X-ray photoelectron spectroscopy study of Pd oxidation by RF discharge in oxygen

The low-temperature oxidation of polycrystalline palladium by RF oxygen plasma was studied via X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Detailed information about the electronic states of palladium and oxygen was obtained based on the XPS curve fitting analysis of Pd3d and Pd3p + O1s lines. The results showed that Pd oxidation by oxygen plasma was different from Pd oxidation in pure O₂ at high temperature. SEM shows well-structured submicron PdO particles result from oxidation in pure O₂, whereas plasma oxidation results in the predominant formation of two-dimensional PdO structures covering the initial crystallites of the Pd foil. Further oxidation to a three-dimensional PdO phase occurs under prolonged treatment with oxygen plasma. The formation of a PdO_x (x > 1) species, characterized by a E_b(Pd3d_5/2) = 338.0–338.2 eV value that is close to the Pd⁴⁺ oxidation state, was also observed. This PdO_x species was found to have low thermal stability (T < 400 K). It is proposed that the PdO_x species can be localized within the boundaries of crystallites.     

On the low-temperature chemistry of 1,3-butadiene

In this paper, species versus temperature profiles were measured during the oxidation of 1,3-butadiene in a jet-stirred reactor (JSR) at 1 atm, at different equivalence ratios (φ = 0.5, 1.0 and 2.0), in the temperature range 600 – 1020 K. Both synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) and gas chromatography (GC) methods were used to analyze the species. The experimental results show that a large proportion of the products are aldehydes (formaldehyde, acetaldehyde, acrolein, etc.) and ketenes (ketene, methyl-ketene), with acrolein being one of the major products. Moreover, furan, 1,3-cyclopentadiene and benzene are also present as intermediates in significant amounts. The reaction pathways leading to the formation of these species are discussed in detail. A new detailed mechanism, NUIGMech1.3, was developed to simulate these new data as well as other experimental data available in the literature. The validation results indicate that quantum calculations are also needed to explore the formation of some important species formed in the oxidation of 1,3-butadiene. Overall, the new 1,3-butadiene mechanism agrees well with various experimental data in the low- to high-temperature regimes and at different pressures. Flux and sensitivity analyses show that 1,3-butadiene shares some common reaction chemistry pathways with 1- and 2-butene via Ḣ atom and HȮ₂ radical addition to the C = C double bond in 1,3-butadiene, reactions which are important for both systems. The low temperature chemistry of 1,3-butadiene is mainly controlled by the reaction pathways of ȮH radical addition to the C = C double bond of the fuel molecule. The 1-buten-4-ol-3-yl radicals so formed subsequently add to O₂ and react via the Waddington mechanism, which is important in accurately simulating the oxidation and auto-ignition of 1,3-butadiene at engine relevant conditions.     

Methanol oxidation up to 100 atm in a supercritical pressure jet-stirred reactor

Methanol (CH₃OH) has attracted considerable attention as a renewable fuel or fuel additive with low greenhouse gas emissions. Methanol oxidation was studied using a recently developed supercritical pressure jet-stirred reactor (SP-JSR) at pressures of 10 and 100 atm, at temperatures from 550 to 950 K, and at equivalence ratios of 0.1, 1.0, and 9.0 in experiments and simulations. The experimental results show that the onset temperature of CH₃OH oxidation at 100 atm is around 700 K, which is more than 100 K lower than the onset at 10 atm and this trend cannot be predicted by the existing kinetics models. Furthermore, a negative temperature coefficient (NTC) behavior was clearly observed at 100 atm at fuel rich conditions for methanol for the first time. To understand the observed temperature shift in the reactivity and the NTC effect, we updated some key elementary reaction rates of relevance to high pressure CH₃OH oxidation from the literature and added some new low-temperature reaction pathways such as CH₂O + HO₂ = HOCH₂O₂ (RO₂), RO₂ + RO₂ = HOCH₂O (RO) + HOCH₂O (RO) + O₂, and CH₃OH + RO₂ = CH₂OH + HOCH₂O₂H (ROOH). Although the model with these updates improves the prediction somewhat for the experimental data at 100 atm and reproduces well high-temperature ignition delay times and laminar flame speed data in the literature, discrepancies still exist for some aspects of the 100 atm low-temperature oxidation data. In addition, it was found that the pressure-dependent HO₂ chemistry shifts to lower temperature as the pressure increases such that the NTC effect at fuel-lean conditions is suppressed. Therefore, as shown in the experiments, the NTC phenomenon was only observed at the fuel-rich condition where fuel radicals are abundant and the HO₂ chemistry at high pressure is weakened by the lack of oxygen resulting in comparatively little HO₂ formation.     

