Relation between oxidation microstructure and the maximum energy product loss of a Sm2Co17 magnet oxidized at 500 ℃

The oxidation microstructure and maximum energy product (BH)_max loss of a Sm(Co_0.76, Fe_0.1, Cu_0.1, Zr_0.04)₇ magnet oxidized at 500 ℃ were systematically investigated. Three different oxidation regions were formed in the oxidized magnet: a continuous external oxide scale, an internal reaction layer, and a diffusion zone. Both room-temperature and high-temperature (BH)_max losses exhibited the same parabolic increase with oxidation time. An oxygen diffusion model was proposed to simulate the dependence of (BH)_max loss on oxidation time. It is found that the external oxide scale has little effect on the (BH)_max loss, and both the internal reaction layer and diffusion zone result in the (BH)_max loss. Moreover, the diffusion zone leads to more (BH)_max loss than the internal reaction layer. The values of the oxidation rate constant k for internal reaction layer and oxygen diffusion coefficient D for diffusion zone were obtained, which are about 1.91 × 10^-10 cm²/s and 6.54 × 10^-11 cm²/s, respectively.     

Initial oxidation of the Mg(0001) surface,an electron spectroscopy study

The initial oxidation of Mg(0001) has been studied using AES (Auger electron spectroscopy), LEED (low energy electron diffraction), and EELS (electron energy loss spectroscopy). The oxidation proceeds through different stages; first oxygen atoms are incorporated to chemisorption sites below the top layer magnesium. This chemisorption phase is followed by the formation of an oxide layer. The oxide layer covers the Mg surface after an oxygen exposure of ～ 10 L O₂. After this exposure the bulk-like MgO formation slowly increases the oxide thickness. The oxide layer formed for exposures up to ≤ 10 L O₂ gives rise to a diffuse LEED pattern of the same symmetry as the original “clean” LEED pattern; the possibility of an epitaxial oxide formation at this stage is discussed.     

The interference of an electron beam with the surface reaction between oxygen and germanium

Electron beam assisted adsorption and desorption of oxygen was studied by Auger electron spectroscopy (AES). Beam assisted adsorption was observed on clean as well as on oxidized surfaces. After an oxygen exposure of 1000 × 10^?7 Torr min and continuous irradiation with beam voltage of 1.5 kV and beam current density 2 microA mm^?2, the oxygen 510 eV signal amplitude from the point of beam impact was 2.5 times greater than the signal from the non-irradiated region. The Ge 89 eV signal showed a corresponding decrease. Enhanced adsorption occurred at beam energies as low as 16.5 eV. After irradiation, the oxidized surface was not carbon contaminated. Following an oxygen exposure of 30 min at 0.1 Torr and 550°C and subsequent additional beam assisted exposure of 1000 × 10^?7 Torr min, the maximum oxide thickness was about 18 Å. Beam assisted desorption did not occur from thin oxygen layers (0–510 eV signal strength less than 5 units, calculated oxide thickness about 6 Å), but occurred from thick oxides and stopped after the signal amplitude had decreased to 5 units. Based on these results, a model for the structure of the oxygen layer covering the Ge(111) surface is proposed. Mechanisms for adsorption and desorption are discussed. The implications of beam assisted adsorption and desorption on electron beam operated surface measurements (LEED, AES, ELS, APS etc.) are stressed.     

Studies of clean and oxidized tellurium surfaces

Clean and oxidized surfaces of tellurium films have been studied using electron-excited Auger electron spectroscopy, X-ray photoelectron spectroscopy, energy loss spectroscopy, and electron-stimulated desorption. The results for clean tellurium are in general agreement with previous studies, but the oxidation studies have provided new information. Reaction between oxygen gas and tellurium was found to be an activated process requiring tellurium temperatures in excess of 60°C to produce detectable oxide for 30 min exposures to ~800 Torr of oxygen. Increasing the temperature to 200°C produced a 10.6 A layer of TeO₂. This layer was rapidly removed by electron irradiation with a cross-section of ~3 × 10^?18 cm² for electron-stimulated desorption of oxygen by 2 keV electrons; however, there was evidence for reduced cross sections for thinner TeO₂ layers.     

