atm.     

Low Loss Dielectrics in the Ca(B'1/2Nb1/2)O3 [B'=Lanthanides, Y] System

The Ca(B'_1/2Nb_1/2)O₃ [B'=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Yb, and In] complex perovskites have been prepared by conventional solid-state ceramic route. The structure and microstructure of the ceramics have been characterized by X-ray diffraction and scanning electron microscopy methods. The ceramics have dielectric constant (ɛ_r) in the range 23–32, normalized Q -factor ( Q _u× f ) 11 000–38 000 GHz and temperature coefficient of resonant frequency (τ_f) −43–5.2 ppm/°C. The microwave dielectric properties of Ca(B'_1/2Nb_1/2)O₃ ceramics are found to depend on the ionic radii of B'-site elements and tolerance factor ( t ). The substitution of Ba²⁺ and Sr²⁺ for Ca²⁺ resulted a phase transition in Ca(B'_1/2Nb_1/2)O₃ ceramics. The (Ca_0.05Ba_0.95) (Y_1/2Nb_1/2)O₃ has τ_f close to zero (1.2 ppm/°C) with ɛ_r=35 and Q _u× f =48 500 GHz and is proposed as a useful material for base station applications. Dielectric properties of the Ca(B'_1/2Nb_1/2)O₃ ceramics were tailored by the addition of TiO₂ and CaTiO₃.     

Co2+-Substitution Effect in Ce-TZP/La M-type Hexaferrite Composites

A Ce-TZP/platelike La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ composite was synthesized in situ while sintering from a mixture of Ce-TZP, La(Fe_0.9Al_0.1)O₃, Fe₂O₃, Al₂O₃, and CoO powders. Platelike La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ crystals were grown in a dense Ce-TZP matrix after sintering at temperatures of 1200°–1350°C. The temperature range for sintering Ce-TZP/La(Fe,Al)₁₂O₁₉ composites was expanded widely by substituting Co²⁺ ions for Fe²⁺ ions in its structure. The highest value of the bending strength of the Ce-TZP/La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ composites was 880 MPa, which was higher than that of the Ce-TZP/La(Fe,Al)₁₂O₁₉ composite (780 MPa) and Ce-TZP (513 MPa). The saturation magnetization of the Ce-TZP/La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ composite was a constant value of 7.7 emu/g after the composite was sintered at 1200°–1350°C.     

High-Temperature Defect Structure of Cobalt-Doped α-Alumina

Room-temperature optical absorption spectra, electron spin resonance spectra at 15° to 18°K, electrical conductivity, and emf measurements on concentration cells at 1620°C are analyzed and used to determine the defect structure of Codoped α-Al₂O₃. The crystals are mixed ionic and electronic conductors at 1620°C: ionic conduction occurs at 10^-8 atm< p O₂ < 10_-3 atm, with triply charged interstitial Al ions as the major charge carriers, and electronic conduction occurs at 10^-3 atm < p O₂ < 1 atm, with holes as the major charge carriers. A defect model based on the charge compensation of divalent Co at Al sites by triply charged Al interstitials is proposed. The mobilities and activation energy of ions and holes, the oscillator strengths of Co²⁺ and Co³⁺ absorption bands, parameters for electron spin resonance spectra, level positions of substitutional Co²⁺ and an unknown donor, and equilibrium constants for defect formation reactions are determined.     

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.     

Electrochemical Determination of the Gibbs Energy of Formation of MgAl2O4

The standard Gibbs energy of formation of the spinel MgAl₂O₄ from component oxides, MgO and α-Al₂O₃, has been determined in the temperature range 900 to 1250 K using a solid-state cell incorporating single-crystal CaF₂ as the solid electrolyte. The cell can be represented as—Pt,O₂,MgO+MgF₂|CaF₂|MgF₂+MgAl₂O₄+α-Al₂O₃,O₂,Pt—The standard Gibbs energy of formation from binary oxides, computed from the reversible emf, can be represented by the expression—capdelta G °_f,ox=−23600 − 5.91 T (±150) J/mol—The 'second-law' enthalpy of formation of MgAl₂O₄ obtained in this study is in good agreement with high-temperature solution calorimetric studies reported in the literature.     

