Interaction of amines with native aluminium oxide layers in non-aqueous environment: Application to the understanding of the formation of epoxy-amine/metal interphases

Interaction of propylamine (PA), 1,2-diaminoethane (DAE) or 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophorone diamine, IPDA) with native aluminium oxide layers in non-aqueous environment has been studied using time-resolved inductively coupled plasma optical emission spectroscopy (ICP-OES) and X-ray photoelectron spectroscopy (XPS). The formation of several surface complexes has been evidenced. Monodentate and bidentate metal-bond surface complexes (MBSC) result from interactions between the amine terminations of the molecule and aluminium cations by donation of the N lone electron pair to the metal ion (Lewis-like mechanism leading to OAl?N bonds). Monodentate and bidentate hydrogen-bond surface complexes (HBSC) are due to interaction of the amino group with surface hydroxyl groups by protonation of the amine termination (Brønsted-like mechanism leading to the formation of AlOH?N bonds) or interaction with carbonaceous contamination (C_xO_yH_z?N bonds). Diamines can also form mixed complexes with one amino group forming an O-Al?N bond and the other group forming an AlOH…N or C_xO_yH_z?N bond. AlOH?N and C_xO_yH_z…N bonds are less stable under vacuum than OAl?N bonds, leading to partial desorption of the DAE molecules in vacuum and modification of the interaction modes. Only DAE and IPDA can lead to partial dissolution of the aluminium native (hydr)oxide films. A detailed mechanism of dissolution has been proposed based on the formation of mononuclear bidentate (chelate) MBSC by ligand exchange between the terminal η¹-OH and bridged μ₂-OH surface sites and the amino terminations of the molecule. The detachment of this complex from the surface is likely to be the precursor step to the formation of the interphase in epoxy-amine/metal systems.     

Luminescence of Ytterbium and Neodymium in Complexes with Bis-Macrocyclic Ligands

We have studied the spectral-luminescent characteristics of ytterbium and neodymium ions in complexes with new polydentate bis-crown-ether and bis-azacyclic ligands both of whose parts are bound by 2,9-substituted 1,10-phenanthroline. The relationship between the intensity, rare-earth ion luminescence lifetime, and the composition of the coordination sphere of the complexes is established. Using the considered compounds as an example, we show the advantage of the joint influence of screening of the central ion from the effect of high-frequency O–H- and C–H vibrations of the solvent molecules and of the photoantenna effect in improvement of the luminescent characteristics of lanthanides.     

Analysis of the DNA Fourier transform-infrared microspectroscopic signature using an all-reflecting objective

The Fourier transform-infrared (FT-IR) signature of dry samples of DNA and DNA-polypeptide complexes, as studied by IR microspectroscopy using a diamond attenuated total reflection (ATR) objective, has revealed important discriminatory characteristics relative to the PO₂⁻ vibrational stretchings. However, DNA IR marks that provide information on the sample's richness in hydrogen bonds have not been resolved in the spectral profiles obtained with this objective. Here we investigated the performance of an “all reflecting objective” (ARO) for analysis of the FT-IR signal of hydrogen bonds in DNA samples differing in base richness types (salmon testis vs calf thymus). The results obtained using the ARO indicate prominent band peaks at the spectral region representative of the vibration of nitrogenous base hydrogen bonds and of NH and NH₂ groups. The band areas at this spectral region differ in agreement with the DNA base richness type when using the ARO. A peak assigned to adenine was more evident in the AT-rich salmon DNA using either the ARO or the ATR objective. It is concluded that, for the discrimination of DNA IR hydrogen bond vibrations associated with varying base type proportions, the use of an ARO is recommended.     

XPS analysis of down stream plasma treated wool: Influence of the nature of the gas on the surface modification of wool

A microwave plasma treatment in a down stream configuration was used to modify the natural hydrophobocity of untreated wool fibers. This property is a consequence of the presence of a Fatty acid monolayer (F-layer) on the outermost part of the fiber surface. The wool fibers treated with plasma were analyzed by means of X-ray photoelectron spectroscopy (XPS) without previous exposure to the air. Experiments have been carried out with air, water vapor, oxygen and nitrogen as plasma gas. The “in situ” analysis of the treated samples has permitted to differentiate between the plasma effects and those other linked to the exposure of the fibers to the air after their treatment. The results have evidenced the effects induced by the different active species generated by plasma from the different components of the air. In general, the intensity of CC peaks decreases and that of the CO, CO and OCO increases when using a gas containing oxygen species. Simultaneously, the intensity of the SS groups decreases and that of the sulphonate (SO₃⁻) increases. Other changes are also detected in the intensity of the N 1s level. The extent and characteristics of the oxidation and functionalisation of the hydrocarbon chains of the F-layer depend on the nature of gas. Thus, whereas treatments with plasmas of air and water vapor strongly affect the hydrocarbon chains of the F-layer, oxygen is less effective in the oxidation process. It has been also noted that the active species formed in the nitrogen plasma do not induce any significant change in the surface composition of the wool fibers.     