Oxygen non-stoichiometry and electrical conductivity of Pr2−xSrxNiO4±δ with x = 0–0.5

Oxygen non-stoichiometry and electrical conductivity of the Pr_2−xSr_xNiO_4±δ series with x = 0.0–0.5 were investigated in Ar/O₂ (pO₂ = 2.5 to 21 000 Pa) within a temperature range of 20–1000 °C. The equilibrium values of oxygen non-stoichiometry and electrical conductivity of these nickelates were determined as functions of temperature and oxygen partial pressure (pO₂). The nickelates with x = 0–0.5 appear to be p-type semiconductors in the investigated temperature and pO₂ ranges. The nickelates with x = 0.3–0.5 show very feebly marked pO₂ dependencies of the conductivity. Pr_1.7Sr_0.3NiO_4±δ shows the anomalies of the conductivity versus oxygen partial pressure which can be related to the orthorhombic–tetragonal crystal structure transformations. The conductivity of the Pr_2−xSr_xNiO_4±δ samples correlates with the average oxidation state of the nickel cations. The samples with x = 0.5 have the highest nickel oxidation state (≈ 2.5+), the highest [Ni³⁺]/[Ni²⁺] ratio close to 1 and show the highest conductivity (≈ 120 S/cm) in the whole pO₂ and temperature ranges investigated.     

Soft chemistry synthesis and characterizations of fully oxidized and reduced NdBaCo2O5+δ phases δ = 0, 1

The double ordered perovskites NdBaCo₂O₅ and NdBaCo₂O₆ were prepared by soft chemistry. The samples were characterized from a structural and chemical point of view, concomitantly with their physical properties. Upon reduction, NdBaCo₂O₅ is formed with a tetragonal unit cell (a = b = 3.94 Å, c = 7.57 Å) and presents an antiferromagnetic behavior. Upon oxidation, a complete stoichiometric ordered phase NdBaCo₂O₆ with a tetragonal unit cell (a = b = 3.88 Å, c = 7.63 Å) could be obtained with a ferromagnetic and a metallic behavior. Finally it is shown that these phases are able to reversibly catch and release oxygen, suggesting a high anionic conductivity.     

Theoretical study of the reaction 2,5-dimethylfuran + H → products

The reaction of 2,5-dimethylfuran (DMF) with H-atoms was studied using a potential energy surface calculated at the CBS-QB3 level of theory and master equation/RRKM modeling. Hydrogen abstraction by H-atom and hydrogen additions on DMF were considered. As the decomposition pathways of the initial adducts were unknown, a large number of decomposition routes was explored for these adducts. An important number of interconnected product channels were found and preliminary master equation calculations were performed to select the crucial wells and exit channels. The ipso substitution DMF + H → methylfuran (MF) + CH₃ and the formation of 1,3-butadiene and acetyl radical (CH₃CO) were found to be the major product channels in the addition process. The total calculated rate constant was found in good agreement with experimental data and is nearly pressure-independent. A small sensitivity to pressure was found for the computed branching ratios. At 1 bar, the yields of the two product channels of the addition process are maximal at 1100 K with computed branching ratios of 39% (MF + CH₃) and 27% (1,3-C₄H₆ + CH₃CO). Above 1300 K, hydrogen abstraction by H-atom becomes dominant and reaches a branching ratio of 56% at 2000 K.     