Synthesis of Highly Oriented Lead Zirconate–Lead Titanate Film Using Metallo-organics

Crack-free Pb(Zr,Ti)O₃ (PZT) thin films with preferred orientation were prepared successfully on MgO (100), SrTiO₃ (100), and Pt/Ti/SiO₂/Si substrates from metal alkoxide solutions. Calcination of precursor films in a H₂O─-O₂ gas mixture was found to be effective not only for low-temperature crystallization of perovskite PZT, but also for obtaining the preferred orientation of PZT films. Single-phase PZT films with high preferred orientation were synthesized on MgO (100) and Pt/Ti/SiO₂/Si substrates at 550° and 600°C for 2 h, respectively. The PZT film on the Pt/Ti/SiO₂/Si substrate showed a permittivity of 520, tan δ of 0.03, a remanent polarization of 24 μC/cm², and a coercive field of 54 kV/cm.     

Phase Equilibrium Studies in the System Iron Oxide-Al2O3-Cr2O3

Subsolidus phase relations in the system iron oride-Al₂O₂-Cr₂O₃ in air and at 1 atm. O₂ pressure have been studied in the. temperature interval 1250° to 1500°C. At temperatures below 1318° C. only sesquioxides with hexagonal corundum structure are present as equilibrium phases. In the temperature interval 1318° to 1410°C. in air and 1318° to 1495° C. at 1 atm. O₂, pressure the monoclinic phase Fe₂O₃. Al₂O₃ with some Cr₂O₃ in solid solution is present in the phase assemblage of certain mixtures. At temperatures above 1380°C. in air and above 1445°C. at 1 atm. O₂ pressure a complex spinel solid solution is one of the phases present in appropriate composition areas of the system. X-ray data relating d- spacing to composition of solid solution phases are given.     

Electrical Properties of β-LixV2O5 Thin Layers Prepared by the Sol—Gel Process

The electrical properties of a highly oriented thin layer of lithium vanadium beta bronze, β-Li_xV₂O₅, were investigated through dc and ac conductivity measurements. The ionic transference number was determined by a simplified polarization method employing ion-blocking electrodes. The electronic conductivity was 10 ^–3to 10^–2 S cm^–1 in air or N₂ at 300–400°C, which was lower than that of a randomly oriented sintered specimen. The ionic conductivity was l0^–2–10^–1s cm^–1 at 350°C, resulting in a high ion transference number of 0.8–0.9; it was higher than that reported for a bulk specimen. The lower electronic conductivity and higher ionic conductivity were assumed to be due to (1) the oriented microstructure, i.e., alignment of the b -axis along the substrate direction which enhanced Li⁺ conduction through tunnels along the b -axis, and (2) an open crystallo-graphic structure, which promoted ionic motion in an open channel between adjacent ( a-c ) places and suppressed the electron hopping process in the b -axis direction.     

Defect Structure of Ta2O5

Electrical conductivity, thermoelectric power, and weight change were measured for polycrystalline Ta₂O₅ from 900° to 1400°C. The predominant ionic and electronic defects in this temperature range are oxygen vacancies and electrons. The oxygen-vacancy and electron mobilities are 8.1 × 10³exp (−1.8 eV/ k T) and ∼0.05 cm²/V-s, respectively. At O₂ partial pressures near 1 atm, the ionic-defect concentration is essentially fixed by the presence of lower-valence cation impurities, and the total electrical conductivity is predominantly ionic, whereas at low P _o2's the conductivity is electronic and proportional to P P _o2^−1/6.     

Effects of Trace O2 Levels on the Nitriding Kinetics of High-Purity Silicon Powders

The effects of trace O₂ levels on the nitridation of compacts made from silane-derived Si powders were studied in N₂ atmospheres, with oxygen levels of either 5 ppm or 10 ppb (approximately). The nitriding kinetics were studied by thermogravimetric analysis as a function of temperature (1100–1200°C) and heating rate (5°C/min and 100°C/min). Reducing the O₂ level in the nitriding gas enhanced conversion to Si₃N₄ at lower temperatures, reduced the composition variations within the samples, and decreased the α/β ratios. The results suggest that nucleation and rapid growth of Si₃N₄ at relatively low temperatures are possible only when the oxygen partial pressure in the system is below the threshold value for passive oxidation.