Reaction of acetonitrile with the silicon(0 0 1) surface: A combined XPS and FTIR study

The adsorption of acetonitrile on the Si(0 0 1) surface has been investigated using X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR). XPS and FTIR spectra indicate that adsorbed acetonitrile forms two correlated binding configurations, a CN species with a strong FTIR absorption at 1540 cm⁻¹ and a CCN (ketenimine) species that has a very strong FTIR absorption at 1952 cm⁻¹. The CCN FTIR peak at 1952 cm⁻¹ shows a striking polarization dependence, with the infrared transition dipole almost entirely in the plane of the sample and parallel to the SiSi dimer axis. Our data suggests that the primary CCN structure results from cleavage of two C-H bonds, forming a structure in which the N and terminal C atom are both linked to the surface. Temperature-dependent experiments help to elucidate the complicated reaction mechanism for acetonitrile adsorbing onto the Si(0 0 1) surface. Dosing at higher temperature increases the amount of CCN relative to CN species while heating leads to direct transformation of the CN to the CCN species. Our results indicate that previous studies, which considered only products formed by cleavage of a single C-H bond, have misidentified the primary ketenimine product. A reinterpretation of the earlier results, combined with data presented here, sheds new light onto the products and mechanism of interaction of acetonitrile with Si(0 0 1).     

Surface morphology and composition of c-, a- and m-sapphire surfaces in O2 and H2 environments

This paper reports that monitoring the composition of the c(0 0 0 1), a(11–20) and m(10–10) sapphire surfaces is essential for a proper interpretation of the surface morphologies obtained after annealing at 1253 and 1473 K in ArH₂ or ArO₂ atmospheres. Our experimental investigations, which have used Auger electron spectroscopy (AES) and atomic force microscopy (AFM) on the surfaces of 99.99% pure sapphire wafers, have led to the following original conclusions: (i) Calcium segregates at the c-surface of sapphire both under ArO₂ and ArH₂. (ii) Potassium adsorption enhances the kinetics of step-bunching on the c-surface under ArO₂. (iii) The step edges on the a-surface may develop a comb-like morphology made of parallel strips along the [10–10] direction. (iv) At 1253 K, clean m-surfaces may be stable. (v) Under ArH₂, alumina surface diffusion is much slower than under ArO₂ for all surface orientations, the surface concentration of impurities is low, and the Al–O ratio of the AES signals at the surface is significantly larger.     

Selective surface chemistry of allyl alcohol and allyl aldehyde on Si(1 0 0)2×1: Competition of [2 + 2] CC cycloaddition with O-H dissociation and with [2 + 2] CO cycloaddition in bifunctional molecules

Competition between the CC functional group with the OH group in allyl alcohol and with the CO group in allyl aldehyde in the adsorption and thermal chemistry on Si(1 0 0)2×1 has been studied by X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD), as well as density-functional theory (DFT) calculations. The similarities found in the C 1s and O 1s spectra for both molecules indicate that the O-H dissociation product for allyl alcohol and [2 + 2] CO cycloaddition product for allyl aldehyde are preferred over the corresponding [2 + 2] CC cycloaddition products. Temperature-dependent XPS and TPD studies further show that thermal evolution of these molecules gives rise to the formation of ethylene, acetylene, and propene on Si(1 0 0)2×1, with additional CO evolution only from allyl alcohol. The formation of these desorption products also supports that the [2 + 2] CC cycloaddition reaction does not occur. In addition, the formation of SiC at 1090 K is observed for both allyl alcohol and allyl aldehyde. We propose plausible surface-mediated reaction pathways for the formation of these thermal evolution products. The present work illustrates the crucial role of the Si(1 0 0)2×1 surface in selective reactions of the Si dimers with the O−H group in allyl alcohol and with the CO group in allyl aldehyde over the CC functional group common to both molecules.     

