Kinetics of oxide film growth on metal crystals - Electron tunneling and ionic diffusion.
Growth rate of oxide and other dielectric contact films on metal crystals computed for ionic diffusion and electron tunneling
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Growth rate of oxide and other dielectric contact films on metal crystals computed for ionic diffusion and electron tunneling
Thin-oxide (40-50 A) metal oxide semiconductor (MOS) structures are shown to exhibit, before large levels of electron tunnel injection, the near-ideal behavior predicted for a uniform trapezoidal barrier with thick-oxide properties. The oscillatory field dependence caused by electron-wave interference at the Si/SiO2 interface suggests an abrupt, one-monolayer barrier transition (approximately 2.5 A) consistent with earlier work. After tunnel injection of 10 to the 17th - 5 x 10 to the 18th electrons/sq cm, the barrier undergoes appreciable degradation, leading to enhanced tunneling conductance. Reproducible behavior is observed among different samples. This effect is found to be consistent with the generation of positive states in the region of the oxide near the Si/SiO2 interface (less than 20 A), where the tunneling electrons emerge into the oxide conduction band.
Refractory oxide materials for use in high temperature pebble-bed wind tunnel heat exchangers
The oxidation of dissolved Mn 2+ (aq) plays a critical role in driving manganese cycles and regulating the fate of essential elements and contaminants in environmental systems. Based on sluggish oxidation rate, abiotic processes have been considered less effective oxidation pathway for manganese oxidation in environmental systems. Interestingly, a recent study (Jung et al., 2021) has shown that the rapid photochemical oxidation of Mn 2+ (aq) could be a feasible scenario to uncover the potential significance of abiotic Mn 2+ (aq) oxidation. Nevertheless, the significance of photochemical oxidation of Mn 2+ (aq) under natural sunlight exposure remains unclear. Here, we demonstrate the rapid photocatalytic oxidation of Mn 2+ (aq) and the heterogeneous growth of tunnel-structured Mn oxides under simulated freshwater and seawater conditions in the presence of natural sunlight and hematite. The natural sunlight-driven photocatalytic oxidation of Mn 2+ (aq) by hematite showed kinetic constants of 1.02 h -−1 and 0.342 h −1 under freshwater and seawater conditions, respectively. The natural sunlight-driven photocatalytic oxidation rates are quite comparable to the results obtained from the previous laboratory test using artificial sunlight, which has ∼4.5 times stronger light intensity. It is likely because of ∼5.5 times larger light exposure area in the natural sunlight-driven photocatalytic oxidation than that of the laboratory test using artificial sunlight. We also elucidate the roles of cation species in controlling the oxidation rate of Mn 2+ (aq) and the crystalline structure of Mn oxide products. Specifically, in the presence of large amounts of cations, the oxidation rate of Mn 2+ (aq) was slower likely because of competitive adsorption. Furthermore, our findings highlight that Mn 2+ contributes significantly to the formation of large-tunneled Mn oxides. These results illuminate the importance of abiotic photocatalytic processes in controlling the redox chemistry of Mn in real environmental aqueous systems on the oxidation of Mn 2+ (aq), and provide an environmentally sustainable approach to effectively remediate water contaminated with Mn 2+ (aq) using natural sunlight.
The MINP solar cell concept refers to a cell structure designed to be a base region dominated device. Thus, it is desirable that recombination losses are reduced to the point that they occur only in the base region. The most unique feature of the MINP cell design is that a tunneling contact is utilized for the metallic contact on the front surface. The areas under the collector grid and bus bar are passivated by a thin oxide of tunneling thickness. Efforts must also be taken to minimize recombination at the surface between grid lines, at the junction periphery and within the emitter. Results of both theoretical and experimental studies of silicon MINP cells are given. Performance calculations are described which give expected efficiencies as a function of base resistivity and junction depth. Fabrication and characterization of cells are discussed which are based on 0.2 ohm-cm substrates, diffused emitters on the order of 0.15 to 0.20 microns deep, and with Mg MIS collector grids. A total area AM 1 efficiency of 16.8% was achieved. Detailed analyses of photocurrent and current loss mechanisms are presented and utilized to discuss future directions of research. Finally, results reported by other workers are discussed.
A new tip for scanning tunneling microscopy and a tip repair procedure that allows one to reproducibly obtain atomic images of highly oriented pyrolytic graphite with previously inoperable tips are reported. The tips are shown to be relatively oxide-free and highly resistant to oxidation. The tips are fabricated with graphite by two distinct methods.
Metal-oxide-metal tunnel diode properties, discussing parametric effects on small and large signals detector operation
Gamma-ray irradiation with doses up to 8 megarad produces no significant change on either the C(V) or the G(V) characteristics of MOS tunnel junctions with intermediate oxide thicknesses (40-60 A), whereas the expected flat-band shift toward negative electrode voltages occurs in control thick oxide capacitors. A simple tunneling model would explain the results if the radiation-generated hole traps are assumed to lie below the valence band of the silicon. The experiments also suggest that the observed radiation-generated interface states in conventional MOS devices are not due to the radiation damage of the silicon surface.
