Solid State Properties of Some Valve Metal Oxides

Vijh, Ashok K.

doi:10.1149/1.2411845

Cited by 14 publications

(12 citation statements)

References 4 publications

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“…Ge), the lattice energy has no significance, i.e., Im and Ax in Eq. Now we note, as has been shown elsewhere (6), that the various fundamental properties, e.g., mp, bp, of several valve metal oxides increase systematically with increasing bond energy and decreasing lattice energy. [8] with [12], we write WL ~_ bond energy [13] i.e., the work for hole formation for a covalent crystal is roughly equal to the bond energy.…”

Section: Wl = ~H~ + Ahsub -T-~ Ahdiss -~-Im -~-Axsupporting

confidence: 77%

“…[6] that the Tafel slope would change with bond energy (Fig. [6] that the Tafel slope would change with bond energy (Fig.…”

Section: Discussionmentioning

confidence: 99%

“…The rates of exchange and self diffusion of sodium in beta-alumina (A ----Na and M = A1) are very large (1) and comparable large alkali ion mobilities have been ooserved in hexagonal ferrites where A ~ Na, K and M = Fe a+ (2). X-ray and magnetic studies (5,6) showed that the beta-alumina form of potassium ferrite was stable above ll00~ but that between 900 ~ and 1100 ~ there was a potassium-rich phase with approximate composition KFe7Oll. The atomic arrangement of NaAlllOlv was described by Beevers and Ross (3) and Braun reported that KFe110~7 crystallized in the same structure (4).…”

Section: Electrical Conductivity Of Potassiummentioning

confidence: 99%

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Influence of Bond Energies of Oxides on the Kinetics of Anodic Oxide Growth on Valve Metals

Vijh¹

1969

J. Electrochem. Soc.

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Average bond energy values have been calculated for the oxides of Bi, V, U, Y, Nb, Zr, Ti, W, Ta, AI, Hf, and Si from the appropriate thermochemical data. An attempt has been made to explore the influence of these bond energies on the magnitude of kinetic parameters for the anodic oxide growth on the corresponding metals. It has been concluded that, in general, with increasing bond energy, the field required for sustaining a given ionic current density tends to increase, as also does the "Tafel slope." Further, the magnitude of the "activation dipole" in Dignam's theory, both for the steady-state and the transient kinetics, tends to decrease with increase in bond energy.

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Section: Wl = ~H~ + Ahsub -T-~ Ahdiss -~-Im -~-Axsupporting

confidence: 77%

“…[6] that the Tafel slope would change with bond energy (Fig. [6] that the Tafel slope would change with bond energy (Fig.…”

Section: Discussionmentioning

confidence: 99%

Section: Electrical Conductivity Of Potassiummentioning

confidence: 99%

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Influence of Bond Energies of Oxides on the Kinetics of Anodic Oxide Growth on Valve Metals

Vijh¹

1969

J. Electrochem. Soc.

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“…The relationship between VFB and fixed surface charge density NFC, is given by N~cq L VFB : ~MS [13] RE o where ~MS is the work function difference between the metal and the semiconductor, q is the charge on the electron, the other quantities have been defined previously. Figure 16 shows the VFB dependence on thickness, where the data were obtained on a single slice exhibiting a thickness gradient.…”

Section: Metal-insulator-semiconductor (Mis) Propertiesmentioning

confidence: 99%

“…Figure 16 shows the VFB dependence on thickness, where the data were obtained on a single slice exhibiting a thickness gradient. The straight-line dependence predicted by [13] The distribution of interface states in the band gap was measured using the quasi-static technique developed by Kuhn (30). Figure 17 is a plot showing the distribution of interface states (Nss in cm -~ eV-1).…”