X-ray photoelectron spectroscopy of CeO2–Na2O–SiO2 glasses

A series of (CeO₂)_x–(Na₂O)_0.3–(SiO₂)_(0.7−x) glasses, where 0.025 ≤ x ≤ 0.075, have been synthesized and investigated by mean of X-ray photoelectron spectroscopy (XPS). The Ce 3d spin-orbit doublet was curve fitted in order to quantify the proportions of each cerium oxidation state in these glasses. It was found that Ce ions are predominantly in the Ce(III) state in glasses with compositions x ≤ 0.075, while mixed Ce valences were found in the glass with composition x = 0.10. The O 1s spectra have also been curve fitted with two components, one from bridging oxygen (BO) and the other from non-bridging oxygen atoms (NBO). The measured number of NBO, based on the fact that only oxygen atoms in the site Si–O–Na⁺ contribute to the NBO peak, was found to be constant at ∼35% for all samples, in good agreement with the value calculated from the glass composition and inductively coupled plasma (ICP) suggesting that Ce ions enter the network as a glass intermediate. The thermal measurements done on these glasses agree well with the XPS findings.     

An experimental and modeling study of the autoignition of 3-methylheptane

An experimental and kinetic modeling study of the autoignition of 3-methylheptane, a compound representative of the high molecular weight lightly branched alkanes found in large quantities in conventional and synthetic aviation kerosene and diesel fuels, is reported. Shock tube and rapid compression machine ignition delay time measurements are reported over a wide range of conditions of relevance to combustion engine applications: temperatures from 678 to 1356 K; pressures of 6.5, 10, 20, and 50 atm; and equivalence ratios of 0.5, 1.0, and 2.0. The wide range of temperatures examined provides observation of autoignition in three reactivity regimes, including the negative temperature coefficient (NTC) regime characteristic of paraffinic fuels. Comparisons made between the current ignition delay measurements for 3-methylheptane and previous results for n-octane and 2-methylheptane quantifies the influence of a single methyl substitution and its location on the reactivity of alkanes. It is found that the three C₈ alkane isomers have indistinguishable high-temperature ignition delay but their ignition delay times deviate in the NTC and low-temperature regimes in correlation with their research octane numbers. The experimental results are compared with the predictions of a proposed kinetic model that includes both high- and low-temperature oxidation chemistry. The model mechanistically explains the differences in reactivity for n-octane, 2-methylheptane, and 3-methylheptane in the NTC through the influence of the methyl substitution on the rates of isomerization reactions in the low-temperature chain branching pathway, that ultimately leads to ketohydroperoxide species, and the competition between low-temperature chain branching and the formation of cyclic ethers, in a chain propagating pathway.     

Anomalous high salt conductivity in primary diamines as solvents

It is shown that the conductivities of LiBF₄, LiPF₆, LiN(SO₂CF₃)₂ (LiTFSI), NaPF₆, KPF are abnormally high in two diamine solvents: ethylenediamine (EDA) and 1,3-diaminopropane (1,3 DAP). This is particularly evident for KPF₆, κ_MAX(EDA) = 35 mS cm^− 1 and κ_MAX(1,3 DAP) = 17.4 mS cm^− 1. Compared to three other organic solvents having the same viscosity, η ≅ 1.6 cP, but higher relative permittivity, NMF ε = 186.9, NMP ε = 32, γ-Bu ε = 39.1, the maxima of conductibility of EDA and 1,2 DAP, which have a low relative permittivity, ε ≅ 13–11, are largely superior or equal to those of NMF, NMP, γ-Bu. For KPF₆, κ_MAX(NMF) = 15.4mS cm^− 1, κ_MAX(NMP) = 7.8 mS cm^− 1 and κ_MAX(γ-BL) = 10.8 mS cm^− 1. We assume that this is due to a non-Stokesian conductivity mechanism.     