Direct detection experiments have demonstrated the coherent coupling of 10.6 micrometer radiation into photolithographically fabricated metal-oxide-metal tunnel junctions. A CO2 laser beam mechanically chopped at 1 KHz was focused at a variable angle of incidence with a power density of about 10 W/sq cm at the diodes. Diodes in which the junction resistance was much greater than the lead resistance displayed angular characteristics dominated by coherent antenna coupling.
A new switching phenomenon in metal-oxide semiconductor tunnel junction has been discovered. With a sufficiently large negative bias applied to the electrode, incident visible light of intensity greater than about 1 microW/sq cm causes the reverse-biased junction to switch from a low-current to a high-current state. It is believed that hot-electron-induced impact ionization provides the positive feedback necessary for switching, and causes the junction to remain in its high-current state after the optical excitation is removed. The junction may be switched back to the low-current state electrically. The basic junction characteristics have been measured, and a simple model for the switching phenomenon has been developed.
Photolithographic techniques have been developed to fabricate high-quality Al-Al oxide-Al superconducting tunnel junctions for use in X-ray detectors. These devices are designed to incorporate about 1-micron-thick superconducting X-ray absorbers for the detection of less than 10-keV single photons. In an effort to increase energy resolution, superconductor bandgap engineering with lateral and vertical trapping has been used to shorten quasi-particle tunneling times and diffusion lengths and to prevent quasi-particle diffusion away from the tunnel junction. Methods that have been developed for overcoming materials imcompatibility and device degradation upon thermal cycling are reported. The authors also report on the use of a nonrectangular tunnel junction geometry which reduces the magnetic field needed to suppress the Josephson current for stable biasing. Work in progress to measure the energy resolution of these X-ray detectors at 0.35 K is also discussed.
Recently developed superalloys that form alumina coatings have a high potential for heat shield applications for advanced aerospace vehicles at temperatures above 1095C. Both INCOLOY alloy MA 956 (of the Inco Alloys International, Inc.), an iron-base oxide-dispersion-strengthened alloy, and CABOT alloy No. 214 (of the Cabot Corporation), an alumina-forming nickel-chromium alloy, have good oxidation resistance and good elevated temperature strength. The oxidation resistance of both alloys has been attributed to the formation of a thin alumina layer (alpha-Al2O3) at the surface. Emittance and oxidation data were obtained for simulated Space Shuttle reentry conditions using a hypersonic arc-heated wind tunnel. The surface oxides and substrate alloys were characterized using X-ray diffraction and scanning and transmission electron microscopy with an energy-dispersive X-ray analysis unit. The mass loss and emittance characteristics of the two alloys are discussed.
Akaganeite (β-FeO(OH,Cl)) is a Fe(III) (hydr)oxide with a tunnel structure typically occupied by chloride. This mineral was first proposed to be present in Meridiani Planum and Gusev crater on Mars and akaganeite was subsequently detected by X-ray diffraction in Yellowknife Bay and Vera Rubin Ridge locations in Gale crater. Akaganeite in Gale crater has been proposed to form from Fe(II) sulfides but formation conditions remain unconstrained. We investigated akageneite formation by oxidative alteration of natural Fe(II) sulfide pyrrhotite exposed to HCl and oxidation-hydrolysis of Fe(II) HCl-leached from pyrrhotite at initial pH0 1.5, 2, 3, and 4. X-ray diffraction and Mössbauer analyses revealed formation of poorly-crystallized akageneite in oxidative alteration experiments. Air-exposure of the HCl-reacted dry pyrrhotite led to an increase in akageneite formation and precipitation of Fe(II) hydrated sulfates, goethite, and hydronium jarosite. Iron(II) oxidation-hydrolysis was sensitive to Si dissolved from phyllosilicates in one pyrrhotite sample. Akaganeite and goethite formed at pH0 1.5 and 2 with akageneite more abundant at dissolved Si/Fe ratio of 0.08 and goethite more abundant at Si/Fe of 0.01. Akaganeite formed together with hematite, ferrihydrite, and goethite at pH0 3, and formation was suppressed at pH0 4. Well-crystallized akageneite precipitated at pH0 1.5 while akaganeite of poorer crystallinity formed at pH0 2 and 3. Akageneite in Gale crater could form from sulfides by both mechanisms: oxidative alteration of sulfide minerals and oxidation-hydrolysis of leached Fe(II). The processes likely occurred during late diagenetic events triggered by interactions of acidic Cl-bearing groundwater with Fe(II) sulfides. Akaganeite in Yellowknife Bay, Gale crater could have formed by Fe(II) oxidation-hydrolysis either as a sole Fe(III) (hydr)oxide at pH<2 or along with ferrihydrite and hematite at 2<pH<4 in Si-enriched conditions. Akaganeite formation at Vera Rubin Ridge, Gale crater could have occurred through oxidative alteration of sulfides in Cl-bearing pH 1.2-1.5 solutions. The presence of well-crystalline akageneite in Vera Rubin Ridge indicates that Fe(II) oxidation-hydrolysis contributed to akageneite formation.
