Electrical Properties and Defect Structure of Y2O3

Guarded measurements of the electrical conductivity of high-purity, polycrystalline Y₂O₃ in thermodynamic equilibrium with the gas phase were made under controlled temperature and oxygen partial pressure conditions. Data are presented as isobars from 1200° to 1600°C, and as isotherms from oxygen partial pressures of 10⁻¹ to 10⁻¹⁷ atm. The ionic contribution to the total conductivity, determined by the blocking electrode polarization technique, was less than 1% over the entire range of temperatures and oxygen partial pressures studied. Yttria is shown to be an amphoteric semiconductor with the region of predominant hole conduction shifting to higher pressures at higher temperatures. In the region of p -type conduction, the conductivity is represented by the expression σ= 1.3 × 10³ p O₂^3/16 exp (-1.94/kT). The observed pressure dependence is attributed to the predominance of fully ionized yttrium vacancies. Yttria is shown to be a mixed conductor below 900°C.     

Electrical Conduction in Sintered α-Sb2O4

Electrical conductivity and thermoelectric power were measured on sintered α-Sb₂O₄ at 250° to 780°C. Oxygen partial pressure dependence of the conductivity and sign of the Seebeck coefficient showed α-Sb₂O₄ to be a p -type semiconductor above 600°C in the oxygen pressure range of lo⁵ to 10² Pa. A hopping conduction was proposed from very small hole mobility with an activation energy of 18 kJ/mol.     

Electrical Properties and Defect Structure of HfO2

The defect structure of high-purity, polycrystalline HfO₂ was investigated by measuring the oxygen partial pressure dependence of the electrical conductivity and the sample weight. From 1000° to 1500°C and above oxygen partial pressures of 10 ⁻⁶, the conductivity is electronic and proportional to p o₂^1/5. The predominant defect is completely ionized hafnium vacancies. At lower oxygen partial pressures a broad shallow minimum in the lower temperature conductivity isotherms indicates the presence of an oxygen pressure independent source of electronic charge carriers. By combining the weight change and conductivity data, mobility values were found to vary from 1.6 × 10⁻³ to 3 × 10⁻⁴ cm²/V-sec. The activation energies for the hole mobilities were calculated to be 0.2 ev above 1300° C and 0.7 ev below this temperature.     

Electrical Properties and Defect Structure of a (0.13YO1.5·0.87ThO2) Electrolyte

High-density sintered disks of the composition 0.13YO_1.5·0.87ThO₂ are shown to be mixed conductors at high oxygen pressures (>10⁻⁶ atm) by electrical conductivity and electrochemical cell measurements. The ac and dc conductivity measurements were made between 900° and 1600°C over a wide range of oxygen partial pressures. A blocking-electrode polarization technique for determining transference numbers was not applicable at high oxygen pressures but appeared to work at the lower pressures, indicating a transition to n -type behavior. The electrochemical cell measurements show essentially completely ionic behavior at low oxygen pressure but indicate at least 0.1% electronic contribution at 10⁻¹³ atm at 1000°C. The lower oxygen pressure limit for completely ionic behavior has not been determined but extends below the equilibrium pressures of an Mn-MnO₂, Cr-Cr₂O₃ electrochemical cell at 1000°C.     

Electrical Properties of Single-Crystal and Polycrystalline Alumina at High Temperatures

The electrical conductivity of single-crystal and polycrystalline aluminum oxide has been measured over the temperature range 1300° to 1750°C. and at oxygen partial pressures of 10° to 10⁻¹⁰ atmospheres. Alumina exhibits p- type conductivity at high oxygen pressures and n -type conductivity at low oxygen pressures. The variation of conductivity with temperature depends on the specimen purity, oxygen pressure, and temperature level. Activation energies varying between 2.6 and 5.8 e.v. were found. The conductivity of alumina does not result from any single simple process over wide ranges of temperature and oxygen partial pressure. Apparently intrinsic conduction is found for single crystals at temperatures above 1600°C.     

Electrical Conduction in β-Bi2O3 Doped with Sb2O3

Electrical conduction in tetragonal β-Bi₂O₃ doped with Sb₂O₃ was investigated by measuring electrical conductivity, ionic transference number, and Seebeck coefficient. The β-Bi₂O₃ doped with 1 to 10 mol% Sb₂O₃ was stable up to 600°C and showed an oxygen ionic and electronic mixed conduction, where the electron conduction was predominant at low oxygen pressures. The oxygen-ion conductivity showed a maximum at 4 mol% Sb₂O₃, whereas the activation energy for the ionic conduction remained unchanged for 4 to 10 mol% Sb₂O₃-doped specimens. These results were interpreted in terms of the oxygen vacancy concentration and the distortion of the tetragonal structure. The electron conductivity and its oxygen pressure dependence decreased with increasing Sb₂O₃ content. The fact that Sb⁵⁺ is partially reduced by excess electrons in heavily doped β specimens at low oxygen pressures is explained.     

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.     

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.     

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.     

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 the Solid Solutions XNiO + (1 − X)Tm2O3 (0.01 X 0.05)

NiO-doped Tm₂O₃ systems (NDT) containing 1, 3, and 5 mol% NiO were found to be solid solutions by X-ray diffraction (XRD) analysis. The lattice parameters ( a ) were obtained by the Nelson-Riley method, and the values decreased with increasing dopant content. Thermal analysis showed that no phase transition occurred in the temperature range covered in this experiment. The electrical conductivities were measured in the range of temperatures from 400° to 1100°C and of oxygen partial pressures from 1 × 10⁻⁵ to 2 × 10⁻¹ atm. The conductivity increases with temperature but there is a break in the conductivity curve, dividing it into two temperature regions. At the high temperatures of 700° to 1100°C, the activation energy ( E_a ) and oxygen partial pressure dependence of conductivity are found experimentally to be 1.4 to 1.5 eV and 1/ n = 1/5.4, and the possible defects and charge carriers are suggested to be metal vacancies and electron holes, respectively. At the lower temperatures of 400° to 600°C, the E_a and 1/ n values obtained are 0.8 to 0.9 eV and 1/ n = 1/7.2 to 1/8.8, respectively. At the lower temperature, the NDT system seems to display a mixed conduction involving ionic conductivity due to diffusion of oxygen.     