Reaction kinetics of OH radicals with 1,3,5-trimethyl benzene: An experimental and theoretical study

Alkylated aromatics are ubiquitous in transportation fuels. 1,3,5-Trimethyl benzene (135TMB) is a popular surrogate for the aromatic content of distillate fuels due to its symmetry (point group, C_3h), which facilitates the construction of an accurate chemical kinetic model. The reaction of OH radicals with 135TMB plays a crucial role in the oxidation kinetics of 135TMB. In this work, the reaction kinetics of OH-initiated oxidation of 135TMB were investigated behind reflected shock waves over 975–1318 K and atmospheric pressure. The reaction was followed by monitoring OH radicals near 307 nm. The rate coefficients were extracted from detailed chemical kinetic modeling of OH concentration-time profiles. Our measured data clearly showed a positive temperature dependence, in contrast to the negative temperature dependence of the literature low-temperature data. At 1000 K, our measured rate coefficient is 1.3 × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹, which is roughly a factor of 5 lower than the room-temperature data reported in the literature. This observation reflects the complex nature of the OH + 135TMB reaction, similar to that observed for various aromatics + OH chemical systems. Our measurements did not show any discernible pressure dependence over the narrow pressure range of 870 – 1148 Torr. The title reaction has several possible channels in the reactive potential energy surface. The importance of each channel was characterized using ab initio/RRKM-ME calculations over T = 200–2000 K and P = 0.76 -7600 Torr. Our analyses revealed that addition channels and hydrogen abstraction from the methyl site have negative energy barriers. The reaction was found to undergo almost exclusively (∼93%) via the addition channel under ambient conditions. However, beyond 600 K, the abstraction channels take the lead, yielding the positive T-dependence of the overall rate coefficient. Although addition channels display a sharp fall-off behavior beyond 500 K, the general rate coefficients are pressure-independent. The title reaction shows a complex kinetic behavior due to competing channels whose contribution changes significantly with temperature. Our theoretical calculations nicely reproduced the complex T-dependence of the reaction. After adjusting the barrier height, our theory remarkably captured the positive T-dependence of our high-T kinetic data and the negative T-dependence of the low-T literature data. To our knowledge, this is the first detailed study on the reaction kinetics of 135TMB with OH radicals. The reported rate data will be helpful for the combustion modeling of alkylated aromatic species.     

Low-temperature combustion chemistry of biofuels: Pathways in the low-temperature (550–700 K) oxidation chemistry of isobutanol and tert-butanol

Butanol isomers are promising next-generation biofuels. Their use in internal combustion applications, especially those relying on low-temperature autoignition, requires an understanding of their low-temperature combustion chemistry. Whereas the high-temperature oxidation chemistry of all four butanol isomers has been the subject of substantial experimental and theoretical efforts, their low-temperature oxidation chemistry remains underexplored. In this work we report an experimental study on the fundamental low-temperature oxidation chemistry of two butanol isomers, tert-butanol and isobutanol, in low-pressure (4–5.1 Torr) experiments at 550 and 700 K. We use pulsed-photolytic chlorine atom initiation to generate hydroxyalkyl radicals derived from tert-butanol and isobutanol, and probe the chemistry of these radicals in the presence of an excess of O₂ by multiplexed time-resolved tunable synchrotron photoionization mass spectrometry. Isomer-resolved yields of stable products are determined, providing insight into the chemistry of the different hydroxyalkyl radicals. In isobutanol oxidation, we find that the reaction of the α-hydroxyalkyl radical with O₂ is predominantly linked to chain-terminating formation of HO₂. The Waddington mechanism, associated with chain-propagating formation of OH, is the main product channel in the reactions of O₂ with β-hydroxyalkyl radicals derived from both tert-butanol and isobutanol. In the tert-butanol case, direct HO₂ elimination is not possible in the β-hydroxyalkyl + O₂ reaction because of the absence of a beta C–H bond; this channel is available in the β-hydroxyalkyl + O₂ reaction for isobutanol, but we find that it is strongly suppressed. Observed evolution of the main products from 550 to 700 K can be qualitatively explained by an increasing role of hydroxyalkyl radical decomposition at 700 K.     

