A theoretical investigation of the binding of TiCln to MgCl2

The structure of the (0 0 0 1) surface of the -MgCl₂ crystal has been investigated using DFT-GGA periodic calculations. The calculated surface relaxation is in agreement with LEED measurements. Motivated for the use of MgCl₂ as support for the Ziegler–Natta reaction, we have studied the adsorption of the catalyst (titanium chlorides as monomers or dimers) on the (1 0 0) and (1 1 0) MgCl₂ surfaces. The structures of adsorbed species are close to those previously found on cluster models: bridging chlorine atoms connect the Ti to the Mg atoms and the systems remain in high spin states. The (0 0 0 1) surface is the most stable face of the -MgCl₂ crystal; however it is Cl-terminated and henceforth poorly reactive; it had been suggested to deposit metallic Mg in order to improve its reactivity. Our modelling explains the failure of this tentative; the interaction between the deposited metal and the surface is repulsive and uncharged Mg atom does not bind.     

X-ray diffraction evidence of the single solid solution character of bi-metallic Pt-Pd catalyst particles on an amorphous SiO2 substrate

An X-ray diffraction study was carried out on powders of a series of catalysts prepared from aqueous solutions of H₂PtCl₆ and PdCl₄ and amorphous SiO₂ with different concentrations in weight of Pt and Pd at about 4% in overall metallic weight. Measurements of the position of high angle Bragg reflections in the diffractograms show evidence of the fact that the small catalyst particles are bi-metallic Pt-Pd crystals having a face-centred cubic Bravais lattice. The lattice constant of these crystals was found to change with the relative concentration of Pt and Pd by following the Vegard’s rule. This correlation leads to the conclusion that the bi-metallic catalyst particles are made of a single solid solution of Pt and Pd atoms in the whole range of relative concentrations. Relative concentrations of these metals in the samples under study were determined by using energy dispersive X-ray spectrometry and their values were found to be close to the stochiometric relative concentrations in weight of the metals in the precursor aqueous solution. An average size of about 96 Å was estimated for the bi-metallic particles from the full-width at half-maximum value measured for the (2 0 0) diffractometric curve.     

Evolution of morphologic properties on the preparation of Ir/Al2O3 catalysts with high metallic contents

Ir/Al₂O₃ catalysts with high metallic contents are applied on satellite thruster to decompose hydrazine. The present work has as principal aim the study of the morphologic evolution of Ir/Al₂O₃ catalysts with metallic contents from 12 to 30 wt.%. The catalysts were prepared through consecutive impregnations from the H₂IrCl₆ precursor, using three different types of aluminas. The specific surface area, volume and distribution of pore size, specific metallic area and metallic particles average diameter, as well as the mechanical resistance were determined. Results show that the Ir addition leads to a decrease of the specific surface area and the pores volumes, while increases the mechanical resistance. Values for average diameter of metallic particles are comprised between 1.4 and 2.4 nm when the metallic content increases from 12 to 30 wt.%. Catalysts containing 30 wt.% of Ir presents specific metallic areas around 30 m²/g, although pores volumes and distributions of pore size were considerably different for the three supports. Their metallic particles dispersion and size values are very close to those of a commercial catalyst Shell 405, even though the preparation methods were different. These results show that there is a strong interaction between the alumina and the iridium precursor.     

Tetrakis(diethylamido) titanium (TDEAT) interactions with SiO2 and Cu substrates

X-ray photoelectron spectroscopy (XPS) is used to characterize the chemical interactions of tetrakis(diethylamido) titanium (TDEAT) with SiO₂ and Cu surfaces under ultrahigh vacuum (UHV) conditions. XPS studies show that TDEAT dissociatively chemisorbs on SiO₂ at room temperature or above, resulting in Ti---N bond scission, and Ti---O bond formation. No Ti carbide or Si carbide formation is observed. In the presence of co-adsorbed NH₃, Ti---N bond formation is enhanced and is stable at temperature up to 900 K in UHV. Continuous exposures of TDEAT on SiO₂ at 500 K produce both Ti oxides and nitride formation. The presence of an overpressure of NH₃ enhances Ti nitride formation. In contrast, TDEAT physisorbed on Cu at 120 K and annealed to 500 K results in desorption of Ti-containing species from the surface. Successive exposures of TDEAT on Cu at 500 K yield a Ti-alkyl reaction product. The presence of NH₃ does not significantly alter TDEAT interaction with Cu.     

