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A full understanding of chemical reaction dynamics at the gas/organic-surface interface requires knowledge of energy-transfer processes that happen during the initial gas/surface collision. We have examined the influence of mass and rovibrational motion on the energy-transfer dynamics of gas-phase species scattering from model organic surfaces using theory and experiment. Molecular-beam scattering techniques were used to investigate the rare gases, Ne, Ar, Kr, and Xe, and the diatomics, N₂ and CO, in collisions with CH₃- and CF₃-terminated self-assembled monolayer (SAM) surfaces. Complementary molecular-dynamics simulations were employed to gain an atomistic view of the collisions and elucidate mechanistic details not observable with our current experimental apparatus. We developed a systematic approach for obtaining highly accurate analytic intermolecular potential-energy surfaces, derived from high-quality ab initio data, for use in our classical-trajectory simulations. Results of rare gas scattering experiments and simulations indicate mass to be the determining factor in the energy-transfer dynamics, while other aspects of the potential-energy surface play only a minor role. Additionally, electronic-structure calculations were used to correlate features of the potential-energy surface with the energy-transfer behavior of atoms and small molecules scattering from polar and non-polar SAM surfaces. Collisions of diatomic molecules with SAMs are seen to be vibrationally adiabatic, however translational energy transfer to and from rotational modes of the gas species, while relatively weak, is readily apparent. Examination of the alignment and orientation of the final rotational angular momentum of the gas species reveals that the collisions induce a stereodynamic preference for the expected "cartwheel" motion, as well as a surprising propensity for "corkscrew" or "propeller" motion. The calculated stereodynamic trends suggest that the CH₃-SAM is effectively more corrugated than the CF₃-SAM. Finally, the feasibility for collisional-energy promoted, direct gas/organic-surface reactions was interrogated using the 1,3-dipolar azide-alkyne cycloaddition reaction. We found that geometrical constraints prevented the reaction from proceeding at the probed conditions. / Ph. D.

When approaching a metal surface, the electronic structure of Rydberg atoms or molecules is perturbed by the surface potential and at close enough distances resonant ionisation of the Rydberg electron into the conduction band of the surface can occur. It is possible to interfere in this process and steer the ionisation distance by making use of the polarisability of the Rydberg orbital in the presence of electric fields. The resulting ions from the surface can extracted via electric fields and subsequently detected via well established ion detection schemes. The question of how this charge-transfer process is affected by different properties of the surface (both electronic and structural) represents the main aspect of the work presented in this thesis. At first, the charge transfer of atomic hydrogen Rydberg atoms with a flat gold metal surface is investigated. While such a surface might appear homogeneous, stray fields are present in its vicinity due to local variations in the surface work function. The surface ionisation process as a function of applied electric field is therefore measured experimentally and the results are compared with classical Monte-Carlo simulations (which include stray field effects). This way the possibility to utilize Rydberg states as a probe of the magnitude of such stray fields is demonstrated. To investigate the effect the surface structure can have on the ionisation process, the interaction of Rydberg atoms with surfaces covered by nanoparticles is investigated. Surface ionisation is measured at a 5 nm nanoparticle monolayer surface and it is shown that population transfer between surface- and vacuum-oriented Rydberg states occurs. In addition, results are presented, which suggest a dependence of the ionisation process on the relative size of Rydberg orbital and nanoparticle. Furthermore, charge transfer between a Rydberg state and discrete electronic states at the surface vacuum interface are investigated by performing experiments with a Cu(100) band-gap semiconductor surface. By analysing surface ionisation as a function of collisional velocity ionisation rates can be determined and are subsequently compared with theoretical predictions. The potential of identifying resonant ionisation is thereby demonstrated. Last, a new method to produce 2s atomic hydrogen via mixing of the 2s and 2p state in an electric field is proposed and first experimental results are presented, thus demonstrating viability of the idea. The experiments presented in this thesis represent the most in depth analysis of the charge-transfer process between atomic hydrogen Rydberg states and a range of different surfaces to date. As such, they demonstrate the potential of utilizing the unique properties of Rydberg states and their applicability as surface probes. In addition, these results pave the way for further experiments involving thin films or the phenomenon of quantum reflectivity.