Mixed conductivity and oxygen permeability of doped Pr2NiO4-based oxide

Pr₂NiO₄-based oxide was studied as a new mixed electronic and oxide ionic conductor for the oxygen permeation membrane. It was found that Pr₂NiO₄ doped with Cu and Fe for Ni site exhibits the relatively high oxygen permeation rate. Doping second cation to Ni site is effective for improving the oxygen permeation rate and the trivalent cation seems to be effective for increasing the oxygen permeation rate. Among the examined cation, the highest oxygen permeation rate was obtained by doping 5 mol% Fe. The oxygen permeation rate was also significantly affected by the surface catalyst and the highest oxygen permeation rate of 80 μmol·min^− 1·cm^− 2 at 1273 K was achieved by using La_0.1Sr_0.9Co_0.9Fe_0.1O₃ for the surface catalyst. Since the electrical conductivity slightly decreased with decreasing P_O2 and it dropped significantly at P_O2 = 10^− 19 atm, chemical stability of Pr₂NiO₄-based oxide seems to be reasonably high. Application of this new mixed conductor for the oxygen permeation membrane under the CH₄ partial oxidation was also studied and it was confirmed that the oxygen permeation rate much improved under the CH₄ oxidation condition and this Pr₂NiO₄ can be used for the oxygen permeation membrane for the CH₄ partial oxidation.     

Influence of the orthorhombic distortion on the van Hove singularities in the DOS and ARPES spectra of layered cuprates

Four atom states Cu3d_{x² −  y²}, Cu4s, O_a2p_xare involved in a tight-binding model for the superconducting CuO₂plane. The orthorhombic distortion is taken into account by the differences of Cu–O hopping amplitudes and single-site oxygen energies ε_aand ε_bof two oxygen positions in the elementary cell as well. An effective ‘oxygen’ Hamiltonian including only the electron amplitudes at the oxygen ions is derived. Simple expressions for the constant energy contours and the Fermi surface are obtained and they qualitatively describe the photoemission spectra. Extended saddle points nearp = (π,0) andp = (0,π) are observed in qualitative agreement with the ARPES data. The van Hove singularities of the density of states (DOS) related to the extended saddle points are calculated by a Monte Carlo method. It is found that the splitting of the singularity of the DOS at the bottom of the conduction band is created by the energy difference ε_a −  ε_b = 2δ.     

Low- and high-temperature study of n-heptane combustion chemistry

n-Heptane has been used extensively in various fundamental combustion experiments as a prototypical hydrocarbon fuel. While the formation of polycyclic aromatic hydrocarbon (PAH) in n-heptane combustion has been studied preferably in premixed flames, this study aims to investigate the combustion chemistry of n-heptane in less-studied diffusion flame and highly rich high-temperature homogeneous oxidation configurations by using a counterflow burner and a flow reactor, respectively. This work addresses the formation of higher-molecular species in the mass range up to about 160 u in both configurations. Samples are analyzed by time-of-flight (TOF) molecular beam mass spectrometry (MBMS) using electron-impact (EI) and single-photon ionization (PI). Highly resolved speciation data are reported. Laminar flow reactor experiments cover a wide temperature range. Especially the measurements at low temperatures provide speciation data of large oxygenates produced in the low-temperature oxidation of n-heptane, which are scarce in the literature. Important precursor molecules for PAH and soot formation, such as C₉H₈, C₁₀H₈, C₁₁H_10, and C₁₂H₈, are formed during the high-temperature combustion process in the counterflow flame, while oxygenated growth species are observed under low-temperature conditions, even at the fuel-rich equivalence ratio of ?=4.00.Numerical modeling for both conditions is performed by using a newly developed kinetic model of n-heptane, which includes the n-heptane and PAH formation chemistry with state-of-the-art kinetic knowledge. Good agreement between model predictions and experimental data of counterflow flame and flow reactor is observed for the major species and some intermediates of n-heptane oxidation. While the concentrations of benzene and toluene measured in the counterflow burner are well-reproduced, the numerical results for flow reactor data are not satisfactory. Differences are found between the formation pathways of fulvene, from whose isomerization benzene is produced in diffusion flame and flow reactor.     