Annealing effects on structure and laser-induced damage threshold of Ta2O5/SiO2 dielectric mirrors

The effects of annealing on structure and laser-induced damage threshold (LIDT) of Ta₂O₅/SiO₂ dielectric mirrors were investigated. Ta₂O₅/SiO₂ multilayer was prepared by ion beam sputtering (IBS), then annealed in air under the temperature from 100 to 400 °C. Microstructure of the samples was characterized by X-ray diffraction (XRD). Absorption of the multilayer was measured by surface thermal lensing (STL) technique. The laser-induced damage threshold was assessed using 1064 nm free pulsed laser at a pulse length of 220 μs.

It was found that the center wavelength shifted to long wavelength gradually as the annealing temperature increased, and kept its non-crystalline structure even after annealing. The absorbance of the reflectors decreased after annealing. A remarkable increase of the laser-induced damage threshold was found when the annealing temperature was above 250 °C.     

Spin-polarized ion scattering spectroscopy of CCl4 adsorption on Fe(0 0 1) surfaces

The interaction of CCl₄ molecules with Fe(0 0 1) surfaces was investigated by spin-polarized ion scattering spectroscopy (SP-ISS). It was observed that CCl₄ molecules adsorb dissociatively on the surface at ambient temperature (290 K), and consequently, iron and chlorine were major surface constituents. It was found that the chlorine adatoms are located atop of iron atoms of the second surface layer (hollow sites of the surface). It is indicated that the spin state of iron atoms at the surface is not affected by exposure to a CCl₄ atmosphere, while almost no spin is induced in the chlorine adatoms. Similar behavior is observed in the spin states of iron and chlorine on an oxygen preadsorbed-Fe(0 0 1) surface. The difference in the spin states of iron and chlorine clarifies the local property of the incidence ion neutralization and element selectivity of SP-ISS in this CCl₄/Fe system.     

A quantum chemical study of ZrO2 atomic layer deposition growth reactions on the SiO2 surface

Zirconium oxide (ZrO₂) is one of the leading candidates to replace silicon oxide (SiO₂) as the gate dielectric for future generation metal-oxide-semiconductor (MOS) based nanoelectronic devices. Experimental studies have shown that a 1–3 monolayer SiO₂ film between the high permittivity metal oxide and the substrate silicon is needed to minimize electrical degradation. This study uses density functional theory (DFT) to investigate the initial growth reactions of ZrO₂ on hydroxylated SiO₂ by atomic layer deposition (ALD). The reactants investigated in this study are zirconium tetrachloride (ZrCl₄) and water (H₂O). Exchange reaction mechanisms for the two reaction half-cycles were investigated. For the first half-reaction, reaction of gaseous ZrCl₄ with the hydroxylated SiO₂ surface was studied. Upon adsorption, ZrCl₄ forms a stable intermediate complex with the surface SiO₂–OH^* site, followed by formation of SiO₂–O–Zr–Cl^* surface sites and HCl. For the second half-reaction, reaction of H₂O on SiO₂–O–Zr–Cl^* surface sites was investigated. The reaction pathway is analogous to that of the first half-reaction; water first forms a stable intermediate complex followed by evolution of HCl through combination of a Cl atom from the surface site and an H atom from H₂O. The results reveal that the stable intermediate complexes formed in both half-reactions can lead to a slow film growth rate unless process parameters are adjusted to lower the stability of the complex. The energetics of the two half-reactions are similar to those of ZrO₂ ALD on ZrO₂ and as well as the energetics of ZrO₂ ALD on hydroxylated silicon. The energetics of the growth reactions with two surface hydroxyl sites are also described.     

