Assignment of surface IR absorption spectra observed in the oxidation reactions: 2H + H2O/Si(1 0 0) and H2O + H/Si(1 0 0)

Infrared reflection absorption spectroscopy that used buried metal layer substrates (BML-IRRAS) and density functional cluster calculations were employed to investigate the water related oxidation reactions of 2H + H₂O/Si(1 0 0)-(2 × 1), 2D + H₂O/Si(1 0 0)-(2 × 1), and H₂O + H/Si(1 0 0)-(2 × 1). In addition to the oxygen inserted coupled monohydrides, which were previously reported in the former reaction system, we report several other oxidized Si hydride species in our BML-IRRAS experiments. Three new pairs of vibrational bands are identified between 900 and 1000 cm⁻¹. These vibrational frequencies were calculated using Si9 and Si10 cluster models that included all possible structures from zero to five oxygen insertions into the top layer silicon atoms using a B3LYP gradient corrected density functional method with a polarized 6-31G** basis set for all atoms. The three pairs of vibrational modes are assigned to the scissoring modes of adjacent and isolated SiH₂ with zero, one, and two oxygen atoms inserted into the Si back bonds. All the other newly observed vibrational peaks related to Si oxidation are also assigned in this study. The Si-O stretching bands observed in the reaction 2D + H₂O/Si(1 0 0)-(2 × 1) show an isotope effect, which suggests that in the system 2H + H₂O/Si(1 0 0)-(2 × 1) also, hydrogen atom tunneling plays an important role for the insertion of oxygen atoms into Si back bonds that form oxidized adjacent dihydrides.     

The corrosion behavior of intermetallic compounds Ni3(Si,Ti) and Ni3(Si,Ti) + 2Mo in acidic solutions

The corrosion behavior of the intermetallic compounds homogenized, Ni₃(Si,Ti) (L1₂: single phase) and Ni₃(Si,Ti) + 2Mo (L1₂ and (L1₂ + Ni_ss) mixture region), has been investigated using an immersion test, electrochemical method and surface analytical method (SEM; scanning electron microscope and EPMA: electron probe microanalysis) in 0.5 kmol/m³ H₂SO₄ and 0.5 kmol/m³ HCl solutions at 303 K. In addition, the corrosion behavior of a solution annealed austenitic stainless steel type 304 was studied under the same experimental conditions as a reference. It was found that the intergranular attack was observed for Ni₃(Si,Ti) at an initial stage of the immersion test, but not Ni₃(Si,Ti) + 2Mo, while Ni₃(Si,Ti) + 2Mo had the preferential dissolution of L1₂ with a lower Mo concentration compared to (L1₂ + Ni_ss) mixture region. From the immersion test and polarization curves, Ni₃(Si,Ti) + 2Mo showed the lowest corrosion resistance in both solutions and Ni₃(Si,Ti) had the highest corrosion resistance in the HCl solution, but not in the H₂SO₄ solution. For instance, it was found that unlike type 304 stainless steel, these intermetallic compounds were difficult to form a stable passive film in the H₂SO₄ solution. The results obtained were explained in terms of boron segregation at grain boundaries, Mo enrichment and film stability (or strength).     

Structural evolution of electroless Ni-P coating on Al-12 wt.% Si alloy during heat treatment at high temperatures

The work is concerned with the high-temperature heat treatment of an Al-12 wt.% Si alloy coated by an electroless Ni-P layer. The electroless deposition took place on a pre-treated substrate in a bath containing nickel hypophosphite, nickel lactate and lactic acid. Resulting Ni-P deposit showed a thickness of about 8 μm. The coated samples were heat-treated at 200-550 °C/1-24 h. LM, SEM, EDS and XRD were used to investigate phase transformations. Adherence to the substrate was estimated from the scratch test and microhardness of the heat-treated layers was also measured. It is found that various phase transformations occur, as both temperature and annealing time increase. These include (1) amorphous Ni-P → Ni + Ni₃P, (2) Al + Ni → Al₃Ni, (3) Ni₃P → Ni₁₂P₅ + Ni, (4) Ni₁₂P₅ → Ni₂P + Ni, and (5) Al₃Ni + Ni → Al₃Ni₂. The formation of intermetallic phases, particularly Al₃Ni₂, leads to significant surface hardening, however, too thick layers of intermetallics reduce the adherence to the substrate. Based on the growth kinetics of the intermetallic phases, diffusion coefficients of Ni in Al₃Ni and Al₃Ni₂ at 450-550 °C are estimated as follows: D(Al₃Ni, 450 °C) ≈ 6 × 10⁻¹² cm² s⁻¹, D(Al₃Ni, 550 °C) ≈ 4 × 10⁻¹¹ cm² s⁻¹, D(Al₃Ni₂, 450 °C) ≈ 1 × 10⁻¹² cm² s⁻¹ and D(Al₃Ni₂, 550 °C) ≈ 1 × 10⁻¹¹ cm² s⁻¹. Mechanisms of phase transformations are discussed in relation to the elemental diffusion.     