Defect interactions in La0.3Sr0.7Fe(M′)O3−δ (M′ = Al,Ga) perovskites: Atomistic simulations and analysis of p(O2)-T-δ diagrams

Atomistic modelling showed that a key factor affecting the p(O₂) dependencies of point defect chemical potentials in perovskite-type La_0.3Sr_0.7Fe_1−xM′_xO_3−δ (M′ = Ga, Al; x = 0–0.4) under oxidizing conditions, relates to the coulombic repulsion between oxygen vacancies and/or electron holes. The configurations of A- and B-site cations with stable oxidation states have no essential influence on energetics of the mobile charge carriers, whereas the electrons formed due to iron disproportionation are expected to form defect pair clusters with oxygen vacancies. These results were used to develop thermodynamic models, adequately describing the p(O₂)-T-δ diagrams of La_0.3Sr_0.7Fe(M′)O_3−δ determined by the coulometric titration technique at 923–1223 K in the oxygen partial pressure range from 1 × 10^− 5 to 0.5 atm. The thermodynamic functions governing the oxygen intercalation process were found independent of the defect concentration. Doping with aluminum and gallium leads to increasing oxygen deficiency and induces substantial changes in the behavior of iron cations, increasing the tendencies to disproportionation and hole localization. Despite similar oxygen nonstoichiometry in the Al- and Ga-substituted ferrites at a given dopant content, the latter tendency is more pronounced in the case of aluminum-containing perovskites.     

Controllable oxidation of h-BN monolayer on Ir(111) studied by core-level spectroscopies

The effect of atomic oxygen adsorption on the structure and electronic properties of monolayer hexagonal boron nitride (h-BN) grown on Ir(111) has been studied using near edge X-ray absorption fine structure spectroscopy (NEXAFS), photoelectron spectroscopy (PES), and low-energy electron diffraction (LEED). It has been shown that the oxidation of the h-BN monolayer occurs through a gradual substitution of N by O in the h-BN lattice. This process leads to the formation of defect sites corresponding to three different types of the B atom environment (BN_3 ? xO_x with x = 1,2,3). The oxidation of the h-BN monolayer is very different from the case of graphene on Ir(111), where adsorption of atomic oxygen results mainly in the formation of epoxy groups [J. Phys. Chem. C. 115, 9568 (2011)]. A post-annealing of the h-BN monolayer after oxygen exposure results in further destruction of the B–N bonds and formation of a B₂O₃-like structure.     

Flame chemistry of tetrahydropyran as a model heteroatomic biofuel

The flame chemistry of tetrahydropyran (THP), a cyclic ether, has been examined using vacuum-ultraviolet (VUV)-photoionization molecular-beam mass spectrometry (PI-MBMS) and flame modeling, motivated by the need to understand and predict the combustion of oxygen-containing, biomass-derived fuels. Species identifications and mole-fraction profiles are presented for a fuel-rich (Φ = 1.75), laminar premixed THP–oxygen–argon flame at 2.66 kPa (20.0 Torr). Flame species with up to six heavy atoms have been detected. A detailed reaction set was developed for THP combustion that captures relevant features of the THP flame quite well, allowing analysis of the dominant kinetic pathways for THP combustion. Necessary rate coefficients and transport parameters were calculated or were estimated by analogies with a recent reaction set [Li et al., Combust. Flame 158 (2011) 2077–2089], and necessary thermochemical properties were computed using the CBS-QB3 method. Our results show that under the low-pressure conditions, THP destruction is dominated by H-abstraction, and the three resulting THP-yl radicals decompose primarily by β-scissions to two- and four-heavy-atom species that are generally destroyed by β-scission, abstraction, or oxidation.     