High-Temperature Hall Measurements on BaSnO3Ceramics

Simultaneous Hall and conductivity measurements were performed in situ between 650° and 1050°C on n-type semiconducting BaSnO₃ceramics. The variation of the Hall mobility and the Hall carrier density as a function of oxygen partial pressure between 10² and 10⁵ Pa and of temperature was investigated. At temperatures below 900°C the conductivity exhibits a dependence on temperature and oxygen partial pressure which is mainly determined by variations of the Hall mobility. Above 900°C most of the significant dependence is due to a variation in carrier density. Furthermore, a simple defect model assuming doubly ionized oxygen vacancies and acceptor impurities is discussed for BaSnO₃.     

Oxygen Pressure Effect on the Y2O3—Bao—Cuo Liquidus

Concurrent DTA, TGA, and oxygen pressure measurement were used to determine liquidus temperature for compositions near YBa₂Cu₃O_x. Liquidus temperatures were measured for oxygen partial pressures from 2 × 10⁻⁴ to 1 bar. Liquidus temperatures decreased for lowered oxygen pressure. The ternary eutectic is 930°C for 1 bar and 854°C for 0.02 bar oxygen pressure. Incongruent melting of YB₂Cu₃O_xoccurs at 1034°C for 1 bar and 938°C for 2 × 10⁻⁴ bar oxygen pressure. Some implications for processing are also discussed.     

Electrical Conductivity of the High-Temperature Proton Conductor BaZr0.9Y0.1O2.95

The impedance of the cubic perovskite BaZr_0.9Y_0.1O_3-δ has been systematically investigated in dry and wet atmospheres at high and low oxygen partial pressures. In the grain interior, conductivity contributions from oxygen ions, electron holes, and protons can be identified. Below 300°C, proton conduction dominates and increases linearly with the frozen-in proton concentration. The proton mobility, with an activation energy of 0.44 ± 0.01 eV is among the highest ever reported for a perovskite-type oxide proton conductor. For dry oxygen atmos-pheres, electron hole conduction dominates with an activation energy of ∼0.9 eV. At temperatures <500°C, the grain-boundary conductivity can be separated and increases upon incorporation of protons. The high electrical conductivity and chemical stability make acceptor-doped barium zirconate a good choice for application as a high-temperature proton conductor.     

Oxidation of Si3N4 in the Range 1300° to 1500°C

The isothermal oxidation behavior of commercial hot-pressed Si₃N₄ was evaluated for temperatures from 1300° to 1500°C. Multiphase scales were formed, consisting mainly of α-cristobalite and enstatite. A large increase in reaction rate above 1450°C is believed to be caused by melting in the scale and the consequent increase in the rate of oxygen transport. No oxygen pressure dependence was observed at 1400°C over the oxygen pressure range 10^-9 atm to 600 torr. However, a small decrease in the kinetics was observed when measurements were made in reduced total pressures of oxygen as compared to O₂/N₂mixtures at a constant total pressure.     

Nonstoichiometry in Undoped BaTiO3

Equilibrium electrical conductivity data for large-grained, poly crystalline, undoped BaTiO₃, as a function of temperature, 750° to 1000°C, and oxygen partial pressure, 10⁻²⁰< P _O2<10⁻¹ MPa, were quantitatively fit to a defect model involving only doubly ionized oxygen vacancies, electrons, holes, and accidental acceptor impurities. The latter are invariably present in sufficient excess to control the defect concentrations through the compensating oxygen vacancies, except under the most severely reducing conditions. Singly ionized oxygen vacancies play no discernible role in the defect chemistry of BaTiO₃ within this experimental range. The derived accidental acceptor content has a slight temperature dependence which may reflect some small amount of defect association. Deviation of the conductivity minima from the ideal shape yields a small P _O2-independent conductivity contribution, which is tentatively identified as oxygen vacancy conduction.     

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.     

Electrical Properties of Ceria-Doped Yttria

The electrical conductivity and ionic domain of several ceriadoped yttria compositions, with up to 10 cation% dopant, were studied as a function of temperature (800° to 1100°C) and oxygen partial pressure (10⁻¹⁵ to 10⁵ Pa). The ionic conduction in ceria-doped yttria involves the transport of interstitial oxygen ion defects. The increase of electronic conductivity under reducing conditions with increasing dopant concentration suggests hopping of small polarons between cerium ions with different valences as the dominant conduction mechanism.     

Electrical Conductivity of Pure and Yttria-Doped Uranium Dioxide

The conductivities of both pure urania and urania doped with <10 mol% yttrium were measured as a function of the oxygen partial pressure between 800° and 1400°C. Yttrium enhances the p -type electronic conductivity for near-stoichiometric oxygen concentrations, allowing the hole mobility to be determined as μ=(5547/ T ) exp(-0.032 aJ/ k T) cm²/Vs, confirming a small polaron transport model. Using this mobility, the hole concentration in pure urania was calculated as a function of the degree of nonstoichiometry and temperature and then compared to models for the formation of defect clusters. Increasing numbers of mobile holes created per excess oxygen ion with increasing temperature indicate that the holes must dissociate from the oxygen defect clusters at high temperature and suggest that the oxygen defects may dissociate as well.     

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