H, V and N nuclear magnetic resonance studies of structure and properties of vanadia supported on TiOx/SiO2

¹H magic-angle spinning nuclear magnetic resonance (MAS NMR) spectra of TiO_x/SiO₂ catalysts suggest the interaction of surface TiO_x. species with Si-OH groups of the silica. Simultaneously, Ti-OH groups from surface titania species appear. The distribution of TiO_x species over SiO₂ is non-uniform, since a considerable part of surface OH groups remains unreacted with supported titania. Supported vanadia species interact both with Si-OH and Ti-OH groups. ⁵¹V NMR spectra suggest the interaction of vanadia with supported titania species and show the non-uniform distribution of titania over the SiO₂ surface. Deposition of titania as well as vanadia produces strong electron-accepting (Lewis) sites which interact with the terminal N atom of adsorbed N₂O molecules, resulting in a downfield shift of the resonance in ¹⁵N NMR spectra. The acid strength of electron-accepting sites is similar in both cases. Only about 10% of the total amount of supported titania and vanadia create Lewis sites.     

Studies of sol–gel TiO2 and Pt/TiO2 catalysts for NO reduction by CO in an oxygen-rich condition

The textural properties, morphological features, surface basicity and oxygen reduction behaviours of titania and Pt supported titania catalysts synthesized via a sol–gel method were studied by means of N₂ physisorption, SEM, TEM, CO₂-TPD and H₂-TPR techniques. Mesostructured TiO₂ shows a very narrow pore size distribution that uniformly centred at about 4 nm. High resolution TEM images confirmed that most of Pt particles on Pt/TiO₂-SG had a size smaller than 2 nm. Both the titania support and Pt loaded catalysts chiefly contained weak basic sites with small amount of strong basic sites. Loading Pt did not significantly alter the surface reduction characters of titania, indicating a weak interaction between Pt metals and titania support. Catalytic evaluation revealed that the selectivity of NO reduction over titania was insensitive to variation of textural property. On the bare titania, low NO conversion but high selectivity to N₂O was obtained. However, the Pt/TiO₂-SG catalysts exhibited high NO conversion and high selectivity to N₂, which is assumed to relate to NO dissociation catalysed by the metallic Pt clusters. In addition, when the reaction temperature was above 200 °C, 3–11% NO₂ was yielded over the Pt/TiO₂-SG catalysts, which was discussed on a basis of reaction competition, metal-support interaction and NO dissociation.     

RF-sputtered CrB2 diffusion barrier for Ni/Au Ohmic contacts on p-CuCrO2

Ohmic contacts to p-type CuCrO₂ using Ni/Au/CrB₂/Ti/Au contact metallurgy are reported. The samples were annealed in the 200–700 °C range for 60 s in flowing oxygen ambient. A minimum specific contact resistance of 2 × 10⁻⁵ Ω cm² was obtained after annealing at 400 °C. Further increase in the annealing temperature (>400 °C) resulted in the degradation of contact resistance. Auger Electron Spectroscopy (AES) depth profiling showed that out-diffusion of Ti to the surface of the contact stacks was evident by 400 °C, followed by Cr at higher temperature. The CrB₂ diffusion barrier decreases the specific contact resistance by almost two orders of magnitude relative to Ni/Au alone.     

Si–SiO2 interface formation in low-dose low-energy separation by implanted oxygen materials

The evolution of the Si–SiO₂ interface morphology of low-dose low-energy separation by implanted oxygen materials was investigated by transmission electron microscopy and atomic force microscopy. The Si–SiO₂ interface morphology and the RMS roughness are strongly affected by the implantation conditions and the annealing process. Three main types of the domains including round, square, and pyramid shapes with the step-terrace structure were observed on the buried SiO₂ surface. Round domains are observed in the early stage of the annealing process, while the square and pyramid domains are observed after the high temperature annealing. The mean RMS roughness decreases with increasing time and annealing temperature, while in the 1350 °C 4-h annealed samples, the mean RMS roughness decreases with either increasing the implantation dose or decreasing implantation energy. The scaling analysis shows that the Si–SiO₂ interfaces were found to be self-affine on the short length scales with a roughness exponent above 0.50. Qualitative mechanisms of Si–SiO₂ surface flattening are presented in terms of the variations of morphological features with the processing conditions.     