(Mo + N) codoped TiO2 for enhanced visible-light photoactivity

A series of Ti_1−xMo_xO_2−yN_y samples were prepared by using sol-gel method and characterized by X-ray diffraction, transmission electron microscopy and UV-vis absorption spectroscopy. All Ti_1−xMo_xO_2−yN_y samples are anatase phase. It is found that Mo, N mono-doping can increase visible light absorption, while (Mo + N) co-doping can greatly enhance absorption in whole visible region. Results of our first-principles band structure calculations reveal that (Mo + N)-doping, especially passivated co-doping can increase the up-limit of dopant concentration and create more impurity bands in the band gap of TiO₂, which leads to a greatly increase of its visible-light absorption without a decrease of its redox potential. It reveals that (Mo + N) co-doped TiO₂ is promising for a photocatalyst with high photocalystic activity under visible light.     

Characterization of cubic phase MgZnO/Si(1 0 0) interfaces

The microstructural properties of the Mg_xZn_1−xO/Si(1 0 0) interface were investigated using transmission electron microscopy (TEM) and chemical states of the heterostructure were studied by high resolution X-ray photoelectron spectroscopy (XPS). By analyzing the valence band spectra of thin Mg_xZn_1−xO/Si(1 0 0) heterostructures, the valence band offset between such Mg_0.55Zn_0.45O and Si(1 0 0) was obtained to be 2.3 eV. Using the cubic ternary thin films as insulators, metal-insulator-semiconductor (MIS) capacitors have been fabricated. Leakage current density lower than 3 × 10⁻⁷ A/cm² is obtained under the electrical field of 600 kV/cm by current-voltage (I-V) measurement. Frenkel-Poole conduction mechanism is the main cause of current leakage under high electrical field.     

Theoretical study on adsorption of Au and hydrated Au cations on clean Si(1 1 1) surface

To model the adsorption of Au⁺ cation in aqueous solution on the semiconductor surface, the interactions of Au⁺ and hydrated Au⁺ cations with clean Si(1 1 1) surface were investigated by using hybrid density functional theory (B3LYP) and Møller-Plesset second-order perturbation (MP2) methods. Si(1 1 1) surface was described with Si₇H₁₁, Si₁₁H₁₇ and Si₂₂H₂₁ clusters. The effect of the basis set superposition error (BSSE) was taken into account by applying the counterpoise correction. The calculated results indicated that the binding energies between hydrated Au⁺ cations and clean Si(1 1 1) surface are large, suggesting a strong interaction between hydrated Au⁺ cations and the semiconductor surface. The bonding nature of the chemical adsorption of Au⁺ to Si surface can be classified as partial covalent as well as ionic bonding. As the number of water molecules increases, the water molecules form hydrogen bond network with one another and only one water molecule binds directly to the Au⁺ cation. The Au⁺ cation in aqueous solution will safely attach to the clean Si(1 1 1) surface.     

Microstructure and electrical properties of (Zr, Sn)TiO4 thin film deposited on Si(1 0 0) using a sol-gel process

Polycrystalline zirconium tin titanate (Zr_0.8Sn_0.2TiO₄, ZST) thin films with thickness of 81 nm were deposited successfully along the (1 0 0) on a p-type Si substrate by an improved sol-gel method. The deposited films were crystallized when annealing temperature was up to 450 °C. The thickness and compositions of the interface layer between the ZST films and Si substrate were identified by high-resolution transmission electron microscope (HRTEM). The electrical properties such as leakage current density, flat-band voltage and capacitance of the films were measured and discussed. Furthermore, the mechanism of the leakage current was also investigated.     