Effect of contact interface configuration on electronic transport in (C20)2-based molecular junctions

Using first-principles calculations, we study the electronic transport properties in Au(C₂₀)₂Au molecular junctions with different contact interface configurations: point contact and bond contact. We observe that the transmission through the bond contact is considerably higher than that of point contact. Furthermore, the I-V characteristics are rather different. For the bond contact, we get a metallic behavior followed by a varistor-type behavior. While as for the point contact, the current increases very slowly in a nonlinear way and is one order of magnitude smaller than that of bond contact. We attribute these obvious differences to the distinct contact configurations.     

A micro-spectroscopy study on the influence of chemical residues from nanofabrication on the nitridation chemistry of Al nanopatterns

We applied spatially resolved photoelectron spectroscopy implemented with an X-ray photoemission electron microscopy (XPEEM) using soft X-ray synchrotron radiation to identify the compositional and morphological inhomogeneities of a SiO₂/Si substrate surface nanopatterned with Al before and after nitridation. The nanofabrication was conducted by a polymethylmethacrylate (PMMA)-based e-beam lithography and a fluorine-based reactive ion etching (RIE), followed by Al metalization and acetone lift-off. Three types of chemical residues were identified before nitridation: (1) fluorocarbons produced and accumulated mainly during RIE process on the sidewalls of the nanopatterns; (2) a thick Al-bearing PMMA layer and/or (3) a thin PMMA residue layer owing to unsuccessful or partial lift-off of the e-beam unexposed PMMA between the nanopatterns. The fluorocarbons actively influenced the surface chemical composition of the nanopatterns by forming AlF compounds. After nitridation, in the PMMA residue-free area, the AlF compounds on the sidewalls were decomposed and transformed to AlN. The PMMA residues between the nanopatterns had no obvious influence on the surface chemical composition and nitridation properties of the Al nanopatterns. They were only partially decomposed by the nitridation. The regional surface morphology of the nanopatterns revealed by the secondary electron XPEEM was consistent with the scanning electron microscopy results.     

Si-nanostructures formation in amorphous silicon nitride SiNx:H deposited by remote PECVD

The formation of silicon nanoclusters embedded in amorphous silicon nitride (SiN_x:H) can be of great interest for optoelectronic devices such as solar cells. Here amorphous SiN_x:H layers have been deposited by remote microwave-assisted chemical vapor deposition at 300 °C substrate temperature and with different ammonia [NH₃]/silane [SiH₄] gas flow ratios (R=0.5−5). Post-thermal annealing was carried out at 700 °C during 30 min to form the silicon nanoclusters. The composition of the layers was determined by Rutherford back scattering (RBS) and elastic recoil detection analysis (ERDA). Fourier transform infrared spectroscopy (FTIR) showed that the densities of SiH (2160 cm⁻¹) and NH (3330 cm⁻¹) molecules are reduced after thermal annealing for SiN:H films deposited at flow gas ratio R>1.5. Breaking the SiH bonding provide Si atoms in excess in the bulk of the layer, which can nucleate and form Si nanostructures. The analysis of the photoluminescence (PL) spectra for different stoichiometric layers showed a strong dependence of the peak characteristics (position, intensity, etc.) on the gas flow ratio. On the other hand, transmission electron microscopy (TEM) analysis proves the presence of silicon nanoclusters embedded in the films deposited at a gas flow ratio of R=2 and annealed at 700 °C (30 min).     

Effect of oxidation on the optical and surface properties of AlGaN

The chemical properties of Al_xGa_1−xN surfaces exposed to air for different time periods are investigated by atomic force microscopy (AFM), photoluminescence (PL) measurement and X-ray photoelectron spectroscopy (XPS). PL and AFM results show that Al_xGa_1−xN samples exhibit different surface characteristics for different air-exposure times and Al contents. The XPS spectra of the Al 2p and Ga 2p core levels indicate that the peaks shifted slightly, from an AlN to an AlO bond and from a GaN to a GaO bond. All of these results show that the epilayer surface contains a large amount of Ga and Al oxides.     

Growth and ordering of CuO chains on Ag(110) surface

Growth of CuO chains and their ordering on Ag(110) surface were monitored by scanning tunneling microscopy (STM). When Cu atoms were deposited on a (2 × 1)AgO/Ag(110) surface at room temperature, the AgO chains in the [001] direction diminished and new strings of CuO grew along the [110] direction and yield a (2 × 2) p2mg ordering. When a Ag(110) surface with coexisting AgO and CuO chains was exposed to CO at room temperature, the AgO chains were selectively reduced.     