Observations on the role of MgCl2 in the Weissler reaction

Aqueous solutions of Nal containing CCl₄ and MgCl₂ at various concentrations were irradiated under air with 1 MHz ultrasound and the yield of I₃⁻ was determined. The yield was not affected by MgCl₂ at concentrations up to 0.1 M. This contrasts with the finding of Lepoint and co-workers, who reported a sharp minimum in the yield at a MgCl₂ concentration of 2.5 × 10⁻³M, the yield decreased to 60% at 1 M MgCl₂, the reason being the lower solubility of CCl₄ at high MgCl₂ concentrations. In the absence of CCl₄, another dependence on the MgCl₂ concentration was observed: the yield was not affected up to 1 M, and at higher MgCl₂ concentrations the yield rapidly decreased owing to the increased viscosity of the solution. On the basis of these observations, there is no strong reason to postulate an electrical mechanism for the initiation of chemical reactions in the cavitation bubbles.     

Single crystal RuO2/Ti and RuO2/TiO2 interface: LEED, Auger and XPS study

The interactions at the evolving RuO₂/titanium interface have been studied by LEED, AES and XPS. Titanium films of up to 5 monolayers were evaporated onto well ordered and ion sputtered ruthenium dioxide crystal surfaces of (110) and (100) orientation. Stabilization of the surface oxygen content under thermal treatment in UHV (up to 600°C) with increasing titanium coverage was established. After extended (up to 4 h) annealing in O₂ at 600°C an epitaxial ordering of TiO₂ on RuO₂(110) was observed. The (1 × 1) LEED patterns from the epitaxial layer exhibit a reduced background level when compared to the RuO₂ substrate itself. These findings are correlated with the XPS data and are interpreted in connection with the disappearance of the defect RuO₂ phase in the surface layer of the RuO₂. The appearance of the (1 × 2) surface reconstruction at the RuO₂(100)/Ti interface is discussed in the context of maximum cation coordination by oxygen atoms.     

The thermal spreading of antimony oxides onto Fe2O3

The uniform antimony-rich surface layer on Fe₂O₃ was carried out via thermal spreading of Sb₂O₃ and Sb₂O₄. TG–DTA results indicate that the oxidation temperature of Sb₂O₃ was decreased ca. 100 K due to thermal spreading effect. Although Sb₂O₄ is almost catalytically inert for oxidation of isobutane and Fe₂O₃ is a typical non-selective catalyst for this reaction, the formation of antimony-rich layer suppresses the combustion reactions and favors the partial oxidation reactions. When Sb₂O₄ instead of Sb₂O₃ was used as antimony resource, the enrichment of antimony on Fe₂O₃ surface was much lower. However, the reaction atmosphere of isobutane oxidation enhances antimony spreading over Fe₂O₃ surface. According to Mars–Van Krevelen mechanism, some Sb₂O₄ in catalysts could be intermediately reduced into Sb₂O₃ during reaction of isobutene oxidation, which thermal spreading is much easier. As shown by Raman results, the Sb₂O₄ that has been spread on Fe₂O₃ surface is probably amorphous.     

Defect versus nanocrystal luminescence emitted from room temperature and hot-implanted SiO2 layers

Silicon nanocrystals have been synthesized in SiO₂ matrix using Si ion implantation. Si ions were implanted into 300-nm-thick SiO₂ films grown on crystalline Si at energies of 30–55 keV, and with doses of 5×10¹⁵, 3×10¹⁶, and 1×10¹⁷ cm⁻². Implanted samples were subsequently annealed in an N₂ ambient at 500–1100°C during various periods. Photoluminescence spectra for the sample implanted with 1×10¹⁷ cm⁻² at 55 keV show that red luminescence (750 nm) related to Si-nanocrystals clearly increases with annealing temperature and time in intensity, and that weak orange luminescence (600 nm) is observed after annealing at low temperatures of 500°C and 800°C. The luminescence around 600 nm becomes very intense when a thin SiO₂ sample is implanted at a substrate temperature of 400°C with an energy of 30 keV and a low dose of 5×10¹⁵ cm⁻². It vanishes after annealing at 800°C for 30 min. We conclude that this luminescence observed around 600 nm is caused by some radiative defects formed in Si-implanted SiO₂.     