Formation of strontium template on Si(1 0 0) by atomic layer deposition

The formation of ordered Sr overlayers on Si(1 0 0) by Atomic Layer Deposition (ALD) from bis(triisopropylcyclopentadienyl) Strontium (Sr(C₅ⁱPr₃H₂)₂) and H₂O has been investigated. SrO overlayers were deposited on a 1-2 nm SiO₂/Si(1 0 0) substrate, followed by a deoxidation process to remove the SiO₂ layer at high temperatures. Auger electron spectroscopy, Rutherford backscattering spectrometry, spectroscopic ellipsometry, and low-energy electron diffraction were used to investigate the progress of both ALD and deoxidation processes. Results show that an ordered Sr/Si(1 0 0) surface with 2 × 1 pattern can be obtained after depositing several monolayers of SrO on Si using ALD followed by an anneal at 800-850 °C. The (2 × 1) ordered Sr/Si(1 0 0) surface is known to be an excellent template for the epitaxial growth of SrTiO₃ (STO) oxide. The present results demonstrate that ALD is a potential alternative to molecular beam epitaxy methods for the fabrication of epitaxial oxides on semiconductor substrates.     

Characterization of Cr/6H-SiC(0 0 0 1) nano-contacts by current-sensing AFM

The electrical properties and interface chemistry of Cr/6H-SiC(0 0 0 1) contacts have been studied by current-sensing atomic force microscopy (CS-AFM) and X-ray photoelectron spectroscopy (XPS). Cr layers were vapor deposited under ultrahigh vacuum onto both ex situ etched in H₂ and in situ Ar⁺ ion-bombarded samples. The Cr/SiC contacts are electrically non-uniform. Both the measured I-V characteristics and the modeling calculations enabled to estimate changes of the Schottky barrier height caused by Ar⁺ bombardment. Formation of ohmic nano-contacts on Ar⁺-bombarded surfaces was observed.     

Effect of residual oxygen on ionization processes of Si and Si sputtered from Si(1 1 1)-7 × 7 surface

The effect of residual oxygen impurity on ionization processes of Si⁺ and Si²⁺ has been studied quantitatively. In this study, ion sputtering experiments were carried out for a Si(1 1 1)-7 × 7 surface, irradiated with 9-11 keV Ar⁰ and Kr⁰ beam. Even if the oxygen concentration is less than the detection limit of Auger electron spectrometry, SiO⁺ and SiO₂⁺ ions have been appreciably observed. Moreover, as the SiO⁺ and SiO₂⁺ yields increases, the Si⁺ yield is slightly enhanced, whereas the Si²⁺ yield is significantly reduced. From the incidence angle dependence of secondary ion yields, it is confirmed that Si⁺* (Si⁺ with a 2p hole) created in the shallow region from the surface exclusively contributes to Si²⁺ formation. By assuming that the SiO⁺ and SiO₂⁺ yields are proportional to the residual oxygen concentration, these observations are reasonably explained: The increase of Si⁺ with the increase of residual oxygen is caused by a similar effect commonly observed for oxidized surfaces. The decrease of Si²⁺ yield can be explained by the inter-atomic Auger transition between the residual oxygen impurity and Si⁺*, which efficiently interferes the Si²⁺ formation process.     

Effect of erbium interlayer on nickel silicide formation on Si(1 0 0)

To reveal the influence of erbium interlayer on the formation of nickel silicide and its contact properties on Si substrate, Er(0.5-3.0 nm) and Ni(20 nm) are successively deposited onto Si(1 0 0) substrate and are treated by rapid thermal annealing in pure N₂ ambient. The NiSi formation temperature is found to increase depending on the Er interlayer thickness. The formation temperature of NiSi₂ (700 °C) is not influenced by Er addition. But with 2 nm Er interlayer, the formed NiSi₂ is observed textured with preferred orientation of (1 0 0). During the formation of NiSi, Er segregates to the surface and little Er remains at the NiSi/Si(1 0 0) interface. Therefore, the Schottky barrier height of the formed NiSi/n-Si(1 0 0) contact is measured to be 0.635 ∼ 0.665 eV which is nearly invariable with different Er addition.     

Scaling behavior of island density in submonolayer growth of CaF2 on vicinal Si(1 1 1)

We have studied the scaling behavior of two-dimensional island density during submonolayer growth of CaF₂ on vicinal Si(1 1 1) surfaces using scanning tunneling microscopy. We have analyzed the morphology of the Si(1 1 1) surfaces where CaF₂ partial monolayers with coverages of about 0.1 monolayer are deposited at ∼600 °C. The number density of terrace nucleated islands increases with substrate terrace width l as ∼l⁴ in a low island density regime. This scaling behavior is consistent with predictions for the case of the irreversible growth of islands.     

