Anne Hémeryck

Difficulty for oxygen to incorporate into the silicon network during initial O2 oxidation of Si(100)-(2×1)

First principles calculations and scanning tunneling microscopy studies of the oxidation of Si(100)-(2x1) surfaces by molecular oxygen reveal that the surface silanone (O)(Si=O) species is remarkably stable, constituting the key intermediate for initial oxidation. The propensity for oxygen to remain within the top surface layer as opposed to incorporating within Si-Si backbonds is surprisingly high. This resistance to incorporation into a cubic lattice even at higher coverages could be a factor to facilitate surface amorphization in subsequent steps.

On the early stage of aluminum oxidation: An extraction mechanism via oxygen cooperation

We propose a barrierless mechanism for describing the oxidation of Al(111) in which oxygen atoms located on the outer surface extract aluminum atoms of the surface layers through local cooperation of other pre-adsorbed oxygen atoms. We show the details of this complex chemical process that kinetically competes with the non-destructive formation of an oxygen monolayer onto the Al surface, thus elucidating the initial aluminum oxidation regime. We demonstrate that further stripping of the complete surface Al layer is consistent with both (i) the formation of a defective alumina structure and (ii) an oxide capping layer preventing further oxidation at low temperature.

A computational chemist approach to gas sensors: Modeling the response of SnO2 to CO, O2, and H2O Gases

A general bottom‐up modeling strategy for gas sensor response to CO, O2, H2O, and related mixtures exposure is demonstrated. In a first stage, we present first principles calculations that aimed at giving an unprecedented review of basic chemical mechanisms taking place at the sensor surface. Then, simulations of an operating gas sensor are performed via a mesoscopic model derived from calculated density functional theory data into a set of differential equations. Significant presence of catalytic oxidation reaction is highlighted.

Elementary surface chemistry during CuO/Al nanolaminate-thermite synthesis: copper and oxygen deposition on aluminum (111) surfaces.

The surface chemistry associated with the synthesis of energetic nanolaminates controls the formation of the critical interfacial layers that dominate the performances of nanothermites. For instance, the interaction of Al with CuO films or CuO with Al films needs to be understood to optimize Al/CuO nanolaminates. To that end, the chemical mechanisms occurring during early stages of molecular CuO adsorption onto crystalline Al(111) surfaces are investigated using density functional theory (DFT) calculations, leading to the systematic determination of their reaction enthalpies and associated activation energies. We show that CuO undergoes dissociative chemisorption on Al(111) surfaces, whereby the Cu and O atoms tend to separate from each other. Both Cu and O atoms form islands with different properties. Copper islanding fosters Cu insertion (via surface site exchange mechanism) into the subsurface, while oxygen islands remain stable at the surface. Above a critical local oxygen coverage, aluminum atoms are extracted from the Al surface, leading to oxygen-aluminum intermixing and the formation of aluminum oxide (γ-alumina). For Cu and O co-deposition, copper promotes oxygen-aluminum interaction by oxygen segregation and separates the resulting oxide from the Al substrate by insertion into Al and stabilization below the oxide front, preventing full mixing of Al, Cu, and O species.

Diaminoethane adsorption and water substitution on hydrated TiO2: a thermochemical study based on first-principles calculations

Epoxy-amines are used as structural adhesives deposited on Ti. The amine adhesion to a Ti surface depends highly on the surface state (oxidation, hydroxylation). Amines may adsorb above preadsorbed water molecules or substitute them to bind directly to surface Ti(4+) Lewis acid sites. The adsorption of a model amine molecule, diaminoethane (DAE), on a model surface, hydrated TiO2-anatase (101) surface, is investigated using Density Functional Theory including Dispersive forces (DFT-D) calculations. DAE adsorption and water substitution by DAE are exothermic processes and turn nearly isoenergetic at high coverage with adsorption-substitution energies around -0.3 eV (including dispersion forces and ZPE). Complementary ab initio molecular dynamics studies also suggest that the formation of an amine-water interaction induces water desorption from the surface at room temperature, a preliminary step towards the amine-Ti bond formation. An atomistic thermodynamic approach is developed to evaluate the interfacial free energy balance of both processes (adsorption and substitution). The main contributions to the energetic balance are dispersive interactions between molecules and the surface on the exergonic side, translational and rotational entropic contributions on the endergonic one. The substitution process is stabilized by 0.55 eV versus the adsorption one when free solvation, rotational and vibrational energies are considered. The main contribution to this free energy gain is due to water solvation. The calculations suggest that in toluene solvent with a water concentration of 10(-4) M or less, a full DAE layer replaces a preadsorbed water layer for a threshold concentration of DAE ≥ 0.1 M.