Section: Metal-insulator-semiconductor (Mis) Propertiesmentioning

confidence: 99%

Preparation and Properties of Pyrolytic Zirconium Dioxide Films

Tauber¹,

Dumbri²,

Caffrey³

1971

J. Electrochem. Soc.

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Zirconium dioxide (ZrO2) films in the thickness range of 500-8000A havc been prepared by chemical vapor deposition in the temperature range of 800 ~ 1000~ The films were identified as fine-grained (~325A), nearly stoichiometric, monoclinic ZrO2, using electron microprobe analysis, infrared absorption, and transmission electron microscopy. The films exhibited r e m a r kable resistance to most aqueous acids and bases, although slight etching occurred in hot (220~ phosphoric acid. The deposits had an index of refraction of 2.1 -+ 0.1 at 546 nm and an optical energy gap of 5.12 eV. ZrO2 deposited on silicon offered little resistance to Na diffusion at 600~ while films deposited on thermal SiO2 were a good barrier due to pile-up of the Na near the ZrO2/SiO2 interface. The current density, J, depended on the field, E, as J -~ A E n, where n was 6 for the metal biased negatively and 2.75 or 5, depending on the magnitude of the field, for the opposite polarity. The dielectric constant in the frequency range of 5 x 10 S to 1 x l0 s Hz was relatively independent of frequency near 300~ and equal to approximately 18, however some dispersion was noted near 573~ The a-c conductivity could be represented by =ac ~ Cy~ where 5 is the measuring frequency and ~ a temperature dependent parameter, decreasing from ~1 at 300~ to ~0.5 at 573~ The dielectric strength of the films varied between 1 to 2 x 106 V/cm, independently of thickness and polarity. High frequency (1 MHz) C-V measurements indicated the presence of negative surface charge, which varied between --6 x 10 n to --1 x 1012 cm -2. The structures exhibited instability under negative bias, indicative of negative charge being injected into the insulator. C-V measurements on the double dielectric system (ZrO2/SiO2) showed that the presence of ZrO2 caused a flatband voltage displacement ~ +0.8V. In addition, the flatband voltage shifted as a function of time under negative bias and was found to obey the relationship aVFB -'-K log t.Recent developments in microelectronics, such as integrated circuit passivation and IGFET technology, have engendered extensive research in the preparation and characterization of insulating thin films (1). Much of the effort has been directed to SiO2, SlaY4, and Al203. Recently, alternatives to these materials have been sought. TiO2 (2) and Nb205 (3) have been investigated. It has been found that chemical vapor deposition (CVD) in the temperature range of 600 ~ 1000~ produces films with the most desirable properties for the above applications.A refractory oxide that has not been investigated in detail is zirconium dioxide (ZrO2). T h i s material is characterized by low electrical conductivity and extreme chemical inertness. Much of the information available on ZrO2 has been obtained on relatively impure bulk, sintered material. This paper reports on the preparation of ZrO2 films by CVD, and a survey of the optical, chemical, electrical, and interfacial properties of the resulting films. Film PreparationThe preparation of oxide films by CVD has been...

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Passivity of Metals, Alloys, and Semiconductors

Schultze

Hassel

2003

Encyclopedia of Electrochemistry

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The sections in this article are Introduction Definition of Passivity Survey of Systems General Principles of Passivity Thermodynamics and Bond Polarity Experimental Techniques for Characterization of Passive Films Thickness and Stoichiometry of Passive Films Chemistry, Crystal Structure and Aging Chemistry and Crystal Structure Aging Potential Distribution at the Interface Electrochemical and Chemical Reactions in Passive Systems Reactions Current Densities i Ionic Properties, Migration and Ion‐Transfer Reactions Electronic Behavior and ETR Band Structure of Oxide Films Electron‐Transfer Reactions ETR at Oxide Films Mixed Ionic/Electronic Conductivity Equivalent Circuit Diagrams Growth of Oxide Films and Ionic Migration Survey on the Growth of Oxide Films Insulating Passive Films on Metals: Growth, and Corrosion of Al as Example Thermodynamic Aspects A Survey on Oxide Formation from CVs The Film Formation Factor k Electrochemical Impedance Spectra EIS and Equivalent Circuit Diagram Kinetics of Film Growth Corrosion and Breakdown Porous Aluminum Oxide Other Types of Passive Aluminum Oxide Films, Anof, Modified Aluminum, Alloys Other Systems Other Metals Forming Insulating Oxide Films Semiconducting and Metallic Oxide Films on Metals Duplex Films Passivation with Participation of the Electrolyte Semiconductors Passivation of Alloys ITR at the Homogeneous Oxide/Electrolyte Interface: Corrosion and Modification Passive Corrosion in the Steady State Corrosion during Oxide Growth Oxide Reduction and Oxidation Modification of Oxide Films by ITR of Other Ions Corrosion at Inhomogeneous Films: Breakdown, Pitting and Localized Attack Microscopic and Molecular Reasons for Local Corrosion Dielectric Breakdown Collision ionization model Tunnel model for thin films Pitting Corrosion Cathodic Breakdown Laser Induced Breakdown or Oxide Growth Applications Conclusions Acknowledgments

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Solid State Properties of Some Valve Metal Oxides

Cited by 14 publications

References 4 publications

Influence of Bond Energies of Oxides on the Kinetics of Anodic Oxide Growth on Valve Metals

Influence of Bond Energies of Oxides on the Kinetics of Anodic Oxide Growth on Valve Metals

Preparation and Properties of Pyrolytic Zirconium Dioxide Films

Passivity of Metals, Alloys, and Semiconductors

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