Mass spectrometric investigation of the low-temperature dimethyl ether oxidation in an atmospheric pressure laminar flow reactor

Low-temperature combustion is a major strategy today to reduce both soot and NO_x emission. Kinetic reaction models for low-temperature combustion which are validated against a wide range of experimental data are necessary e.g. for control purposes or as a basis for subsequent model reduction.In this study, the low-temperature oxidation of dimethyl ether in a highly diluted gas mixture was investigated experimentally in an atmospheric laminar flow reactor. The respective gas composition was analyzed by a time-of-flight mass spectrometer. This technique allows detection of all species simultaneously within the investigated temperature regime. Stoichiometries of ? = 0.8, 1.0, and 1.2 were studied with high temperature resolution in the range of 400–1200 K, and quantitative species mole fraction profiles have been determined.This wide temperature range comprises the different kinetic regimes occurring during the DME oxidation, which have been clearly resolved. The distinct negative temperature coefficient (NTC) region of the system was observed and extensive speciation is available. Special attention is given to species only occurring in the low-temperature region including formic acid and methyl formate.     

First-principles study on the electronic structure and optical properties of La0.75Sr0.25MnO3-σ materials with oxygen vacancies defects

The electronic structure and optical properties of La_0.75Sr_0.25MnO_3-σ (LSMO_3-σ) materials with 1 × 1 × 4 orthorhombic perovskite structure were performed by first-principles calculation. The structural changing of LSMO₃ (ideal structure, σ = 0) was not obvious under generalized gradient approximation (GGA) and GGA + U arithmetic. On the contrary, the structural changing of LSMO_3-σ (σ = 0.25, with oxygen vacancies defects in the z = 0, c/8, c/6, c/4, and c/2) with GGA + U were more obvious than the result of ideal. This structural distortion induced distinct changing in density of states (DOS) for LSMO_3-σ materials. Oxygen vacancy defects caused a shift of the total density of states (TDOS) features toward low binding energies and LSMO_3-σ keep half-metal properties as well as LSMO₃ ideal structure. In addition, the hybridization between the Mn-e_g and O-2p orbital was weakened and the partial density of states (PDOS) of Mn indicated a strong d-d orbital interaction. By the result of oxygen vacancy formation energy, oxygen vacancy defects can be more easily formed in La-O layers (z = 0 and c/6) to compare with other layers (z = c/8, c/4 and c/2). The calculation result of optical properties suggested that the ideal LSMO could be produced strong absorption in the range of ultraviolet and visible light, while the LSMO_3-σ with oxygen vacancies defects were presented weak absorption in the range of visible light.     

Epitaxial growth of well-ordered ultra-thin Al2O3 film on NiAl (1 1 0) by a single-step oxidation

Well-ordered ultra-thin Al₂O₃ films were grown on NiAl (1 1 0) surface by exposing the sample at various oxygen absorption temperatures ranging from 570 to 1100 K at dose rates 6.6 × 10⁻⁵ and 6.6 × 10⁻⁶ Pa. From the results of low-energy electron diffraction (LEED), Auger electron spectrometer (AES) and X-ray photon spectroscopy (XPS) observations, it was revealed that oxidation mechanism above 770 K is different from well-known two-step process. At high temperature, oxidation and crystallization occurred simultaneously while in two-step process oxidation and crystallization occurred one after another. At high-temperature oxidation well-ordered crystalline oxide can be formed by a single-step without annealing. Well-ordered Al₂O₃ layer with thickness over 1 nm was obtained in oxygen absorption temperature 1070 K and a dose rate 6.6 × 10⁻⁶ Pa at 1200 L oxygen.