It is pointed out that inelastic electron tunneling spectroscopy (IETS) is a useful technique for the study of vibrational modes of molecules adsorbed on the surface of the insulating layer in a metal-insulator-metal tunnel junction. A detailed study of electron tunneling in aluminum-aluminum oxide-gold (Al-Al2O3-Au) tunnel junctions has been conducted with an overall goal of exploring possible mechanisms in such a thin film device useful for chemical sensing. For an understanding of the electronic effects in the presence of chemicals in a junction, the electronic surface properties of the metallic films in a clean tunnel junction must be established. The present investigation is concerned with room temperature observations of electronic states on the surface of highly oriented gold film in Al-Al2O3-Au junctions.
Numerical simulations of gas-seeding strategies required for planar laser-induced fluorescence (PLIF) in a Mach 10 air flow were performed. The work was performed to understand and quantify adverse effects associated with gas seeding and to compare different flow rates and different types of seed gas. The gas was injected through a slot near the leading edge of a flat plate wedge model used in NASA Langley Research Center's 31- Inch Mach 10 Air Tunnel facility. Nitric oxide, krypton, and iodine gases were simulated at various injection rates. Simulation results showing the deflection of the velocity field for each of the cases are presented. Streamwise distributions of velocity and concentration boundary layer thicknesses as well as vertical distributions of velocity, temperature, and mass distributions are presented for each of the cases. Relative merits of the different seeding strategies are discussed.
Akaganeite (beta-FeOOH) is an Fe(III) (hydr)oxide with a tunnel structure usually occupied by chloride. Akaganeite has been recently discovered in a mudstone on the surface of Mars by the Chemistry and Mineralogy (CheMin) and Sample Analysis at Mars (SAM) instruments onboard the Mars Science Laboratory (MSL) Curiosity Rover in Gale crater [1, 2]. Akaganeite was detected together with sulfate minerals [anhydrite (CaSO4) and basanite (2CaSO4·2H2O)] in the drilled Cumberland and John Clein mudstone samples at Yellowknife Bay [2]. Discovery of akaganeite and sulfates in the same samples suggests that sulfate ions could be present in aqueous solution during akaganeite formation. However, mechanism and aqueous environmental conditions of akaganeite formation (e.g., pH and range of sulfate concentration) in Yellowknife Bay remain unknown. The objective of our work was to perform synthesis of akaganeite without or with sulfate addition at variable pHs in order to constrain formation conditions of akaganeite in Yellowknife Bay, Gale crater on Mars.
We show that quantum effects are likely to significantly degrade the performance of MOSFETs (metal oxide semiconductor field effect transistor) as these devices are scaled below 100 nm channel length and 2 nm oxide thickness over the next decade. A general and computationally efficient electronic device model including quantum effects would allow us to monitor and mitigate these effects. Full quantum models are too expensive in multi-dimensions. Using a general but efficient PDE solver called PROPHET, we implemented the density-gradient (DG) quantum correction to the industry-dominant classical drift-diffusion (DD) model. The DG model efficiently includes quantum carrier profile smoothing and tunneling in multi-dimensions and for any electronic device structure. We show that the DG model reduces DD model error from as much as 50% down to a few percent in comparison to thin oxide MOS capacitance measurements. We also show the first DG simulations of gate oxide tunneling and transverse current flow in ultra-scaled MOSFETs. The advantages of rapid model implementation using the PDE solver approach will be demonstrated, as well as the applicability of the DG model to any electronic device structure.
Experimentally, thermal annealing is known to be a factor which enables a number of different integrated circuits (IC's) to recover their operating characteristics after suffering radiation damage in the space radiation environment; thus, decreasing and limiting long term cumulative total-dose effects. This annealing is also known to be accelerated at elevated temperatures both during and after irradiation. Linear response theory (LRT) was applied, and a linear response function (LRF) to predict the radiation/annealing response of sensitive parameters of IC's for long term (several months or years) exposure to the space radiation environment were constructed. Compressing the annealing process from several years in orbit to just a few hours or days in the laboratory is achieved by subjecting the IC to elevated temperatures or by increasing the typical spaceflight dose rate by several orders of magnitude for simultaneous radiation/annealing only. The accomplishments are as follows: (1) the test procedure to make predictions of the radiation response was developed; (2) the calculation of the shift in the threshold potential due to the charge distribution in the oxide was written; (3) electron tunneling processes from the bulk Si to the oxide region in an MOS IC were estimated; (4) in order to connect the experimental annealing data to the theoretical model, constants of the model of the basic annealing process were established; (5) experimental data obtained at elevated temperatures were analyzed; (6) time compression and reliability of predictions for the long term region were shown; (7) a method to compress test time and to make predictions of response for the nonlinear region was proposed; and (8) nonlinearity of the LRF with respect to log(t) was calculated theoretically from a model.