Defects and Pd growth on the reduced SnO2(1 0 0) surface

Scanning tunneling microscopy experiments on a clean, reduced SnO₂(1 0 0)-(1 × 1) surface reveal surface defects with zero-, one-, and two-dimensions. Point defects consist of missing SnO/SnO₂ units. Line defects are probably crystallographic shear planes that extend to the surface and manifest themselves as rows of atoms, shifted half a unit cell along the [0 1 0] direction. Their ends act as preferential nucleation sites for the formation of Pd clusters upon vapor deposition. Areas of a more reduced surface phase, still with a (1 × 1) structure and a half-unit cell deep, form at [0 0 1]-oriented step edges.     

The surface structure of catalysts activated with hydrogen donors as elucidated by multinuclear solid-state NMR

¹H, ²⁷Al and ³¹P MAS, and ¹³C and ²⁹Si CP/MAS NMR spectroscopies, were used to characterize catalysts of Pd supported on various solids including SiO₂, AlPO₄ and Mg₃(PO₄)₂ that were activated with the chiral hydrogen-donor limonene. The above-mentioned techniques were used to check for the formation of an organopalladium complex between Pd²⁺ atoms and the olefin bonds in the limonene molecule on the catalyst surface. The results are compared with those obtained for catalysts activated in a hydrogen stream.     

A theoretical analysis of the TiO2/Sn doped (1 1 0) surface properties

We have used the periodic quantum-mechanical method with density functional theory at the B3LYP level in order to study TiO₂/Sn doped (1 1 0) surfaces and have investigated the structural, electronic and energy band properties of these oxides. Our calculated relaxation directions for TiO₂ is the experimental one and is also in agreement with other theoretical results. We also observe for the doped systems relaxation of lattice positions of the atoms. Modification of Sn, O and Ti charges depend on the planes and positions of the substituted atoms. Doping can modify the Fermi levels, energy gaps as well as the localization and composition of both valence and conduction band main components. Doping can also modify the chemical, electronic and optical properties of these oxides surfaces increasing their suitability for use as gas sensors and optoelectronic devices.     

Mechanism and energetics of dimerization of SiH2 radicals on H-terminated Si(0 0 1)-(2×1) surfaces

The mechanism and energetics are presented of the dimerization of two adsorbed surface SiH₂ groups on the H-terminated Si(0 0 1)-(2 × 1) surface to form Si₂H₄ species during the initial stages of growth in plasma deposition of hydrogenated amorphous silicon (a-Si:H) films. The reactions are observed during classical molecular-dynamics (MD) simulations of a-Si:H film deposition from SiH₂ radical precursors impinging on an initially H-terminated Si(0 0 1)-(2 × 1) surface and substrate temperature, T, over the range 500T700 K. The Si₂H₄ species resulting from the surface SiH₂ dimerization reactions undergo surface conformational changes resulting in either a non-rotated (NRD) or a rotated dimer (RD) configuration. The RD configuration is found to be the energetically favorable one. The MD simulation results for the structure of the NRD and RD surface Si₂H₄ configurations corroborate with ab initio calculations of optimized adsorption configurations of SiH₂ radicals on crystalline Si surfaces, as well as results of STM imaging of the thermal decomposition of disilane on Si(0 0 1).     

SiO2 passivation film effects on microwave characteristics of YBa2Cu3O7−x-based resonators

SiO₂ film coated as a passivation layer for YBa₂Cu₃O_7−x (YBCO)-based microwave devices is investigated by measuring the microwave characteristics of microstrip line resonators. The SiO₂ film is deposited with its 0.3 to 0.4 μm thickness by a sputtering method using Ar + 30%O₂ plasma. These deposition conditions do not degrade the microwave characteristics and the critical temperature (T_c). Next, the SiO₂ film coated resonators are compared with the uncoated ones for two kinds of degradation conditions: a 200°C annealing in air, and an exposure to air at 85°C and 85% RH (relative humidity). We find that the SiO₂ passivation film prevents the YBCO thin film from the surface degradation and reacting with water.