Self-limited growth of Si on B atomic-layer formed Ge(1 0 0) by ultraclean low-pressure CVD system

Utilizing BCl₃ reaction on Ge(1 0 0) and subsequent Si epitaxial growth by SiH₄ reaction at 300 °C, B atomic-layer doping in Si/Ge(1 0 0) heterostructure was investigated. Cl atoms on the B atomic-layer formed Ge(1 0 0) scarcely affect upon the SiH₄ reaction. It is also found that Si atom amount deposited by SiH₄ reaction on Ge(1 0 0) is effectively enhanced by the existence of B atomic layer and the deposition rate tends to decrease at around 2-3 atomic layers which is three times larger than that in the case without B. The results of angle-resolved X-ray photoelectron spectroscopy show that most B atoms are incorporated at the heterointerface between the Si and Ge.     

Rate coefficients measurement for the energy-pooling collisions Cs(5D) + Cs(5D) → Cs(6S) + Cs(nl = 9D, 11S, 7F)

We report experimental rate coefficients for the energy-pooling collisions Cs(5D) + Cs(5D) → Cs(6S) + Cs(nl = 9D, 11S, 7F). In the experiment the Cs(5D) state was populated via photodissociation of Cs₂ molecules using an argon-ion laser at wavelength 488.0 nm. We also consider the competing process 6P_1/2 + 7S → 6S + (nl = 9D, 11S, 7F) that might also populate 9D, 11S and 7F. An intermodulation technique was used to select the fluorescence contributions due only to the process 6P_1/2 + 7S → 6S + (nl = 9D, 11S, 7F). The excited atom (nl_J) density and spatial distribution were mapped by monitoring the absorption of a counterpropagating probe laser beam tuned to various transitions. The measured excited atom densities are combined with measured fluorescence ratios to yield rate coefficients for the energy-pooling collisions Cs(5D) + Cs(5D) → Cs(6S) + Cs(nl = 9D, 11S, 7F). The rate coefficients for nl = 9D, 11S, 7F are (4.1 ± 2.0) × 10⁻¹⁰ cm³ s⁻¹, (1.6 ± 0.8) × 10⁻¹⁰ cm³ s⁻¹ and (3.6 ± 1.8) × 10⁻¹⁰ cm³ s⁻¹, respectively. The contributions to the rate coefficients from other energy transfer processes are also discussed.     

Desorption of chemisorbed Carbon on Mo(1 0 0) by noble gas ion sputtering: Validation of ground test measurements of ion engine lifetimes

We report desorption cross section measurements for one monolayer of chemisorbed carbon on a Mo(1 0 0) surface induced by sputtering with noble gas ions (Ne⁺, Ar⁺, Xe⁺) at different incident angles, ion energies, and substrate temperatures. Desorption cross sections were determined by using low-energy ion scattering (LEIS) to monitor the increase of the signal from the Mo substrate. A monolayer of p(1 × 1) carbon adatoms on the Mo(1 0 0) surface was created by dosing ethylene (C₂H₄) to the substrate at 800 K, and characterized by Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). We find that the carbon desorption cross section increases with increasing mass and energy of the impinging ions, and there is a maximum value for the desorption cross section at an incident angle for the ions of 30° from the surface plane. The desorption cross section also increases up to a substrate temperature of 300 °C. Values for the carbon desorption cross section for carbon adatoms on Mo(1 0 0) by 400-eV Xe⁺ ion sputtering are about 2 × 10⁻¹⁵ cm², which is one order of magnitude higher than those for bulk carbon samples. This information is particularly important for evaluation of ion-engine lifetimes from ground-test measurements in which contaminant carbon is deposited on Mo accelerator grids, potentially altering the sputtering rate of the Mo. Our measurements show that monolayer amounts of carbon on Mo have desorption cross sections that are two orders of magnitude higher than estimates of what would be required to reduce the Mo erosion rate, and thus ground-test measurements can be used with confidence to predict ion-engine wear in space, from this perspective.     

Highly resolved scanning tunneling microscopy study of Si(0 0 1) surfaces flattened in aqueous environment

A surface preparation method with fine SiO₂ particles in water is developed to flatten Si(0 0 1) surfaces on the nanometer scale. The flattening performance of Si(0 0 1) surfaces after the surface preparation method is investigated by scanning tunneling microscopy. The observed surface is so flat that 95% of the view area (100 × 100 nm²) is composed of only three atomic layers, namely, one dominant layer occupying 50% of the entire area and two adjacent layers. Furthermore, a magnified image shows the outermost Si atoms regularly distributed along the 〈1 1 0〉 direction on terraces.     