A LEELS and auger study of the oxidation of liquid and solid tin

The oxidation of liquid and solid tin from 25 to 240°C has been investigated using 75 eV low energy electron loss spectroscopy (LEELS) and Auger spectroscopy over an oxygen exposure range from zero to 10⁷ L. LEELS was chosen for two reasons. First it can distinguish Sn, SnO and SnO₂ from each other. Second, we show that at 75 eV incident energy LEELS has a penetration depth of only one monolayer. As a result the continuity and stoichiometry of the oxide layer could be studied as a function of thickness from submonolayer to several monolayer thicknesses. Although unable to distinguish SnO from SnO₂ the larger penetration depth of the Auger technique complemented the LEELS study. From zero to one monolayer the oxide grows as islands containing both SnO and SnO₂. Above one monolayer coverage the oxide is continuous and free of metallic tin with its outer most surface enriched in SnO₂. Although oxide films grew more rapidly on polycrystalline tin than on single crystal tin the composition and continuity as a function of thickness remained unchanged. Very little change in oxide growth rate, continuity, or stoichiome- try was observed for solid tin up to temperatures near the melting point. However at 229°C, just 3°C below the melting point of tin, dissolution of oxygen into the metal was observed. A continuous, metal free solid oxide, primarily SnO, could be grown on liquid tin at 240°C than remained stable for 20 min after removal of the oxygen gas. Our model for the early stages of the oxidation of tin is different from that previously proposed on the basis of UPS, XPS, and 400 eV LEELS with respect to the continuity and relative ordering of the SnO and SnO₂ phases. Quantitative comparison of our results with those previously reported shows that the previous results are consistent with our model for the structure and stoichiometry of the initial oxide grown on tin.     

Kinetics of electron-stimulated oxygen adsorption on the lead surface

Auger electron spectroscopy has been used to study the kinetics of oxygen adsorption on lead for two cases, i.e., during continuous electron irradiation (0–1000 eV) and without it, depending on exposure to oxygen at a partial pressure of 10^?6 Torr and room temperature. The maximum exposure to oxygen is 5000 L. Lead exposure to oxygen of several hundred Langmuirs with simultaneous irradiation with low-energy electrons shifts Auger lead peaks by 1 eV toward lower energies, which is explained by electron-stimulated adsorption (ESA). It has been shown that ESA is observed only at electron energies below 300 eV; at higher energies, electron-stimulated desorption of oxygen dominates.     

Oxidation of Ni(Pt)Si by molecular vs. atomic oxygen

X-ray photoelectron spectroscopy (XPS) has been used to characterize the oxidation of a clean Ni(Pt)Si surface under two distinct conditions: exposure to a mixed flux of atomic and molecular oxygen (O + O₂; PO+O₂ = 5 × 10⁻⁶ Torr) and pure molecular oxygen (O₂; PO₂ = 10⁻⁵ Torr) at ambient temperatures. Formation of the clean, stoichiometric (nickel monosilicide) phase under vacuum conditions results in the formation of a surface layer enriched in PtSi. Oxidation of this surface in the presence of atomic oxygen initially results in formation of a silicon oxide overlayer. At higher exposures, kinetically limited oxidation of Pt results in Pt silicate formation. No passivation of oxygen uptake of the sample is observed for total O + O₂ exposure <8 × 10⁴ L, at which point the average oxide/silicate overlayer thickness is 23 (3) Å (uncertainty in the last digit in parentheses). In contrast, exposure of the clean Ni(Pt)Si surface to molecular oxygen only (maximum exposure: 5 × 10⁵ L) results in slow growth of a silicon oxide overlayer, without silicate formation, and eventual passivation at a total average oxide thickness of 8(1) Å, compared to a oxide average thickness of 17(2) Å (no silicate formation) for the as-received sample (i.e., exposed to ambient.) The aggressive silicon oxidation by atomic oxygen, results in Ni-rich silicide formation in the substrate and the kinetically limited oxidation of the Pt.     

Laser-induced oxidation of the Si(111) surface

Pulsed laser induced oxidation of clean Si(111) surfaces has been studied by Auger electron spectroscopy and electron energy loss spectroscopy. The short duration time of the pulse has allowed a precise investigation of the first stages of the oxidation. About 1–2 oxide monolayers first grow in less than 10 s. Their stoichiometry evolves from SiO_x towards SiO₂ with increasing beam energy densities. Once this superficial layer has formed, no evolution is seen with further irradiation, suggesting that oxygen diffusion during the pulse duration cannot sustain the oxide growth.     

Electron stimulated oxidation of GaAs,studied by quantitative auger electron spectroscopy

The oxidation properties of the clean polar (111) faces of GaAs, prepared by Ar⁺ bombardment and proper annealing, are investigated. Considering the adsorbed layer as a continuum and using empirical values for the escape depth of the Auger electrons from literature, the coverage of oxygen on these faces is quantitatively determined. For a coverage of up to 10% of a monolayer the sticking coefficients are about 10^?3 for the ($\text{111}$) As face and about 10^?4 for the (111) Ga face, respectively. They decrease rapidly with increasing coverage. The oxidation is strongly stimulated by electron irradiation causing dissociation of the oxygen which is originally adsorbed in molecular form. In this way a compact oxide layer is formed which shows As depletion as a result of sublimation of As₄O₆ and a chemical shift of the Ga Auger peaks is observed. The cross section for the O₂ dissociation is calculated to be 1.8–2.5 Ų depending on electron energy.     