Nanoindentation of NiAl and Ni3Al crystals on (100), (110), and (111) surfaces: A molecular dynamics study

Molecular dynamics simulations were performed to study the nanoindentation of NiAl and Ni3Al crystals on three surfaces: (100), (110), and (111). The calculated load-displacement curves show discrete drops at certain indentation depths, indicating dislocation bursts during indentation. The hardness values for the two materials were found to depend significantly on the indented crystallographic plane: the (100) surface is the softest for NiAl and the hardest for Ni3Al. We also found distinctive deformation activities in the subsurface region in Ni3Al crystals, while dislocation loops propagate deep into the substrate in NiAl systems.

Effects of solvation shells and cluster size on the reaction of aluminum clusters with water

Reaction of aluminum clusters, Aln (n = 16, 17 and 18), with liquid water is investigated using quantum molecular dynamics simulations, which show rapid production of hydrogen molecules assisted by proton transfer along a chain of hydrogen bonds (H-bonds) between water molecules, i.e. Grotthuss mechanism. The simulation results provide answers to two unsolved questions: (1) What is the role of a solvation shell formed by non-reacting H-bonds surrounding the H-bond chain; and (2) whether the high size-selectivity observed in gas-phase Aln-water reaction persists in liquid phase? First, the solvation shell is found to play a crucial role in facilitating proton transfer and hence H2 production. Namely, it greatly modifies the energy barrier, generally to much lower values (< 0.1 eV). Second, we find that H2 production by Aln in liquid water does not depend strongly on the cluster size, in contrast to the existence of magic numbers in gas-phase reaction. This paper elucidates atomistic mechanisms underlying t...

Asymmetric diffusion as a key mechanism in Ni/Al energetic multilayer processing: A first principles study

Adsorption and penetration of Al and Ni atoms into Ni(111) and Al(111), respectively, are investigated through first principles calculations, shedding light into the driving forces impacting Al/Ni interfaces produced during multilayer deposition. The authors show that Ni deposition follows an exothermic path toward penetration associated with small activation barriers while Al on Ni(111) path is endothermic accompanied with high activations. Moreover, Ni and Al penetrations proceed through interstitial and substitutional sites, respectively. These differentiated behaviors at early deposition stages illustrate that dual processing conditions are required to achieve the growth of specific Ni/Al interfaces during multilayer deposition processes and that a local melting process at the interface is mandatory to arrive at the formation of a proper barrier layer.

Surface-interface exploration of Mg deposited on Si(100) and oxidation effect on interfacial layer

Using scanning tunneling microscopy and spectroscopy, Auger electron spectroscopy, and low energy electron diffraction, we have studied the growth of Mg deposited on Si(100)-(2 x 1). Coverage from 0.05 monolayer (ML) to 3 ML was investigated at room temperature. The growth mode of the magnesium is a two steps process. At very low coverage, there is formation of an amorphous ultrathin silicide layer with a band gap of 0.74 eV, followed by a layer-by-layer growth of Mg on top of this silicide layer. Topographic images reveal that each metallic Mg layer is formed by 2D islands coalescence process on top of the silicide interfacial layer. During oxidation of the Mg monolayer, the interfacial silicide layer acts as diffusion barrier for the oxygen atoms with a decomposition of the silicide film to a magnesium oxide as function of O2 exposure.

Bottom-up modeling of Al/Ni multilayer combustion: Effect of intermixing and role of vacancy defects on the ignition process

Vapor deposited multilayered aluminum/oxide and bimetallics are promising materials for Micro Electro Mechanical System technologies as energy carriers, for instance, microinitiators or heat microsources in biological or chemical applications. Among these materials, the Al/Ni couple has received much attention both experimentally and theoretically. However, the detailed relation between the chemical composition of the intermixed interfacial regions and its impact on the ignition capabilities remains elusive. In this contribution, we propose a twofold strategy combining atomistic density functional theory (DFT) calculations and a macroscopic 1D model of chemical kinetics. The DFT calculations allow the description of the elementary chemical processes (involving Al, Ni atoms and vacancies basic ingredients) and to parameterize the macroscopic model, in which the system is described as a stack of infinite layers. This gives the temporal evolution of the system composition and temperature. We demonstrate that the amount of vacancies, originating from the deposition process and the Al and Ni lattice mismatch, plays a critical role on both the ignition time and the temperature. The presence of vacancies enhances the migration of atoms between layers and so dramatically speeds up the atomic mixing at low temperatures far below ignition temperature, also pointing to the relation between experimental deposition procedures and ageing of the nanolaminates. V C 2013 AIP Publishing LLC.