Mécanismes de croissance, structures et propriétés optiques d'assemblages organiques sur surfaces Si(100)-2x1 nue ou passivée

PARIS-BIUSJ-Thèses (751052125) / SudocPARIS-BIUSJ-Physique recherche (751052113) / SudocSudocFranceF

A Possible Application of the Contribution of Aromaticity to Entropy: Thermal Switch

International audienceIt has been known for a long time that the loss of aromaticity of gaseous molecules leads to a large increase of the enthalpy and to a tiny increase of the entropy. Generally, the calculated transition temperature from an aromatic structure towards a non-aromatic structure at which these two contributions cancel is very high. The entropy associated to the loss of aromaticity of adsorbed molecules, such as pyridine on Si(100) and on Ge(100), is roughly the same while the associated enthalpy is much smaller, a consequence of which is a low transition temperature. This allows us to imagine monomolecular devices, such as thermal switches, based on the difference of electrical conductivity between aromatic and non-aromatic species adsorbed on Si(100) or on Ge(100)

Adsorption of phenylacetylene on Si(100)-2 x 1: Kinetics and structure of the adlayer

International audienceDirect adsorption of phenylacetylene on clean silicon surface Si(100)-2 x 1 is studied in ultrahigh vacuum (UHV). The combination of scanning tunnel microscopy (STM)and surface differential reflectance spectroscopy (SDRS) with Monte Carlo calculations are put together to draw a realistic kinetic model of the evolution of the surface coverage as a function of the molecular exposure. STM images of weakly covered surfaces provide evidence of two very distinct adsorption geometries for phenylacetylene, with slightly different initial sticking probabilities. One configuration is detected with STM as a bright spot that occupies two dangling bonds of a single dimer, whereas the other configuration occupies three dangling bonds of adjacent dimers. These data are used to implement a Monte Carlo model which further serves to design an accurate kinetic model. The resulting evolution toward saturation is compared to the optical data from surface differential reflectance spectroscopy (SDRS). SDRS is an in situ technique that monitors the exact proportion of affected adsorption sites and therefore gives access to the surface coverage which is evaluated at 0.65. We investigate the effect of surface temperature on this adsorption mechanism and show that it has no major effect either on kinetics or on structure, unless it passes the threshold of dissociation measured at ca. 200 degrees C. This offers a comprehensive image of the whole adsorption process of phenylacetylene from initial up to complete saturation

Starch functionalized magnetite nanoparticles: New insight into the structural and magnetic properties

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Conditions for the formation of pure birnessite during the oxidation of Mn(II) cations in aqueous alkaline medium

International audienceBirnessite was synthetized through redox reaction by mixing MnO4-, Mn2+ and OH- solutions. The Mn(VII): Mn(II) ratio of 0.33 was chosen and three methods were used consisting in a quick mixing under vigorous stirring of two of the three reagents and then on the dropwise addition of the third one. The obtained solids were characterized by XRD, FTIR and XPS spectroscopies. Their average oxidation states were determined from ICP and CEC measurements while their surface properties were investigated by XPS. This study provides an increased understanding of the importance of dissolved oxygen in the formation of birnessite and hausmannite and shows the ways to obtain pure birnessite. The role of counter-ion ie. Na+ or K+ was also examined

As(V) and As(III) sequestration by starch functionalized magnetite nanoparticles: influence of the synthesis route onto the trapping efficiency

We report the effect of the synthesis route of starch-functionalized magnetite nanoparticles (NPs) on their adsorption properties of As(V) and As(III) from aqueous solutions. NP synthesis was achieved by two different routes implying the alkaline precipitation of either a mixed Fe2+/Fe3+ salt solution (MC samples) or a Fe2+ salt solution in oxidative conditions (MOP samples). Syntheses were carried out with starch to Fe mass ratio (R) ranging from 0 to 10. The crystallites of starch-free MC NPs (14 nm) are smaller than the corresponding MOP (67 nm), which leads to higher As(V) sorption capacity of 0.3 mmol gFe−1 to compare with respect to 0.1 mmol gFe−1 for MOP at pH = 6. MC and MOP starch-functionalized NPs exhibit higher sorption capacities than a pristine one and the difference in sorption capacities between MOP and MC samples decreases with increasing R values. Functionalization tends to reduce the size of the magnetite crystallites and to prevent their agglomeration. Size reduction is more pronounced for MOP samples (67 nm (R0) to 12 nm (R10)) than for MC samples (14 nm (R0) to 9 nm (R10)). Therefore, due to close crystallite size, both MC and MOP samples, when prepared at R = 10, display similar As(V) (respectively, As(III)) sorption capacities close to 1.3 mmol gFe−1 (respectively, 1.0 mmol gFe−1). Additionally, according to the effect of pH on arsenic trapping, the electrostatic interactions appear as a major factor controlling As(V) adsorption while surface complexation may control As(III) adsorption

Interaction of ammonium with birnessite: Evidence of a chemical and structural transformation in alkaline aqueous medium

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Birnessite: A New Oxidant for Green Rust Formation

Iron and manganese are ubiquitous in the natural environment. FeII-FeIII layered double hydroxide, commonly called green rust (GR), and MnIII-MnIV birnessite (Bir) are also well known to be reactive solid compounds. Therefore, studying the chemical interactions between Fe and Mn species could contribute to understanding the interactions between their respective biogeochemical cycles. Moreover, ferromanganese solid compounds are potentially interesting materials for water treatment. Here, a {Fe(OH)2, FeIIaq} mixture was oxidized by Bir in sulphated aqueous media in the presence or absence of dissolved O2. In oxic conditions for an initial FeII/OH− ratio of 0.6, a single GR phase was obtained in a first step; the oxidation kinetics being faster than without Bir. In a second step, GR was oxidised into various final products, mainly in a spinel structure. A partial substitution of Fe by Mn species was suspected in both GR and the spinel. In anoxic condition, GR was also observed but other by-products were concomitantly formed. All the oxidation products were characterized by XRD, XPS, and Mössbauer spectroscopy. Hence, oxidation of FeII species by Bir can be considered as a new chemical pathway for producing ferromanganese spinels. Furthermore, these results suggest that Bir may participate in the formation of GR minerals

Microwave PECVD Silicon Carbonitride Thin Films: A FTIR and Ellipsoporosimetry Study

International audienceAmorphous non-oxide a-SiCxNy:H thin films have been synthesized at 300 or 500K from an Ar/HMDSN/NH3 gas mixture in a lab-scale microwaves PECVD reactor. These thin films have been characterized by FTIR spectroscopy and spectroscopic ellipsometry coupled with gas adsorption, in order to evidence the influence of PECVD synthesis conditions on the materials composition and microstructure. Deposition at high temperature (500K) was found to yield more inorganic and more compact films in comparison with those obtained at room temperature. In addition, when considering long term aging at room temperature for more than 1 month, the films synthesized at high temperature were found to be more stable toward oxidation in (humid) air