The reaction of oxygen and water with iron films studied by X-Ray photoelectron spectroscopy

Adsorption of oxygen on iron at ambient temperature and low pressure is shown by XPS to give a chemisorbed species and the oxide, Fe₂O₃. At low temperatures a further adsorbed species is detected, similar to the nickel-oxygen system. Correction of the intensity of the oxygen signal for depth results in an oxidation curve in agreement with reported work using other techniques, i.e. oxidation is fast until about four layers of oxide are formed, at an exposure of ca. 10² L, and then proceeds slowly to about ten layers. Adsorption of water vapour produces an overlayer less than one layer in depth at an exposure of 10⁵ L. Comparison of the overlayer depths calculated from the decrease in unoxidised iron signal intensity and from the increase in oxygen intensity gives good agreement for the thick oxide film produced by oxygen adsorption, but not for the thin overlayer formed by exposure to water vapour. This suggests a difference in packing of the ions in the thin overlayer compared to the arrangement in the bulk oxide.     

InP清洁表面上电子感应吸附氧的研究

用俄歇电子能谱观察清洁InP表面在电子束照射下与真空室中H₂O和O₂的相互作用,发现水蒸汽所引起的电子束感应吸附氧的作用比氧气要明显得多。在吸附氧的同时,In和P的俄歇信号也发生变化,分析其过程为一种氧化过程,氧一开始先同表面的In结合成为氧化铟,随后向表面以内透入,并不断同In和P结合,氧化层的厚度随时间几乎是线性地增加的。与InP的自体氧化层的俄歇深度分布相比较,二者极为相似,所不同的是,电子束感应吸附的氧不足以使表面层中的磷全部氧化,而ESO的氧化层中磷的 关键词：     

Oxidation behavior and mechanism of powder metallurgy Rene95 nickel based superalloy between 800 and 1000 °C

The oxidation behaviors of powder metallurgy (PM) Rene95 Ni-based superalloy in the temperature range of 800-1000 °C are investigated in air by virtue of isothermal oxidation testing, X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. The results show that the oxidation kinetics follows a square power law as the time extends at each temperature. The oxidation layers are detected to be composed of Cr₂O₃, TiO₂ and a small amount of NiCr₂O₄. The cross-sectional morphologies indicate that the oxidation layer consists of three parts: Cr-rich oxide layer, Cr and Ti duplex oxide layer, and oxidation affected zone. Theoretical analyses of oxidation kinetics and thicknesses of oxidation layers confirm that the activation energy of oxidation of PM Rene95 superalloy is 165.32 kJ mol⁻¹ and the oxidation process is controlled by diffusions of oxygen, Cr, and Ti. Accordingly, a diffusion-controlled mechanism is suggested to understand the oxidation behaviors of PM Rene95 superalloy at elevated temperatures.     

Oxygen diffusion through thin Pt films on Si(100)

We have investigated the diffusion of oxygen through evaporated platinum films on Si(100) upon exposure to air using substrates covered with Pt films of spatially and continuously varying thickness (0–500 Å). Film compositions and morphologies before and after silicidation were characterized by modified crater edge profiling using scanning Auger microscopy, energy-dispersive X-ray microanalysis, scanning tunneling microscopy, and transmission electron microscopy. We find that oxygen diffuses through a Pt layer of up to 170 Å forming an oxide at the interface. In this thickness range, silicide formation during annealing is inhibited and is eventually stopped by the development of a continuous oxide layer. Since the platinum film consists of a continuous layer of nanometer-size crystallites, grain boundary diffusion of oxygen is the most probable way for oxygen incorporation. The diffusion constant is of the order of 10^–19 cm²/s with the precise value depending on the film morphology.     

A LEED-AES study of the initial stages of oxidation of Fe (001)

LEED and AES have been used to study the structural changes and kinetics of the initial interaction between Fe(001) and oxygen at room temperature. The AES oxygen signal was quantified by using a two-dimensional oxide layer as a calibration point. This reproducible oxide layer was prepared by the high temperature reaction of H₂O at 10^?6 torr with Fe(001). The initial oxygen sticking coefficient was observed to be close to unity, which suggests that the chemisorption is non-activated and involves a mobile adsorption step. The rate of chemisorption decreased as (1-Θ) and exhibited a minimum at Θ = 0.5. LEED data indicate that the minimum value of the sticking coefficient corresponded to the completion of a c (2 × 2) surface structure. Upon additional exposure to oxygen, an increase in the sticking coefficient was observed in conjunction with the disappearance of the c (2 × 2) and a gradual fade out of all diffraction features. After mild heating, epitaxial FeO (001) and FeO (111) structures were observed. The simultaneous appearance of a shifted M_2,3M_4,5M_4,5 iron Auger transition with the increase in the sticking coefficient and the disappearance of the c (2 × 2) indicated that oxide nucleated on the surface after the complete formation of the c (2 × 2) structure. The relatively high sticking coefficient during the initial oxidation indicates that formation of a mobile adsorbed oxygen state precedes the formation of oxide.     