Surface morphology of epitaxial lattice-matched Ba0.7Sr0.3O on Si(0 0 1) and vicinal Si(0 0 1)-4°[1 1 0] substrates

Exploring ways for self-organized structuring of insulating thin films, we investigated the possibility to produce replicas of step trains, given by a vicinal Si(0 0 1)-4°[1 1 0] surface, in layers of crystalline and perfectly lattice-matched Ba_0.7Sr_0.3O. For this purpose, we carried out high-resolution spot profile analyses in low-energy electron diffraction (SPA-LEED) both on flat Si(0 0 1) and on Si(0 0 1)-4°[1 1 0]. Oxide layers were generated by evaporating the metals in oxygen ambient pressure with the sample at room temperature. Our G(S) analysis of these mixed oxide layers reveals a strong influence of local compositional fluctuations of Sr and Ba ions and their respective scattering phases, which appears as an unphysically large variation of layer distances. Nevertheless, we are able to show that quite smooth and closed oxide films are obtained with an rms roughness of about 1 ML. These Ba_0.7Sr_0.3O films directly follow the step train of Sr-modified vicinal Si surfaces that form (1 1 3) oriented facets after adsorption of a monolayer of Sr. This proves that self-organized structuring of insulating films can indeed be an effective method.     

Bimodal growth of manganese silicide on Si(1 0 0)

Two different growth modes of manganese silicide are observed on Si(1 0 0) with scanning tunneling microscopy. 1.0 and 1.5 monolayer Mn are deposited at room temperature on the Si(1 0 0)-(2 × 1) substrate. The as-grown Mn film is unstructured. Annealing temperatures between room temperature and 450 °C lead to small unstructured clusters of Mn or Mn_xSi_y. Upon annealing at 450 °C and 480 °C, Mn reacts chemically with the Si substrate and forms silicide islands. The dimer rows of the substrate become visible again. Two distinct island shapes are found and identified as MnSi and Mn₅Si₃.     

Determination of the rate of H + O2 + M → HO2 + M (M = N2, Ar, H2O) from ignition of syngas at practical conditions

In H₂ and H₂/CO oxidation, the H + O₂ + M termination step is one of the most important reactions at elevated pressures. With the recent, increased interest in synthetic fuels, an accurate assessment of its rate coefficient becomes increasingly important, especially for real fuel/air mixtures. Ignition delay times in shock-tube experiments at the conditions selected in this study are only sensitive to the rates of the title reaction and the branching reaction H + O₂ = OH + O, the rate of which is known to a high level of accuracy. The rate coefficient of the title reaction for M = N₂, Ar, and H₂O was determined by adjusting its value in a detailed chemical kinetics model to match ignition delay times for H₂/CO/O₂/N₂, H₂/CO/O₂/Ar, and H₂/CO/O₂/N₂/H₂O mixtures with fuel/air equivalence ratios of ? = 0.5, 0.9, and 1.0. The rate of H + O₂ + N₂ = HO₂ + N₂ was measured to be 2.7 (−0.7/+0.8) × 10¹⁵ cm⁶/mol² s for T = 916-1265 K and P = 1-17 atm. The present determination agrees well with the recent study of Bates et al. [R.W. Bates, D.M. Golden, R.K. Hanson, C.T. Bowman, Phys. Chem. Chem. Phys. 3 (2001) 2337-2342], whose rate expressions are suggested herein for modeling the falloff regime. The rate of H + O₂ + Ar = HO₂ + Ar was measured to be 1.9 × 10¹⁵ cm⁶/mol² s for T = 932-965 K and P = 1.4 atm. The rate of H + O₂ + H₂O = HO₂ + H₂O was measured to be 3.3 × 10¹⁶ cm⁶/mol² s for T = 1071-1161 K and P = 1.3 atm. These are the first experimental measurements of the rates of the title reactions in practical combustion fuel/air mixtures.     

Initial stages of iron silicide formation on the Si(1 0 0)2 × 1 surface

The initial stages of iron silicide growth on the Si(1 0 0)2 × 1 surface during solid-phase synthesis were investigated by photoelectron spectroscopy using synchrotron radiation. The experiments were made on iron films of 1-50 monolayer (ML) thickness in the temperature range from room temperature to 750 °С. Our results support the existence of three stages in the Fe deposition on Si(1 0 0) at room temperature, which include formation of the Fe-Si solid solution, Fe₃Si silicide and an iron film. The critical Fe dose necessary for the solid solution to be transformed to the silicide is found to be 5 ML. The solid-phase reaction was found to depend on the deposited metal dose. At 5 ML, the reaction begins at 60 °С, and the solid-phase synthesis leads to the formation of only metastable silicides (FeSi with the CsCl-type structure, γ-FeSi₂ and α-FeSi₂). A specific feature of this process is Si segregation on the silicide films. At a thickness of 15 ML and more, we observed only stable phases, namely, Fe₃Si, ε-FeSi and β-FeSi₂.