Structure and Dielectric Properties of Amorphous High-kappa Oxides: HfO2, ZrO2 and their alloys

High-$\kappa$ metal oxides are a class of materials playing an increasingly important role in modern device physics and technology. Here we report theoretical investigations of the properties of structural and lattice dielectric constants of bulk amorphous metal oxides by a combined approach of classical molecular dynamics (MD) - for structure evolution, and quantum mechanical first principles density function theory (DFT) - for electronic structure analysis. Using classical MD based on the Born-Mayer-Buckingham potential function within a melt and quench scheme, amorphous structures of high-$\kappa$ metal oxides Hf$_{1-x}$Zr$_x$O$_2$ with different values of the concentration $x$, are generated. The coordination numbers and the radial distribution functions of the structures are in good agreement with the corresponding experimental data. We then calculate the lattice dielectric constants of the materials from quantum mechanical first principles, and the values averaged over an ensemble of samples agree well with the available experimental data, and are very close to the dielectric constants of their cubic form.Comment: 5 pages, 4 figure

Conservation of dielectric constant upon amorphization in perovskite oxides

We report calculations indicating that amorphous RAO$_3$ oxides, with R and A trivalent cations, have approximately the same static dielectric constant as their perovskite crystal phase. The effect is due to the disorder-activated polar response of non-polar crystal modes at low frequency, which compensates a moderate but appreciable reduction of the ionic dynamical charges. The dielectric response was studied via density-functional perturbation theory. Amorphous samples were generated by molecular dynamics melt-and-quench simulations.Comment: 5 pages, 3 figure

Viscosity and glass transition in amorphous oxides

An overview is given of amorphous oxide materials viscosity and glass-liquid transition phenomena. The viscosity is a continuous function of temperature, whereas the glass-liquid transition is accompanied by explicit discontinuities in the derivative parameters such as the specific heat or thermal expansion coefficient. A compendium of viscosity models is given including recent data on viscous flow model based on network defects in which thermodynamic parameters of configurons—elementary excitations resulting from broken bonds—are found from viscosity-temperature relationships. Glass-liquid transition phenomena are described including the configuron model of glass transition which shows a reduction of Hausdorff dimension of bonds at glass-liquid transition

Er-doped aluminium oxide waveguide amplifiers

Within the EU STREP project "Photonic integrated devices in activated amorphous and crystalline oxides" (PI-OXIDE, http://pi-oxide.el.utwente.nl/), 6 partners are developing integrated optical devices based on erbium-doped layers of amorphous $Al_2O_3$ and crystalline $Y_2O_3)$. In $Al_2O_3$:Er channel waveguides structured by chlorine-based reactive ion etching [1], we have recently achieved gain with a maximum of 0.7 dB/cm at 1533 nm and a tuneability of 35 nm [2]

Transition of amorphous to crystalline oxide film in initial oxide overgrowth on liquid metals

It is important to understand the mechanism of oxidation in the initial stage on the free surface of liquid metals. Mittemeijer and co-workers recently developed a thermodynamic model to study the oxide overgrowth on a solid metal surface. Based on this model, we have developed a thermodynamic model to analyse the thermodynamic stability of oxide overgrowth on liquid metals. The thermodynamic model calculation revealed that the amorphous oxide phase is thermodynamically preferred up to 1.3 and 0.35 nm respectively, in the initial oxide overgrowth on liquid Al and Ga at the corresponding melting point. However, the amorphous phase is thermodynamically unstable in the initial oxide overgrowth on liquid Mg. The thermodynamic stability of amorphous phase in the Al and Ga oxide systems is attributed to lower sums of surface and interfacial energies for amorphous phases, compared to that of the corresponding crystalline phases.Financial support under grant EP/H026177/1 from the EPSRC was used

Electrochemical lithium intercalation in nanosized manganese oxides

X-ray amorphous manganese oxides were prepared by reduction of sodium permanganate by lithium iodide in aqueous medium (MnOx-I) and by decomposition of manganese carbonate at moderate temperature (MnOx-C). TEM showed that these materials are not amorphous, but nanostructured, with a prominent spinel substructure in MnOx-C. These materials intercalate lithium with capacities up to 200 mAh/g at first cycle (potential window 1.8-4.3 V) and 175 mAh/g at 100th cycle. Best performances for MnOx-C are obtained with cobalt doping. Potential electrochemical spectroscopy shows that the initial discharge induces a 2-phase transformation in MnOx-C phases, but not in MnOx-I ones. EXAFS and XANES confirm the participation of manganese in the redox process, with variations in local structure much smaller than in known long-range crystallized manganese oxides. X-ray absorption spectroscopy also shows that cobalt in MnOx-C is divalent and does not participate in the electrochemical reaction

On the Unusual Depletions toward Sk 155, or What Are the Small Magellanic Cloud Dust Grains Made of?

The dust in the Small Magellanic Cloud (SMC), an ideal analog of primordial galaxies at high redshifts, differs markedly from that in the Milky Way by exhibiting a steeply rising far-ultraviolet extinction curve, an absence of the 2175 Angstrom extinction feature, and a local minimum at ~12 micron in its infrared emission spectrum, suggesting the lack of ultrasmall carbonaceous grains (i.e. polycyclic aromatic hydrocarbon molecules) which are ubiquitously seen in the Milky Way. While current models for the SMC dust all rely heavily on silicates, recent observations of the SMC sightline toward Sk 155 indicated that Si and Mg are essentially undepleted and the depletions of Fe range from mild to severe, suggesting that metallic grains and/or iron oxides, instead of silicates, may dominate the SMC dust. However, in this Letter we apply the Kramers-Kronig relation to demonstrate that neither metallic grains nor iron oxides are capable of accounting for the observed extinction; silicates remain as an important contributor to the extinction, consistent with current models for the SMC dust.Comment: 12 pages, 3 figures; The Astrophysical Journal Letters, in pres