Combined SIMS,AES, and XPS investigations of tantalum oxide layers

Thick layers of tantalum oxide prepared by thermal and anodic oxidation have been studied by combined SIMS, AES, and XPS during depth profiling by 3keV Ar⁺ ion sputtering. The chemical composition of these films is revealed by the OKLL and O 1s signals and by the “lattice valence” parameter determined from the TaO _n ^± intensities. Thus the anodic film consists of a contamination layer, an oxygen-rich reactive interface and a thick homogeneous oxide layer followed by an interface to the Ta metal. The thermal oxide shows an oxygen concentration decreasing with depth and a broad oxide-metal interface. In both cases, carbon contamination (carbide) prevents the application of the valence model to the clean Ta substrate. The sputtering yield of the oxides was found to be 0.6 Ta₂O₅/ion.     

Initial oxidation of polycrystalline Permalloy surface

X-ray photoelectron spectroscopy (XPS) and work-function measurements were used in combination to investigate the initial steps of Permalloy (Ni₈₀Fe₂₀) oxidation at room temperature. They showed that, after oxygen saturation, the surface is covered by nickel oxide (NiO), nickel hydroxide (Ni(OH)₂) and iron oxides (Fe_xO_y), and there is no preferential oxidation. Iron oxidation proceeds through the formation of FeO (Fe²⁺) followed with Fe₂O₃ growth (Fe³⁺). The oxidation is governed by a dissociative Langmuir-type oxidation: the sticking coefficient is decreasing over oxygen exposure. Oxidation continues by oxygen dissolution into the first layers to form a nano-oxide of about 8 Å in thickness.     

Structure and phase transformations caused by oxygen ion implantation into titanium

Secondary-ion mass spectrometry and transmission electron microscopy are used to investigate structural changes and phase transformations during ¹⁶O and ¹⁸O ion implantation into titanium at 100 and 300 K. For all implanted ion energies, there are the doses (saturation doses) after which the interstitial oxygen profile takes a final steady-state shape. The steady-state profile corresponds to a definite stable set of oxide phases, including TiO, rutile TiO₂, and TiO_1.5 layers. Under steady-state conditions, the film is composed of several oxide phases, whose structures depend on the target temperatures used in the irradiation process. At 100 K, the steady-state oxide system contains an amorphous phase layer with gas-filled bubbles instead of crystalline rutile.     

Low-temperature oxidation of CoCu films with long-term irradiation by oxygen ion beams

The surface and surface layers of Co_xCu_100?x inhomogeneous thin films irradiated by an oxygen ion beam for a long time (to 100 min) are studied. The films are obtained by electrolytic deposition. With X-ray photoelectron spectroscopy and conversion electron Mössbauer spectroscopy, it is shown that the irradiation leads to the formation of an oxidized surface layer. The continuity and thickness of the layer depend on the roughness of the initial film. For a cobalt content of 8≤x≤20 at. %, the oxide layer is continuous and nonuniform in thickness, the mean thickness being estimated at several tens of nanometers. The interface between the layer and the underlying film is sharp. The films irradiated are smoother than the asdeposited ones. The formation of the oxide layer is treated in terms of a qualitative model.     

Comparative analysis of emission and absorption spectra of zinc oxide powders

Photoluminescence and optical absorption spectra induced by proton and electron irradiation in zinc oxide powders have been investigated. It has been found that the emission band in a visible region with a maximum of about 2.3 eV is a superposition of three bands with 2.55, 2.34, 2.12 eV, respectively, caused by oxygen vacancies V _O⁺, interstitial oxygen O _i ⁻, and zinc vacancies V _Zn⁻ absorbing in the 3.03-, 2.83-, and 2.64-eV bands.     

Oxidation of cobalt at room temperature,studied by combined static SIMS,static AES,XPS and work function investigations

The room temperature oxidation of cobalt has been found to proceed in two distinct steps, the first of which (at 0–20 L oxygen exposure) leads to oxygen chemisorption without formation of oxide-like bonds, the second step (at > 20 L) consists of the formation and in-depth growth of a surface oxide. Both stages can be distinguished by their characteristic secondary ion emission, in particular by the energy distribution of the positive secondary ions, which changes with oxygen coverage, and by their characteristic electron spectroscopic signals, in particular the occurrence of CoM₂₃VL(O)₂₃ and CoM₂₃VL(O)₁ cross transitions in the second stage, which have been observed for the first time in surface oxide layers in the monolayer range.