Influences of compositions and ligands on photoluminescent properties of Eu(III) ions in composite europium complex/PMMA systems

Three kinds of europium complexes; Eu(phen)₂Cl₃(H₂O)₂, Eu(DN-bpy)phenCl₃(H₂O)₂ and Eu(DB-bpy)phenCl₃(H₂O)₂ (phen: 1,10-phenanthroline, DN-bpy: 4,4′-Dinonyl-2,2′-dipyridyl, DB-bpy: 4,4′-Di-tert-butyl-2,2′-dipyridyl) were prepared and then incorporated into polymethyl methacrylate (PMMA) matrix with different molar ratios of CO groups/Eu³⁺ ions. The final solid composites were formed by a self-assembly process among Eu³⁺ ion, the ligands and PMMA during the solvent evaporation process, and then the ligands re-coordinate to Eu(III). It was found that the ligands affect not only the emission properties of the pure complexes, but also the miscibility of the complexes and PMMA. More than one kind of symmetric sites of Eu³⁺ ions were formed in the composites due to the coordination of CO in PMMA to Eu³⁺ ions. The micro-environments of Eu(III) in the composites were changed with the compositions and the ligands, leading to the change in the crystalline structure, and consequently, the emission characteristics.     

Interaction of Li ions with ethylene carbonate (EC): Density functional theory calculations

Electronic structures of Li⁺ ion-ethylene carbonate (EC) complexes were studied by density functional theory. The structural, electronic and dynamical properties of Li⁺-EC complexes were studied for both an isolated EC molecule and clusters including Li⁺ ion. Our structural analysis showed only one type of Li⁺ coordination with EC through Li⁺?OC which was supported by the vibration spectral analysis for interaction between Li⁺ ion and a solvent (EC) molecule. It was analyzed that the solvation energy and Mulliken charge of Li+ ion solvated by EC molecule decrease with increase in number of EC molecule. However, electron affinity shows the opposite change. This analysis with solvation energy, electron affinity and Mulliken charge supported the stabilization of 4-coordinated solvation shell among [Li⁺(EC)_n]_n=1-5 complexes.     

Alkali adsorption on Ni(1 1 1) and their coadsorption with CO and O

The adsorption of alkalis (Na, K) on Ni(1 1 1) and their coadsorption with CO and O were studied by high-resolution electron energy loss spectroscopy. Loss measurements of clean alkali adlayers provided the expected behaviour of the alkali-substrate vibration energy as a function of the alkali coverage. This result was achieved by eliminating any trace of CO contamination from the alkali adlayer. As a matter of fact, a significant softening of the alkali-Ni vibration energy was revealed in the alkali + CO coadsorbed phase. Moreover, alkali coadsorption with oxygen caused a weakening of the ONi bond and a strengthening of the alkaliNi bond.     

Enhancement of Ti-containing hydrogenated carbon (TiC:H) films by high-power plasma-sputtering

Ti-containing amorphous hydrogenated carbon (TiC:H) thin films were deposited on stainless steel SS304 substrates by high-power pulsed magnetron sputtering (HPPMS) in an atmosphere of mixed Ar and C₂H₂ gases using titanium metal as the cathodic material. The multilayer structure of the deposited film had a TiTiCDLC gradient to improve adhesion and reduce residual stress. This study investigates the effects of substrate bias and target-to-substrate distance on the mechanical properties of TiC:H films. Film properties, including composition, morphology, microstructure, mechanical, and tribology, were examined by glow discharge spectroscopy (GDS), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, and a nanoindenter and a pin-on-disk tribometer. Experiments revealed impressive results.     

New chalcogenide glasses in the Ag2Te-As2Se3-CdTe system

Chalcogenide glasses from the Ag₂Te-As₂Se₃-CdTe system were synthesized. The basic physicochemical parameters such as density (d), microhardness (HV) and the temperatures of phase transformations (the glass transition T_g, crystallization T_cr and melting T_m) were measured. Compactness and some thermomechanical characteristics such as volume (V_h) and formation energy (E_h) of micro-voids in the glassy network, as well as the module of elasticity E were calculated. The overall mean bond energy 〈E〉, the mean coordination number Z, the mean bond energy of the average cross-linking/atom and the average bond energy per atom of the “remaining matrix”— and , as well as the average heteropolar bond energy E_hb, the degree of “cross-linking/atom” P_p and the radial bond strength were determined.The correlation between the composition and properties of the Ag₂Te-As₂Se₃-CdTe glasses was established and comprehensively discussed.