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Les nanofils (NFs), de par leur propriétés opto et nanoélectroniques sont devenus des éléments indispensable à la fabrication des dispositifs de la nanoélectronique. Le problème principal reste la reproductibilité en terme de densité de NFs, de diamètre... Cette thèse a pour but de développer grâce à la technologie FIB, un procédé permettant l'élaboration de NFs organisés et homogène en taille. / Due to their ease of fabrication and unique physical properties, semiconductor nanowires (NWs) have been proposed as building blocks for new nanoelectronic and photonic devices. Various processes have been developed to obtain large density of ultra-small NWs but naturally forms nanowires often lack reproducibility. We propose to develop a bottom-up (B-U)processes which is based on naturally formed NWs grown on a patterned substrate resulting from self-assembly of metallic clusters or exposition to a focused ion beam (FIB). The major goal consist to obtain organized and homogeneous NWs.

Ce mémoire présente une étude de la synthèse par la méthode Vapeur-Liquide-Solide (VLS) de nanofils de silicium et de germanium par Epitaxie par Jets Moléculaires ainsi que de l'effet de la présence de manganèse sur leur croissance. La croissance des nanofils est fortement modifiée par la présence de manganèse. Les nanofils de silicium élaborés sous un faible flux de manganèse présentent des propriétés morphologiques et structurales remarquables. La présence de manganèse modifie le diamètre d'équilibre des gouttes AuSi utilisées pour la croissance par voie VLS et permet l'élaboration de nanofils de silicium de longueurs élevées et de faibles diamètres. De plus, leur qualité cristalline est considérablement améliorée par rapport aux nanofils de silicium formés sans apport de manganèse. Dans ce mémoire nous proposons quelques explications à ce phénomène. Dans le cas des nanofils de germanium, l'incorporation de manganèse n'a pu être obtenue par codépôt. Aussi, (i) le dopage par implantation ionique de nanofils de germanium et (ii) la fonctionnalisation de nanofils de germanium par la formation d'hétérostructures type cœur/coquille Ge/GeMn ont été considérés : - les mesures d'aimantation effectuées sur des nanofils de germanium implantés au manganèse démontrent l'existence de propriétés ferromagnétiques avec des températures de Curie supérieures à 400K. Il s'agit d'un résultat très prometteur en vue d'applications utilisant des nanofils de germanium ferromagnétiques à température ambiante ; - pour accéder aux propriétés magnétiques des nanofils de germanium fonctionnalisés par dépôt de GeMn, nous avons mis au point une procédure de prises de contacts adaptée à la mesure de leurs propriétés de magnétotransport. Les caractéristiques électriques de ces dispositifs montrent que les propriétés de transport sont dominées par la présence de la couche coquille de GeMn, surtout à basse température. Des mesures de magnétotransport effectuées à 100K indiquent l'existence d'effets de magnétorésistance liés aux propriétés ferromagnétiques des nanofils de Ge ainsi fonctionnalisés. / This thesis presents a study of the Vapour-Liquid-Solid (VLS) synthesis of silicon and germanium nanowires by Molecular Beam Epitaxy and the effect of the presence of manganese on the growth properties. The presence of manganese strongly modifies the growth of nanowires and observed behaviours are very different for AuSi and AuGe systems. Silicon nanowires grown in the presence of manganese exhibit very interesting morphological and structural properties. The presence of manganese modifies AuSi droplets' diameter and allows manufacturing long nanowires with relatively small diameters. Moreover, the crystalline quality is dramatically improved as compared to that of silicon nanowires grown without manganese. In this manuscript we propose some explanation for the growth phenomena. In the case of germanium nanowires, manganese incorporation could not be obtained by concomitant deposition of germanium and manganese. Consequently, (i) the doping of germanium nanowires by ion implantation as well as (ii) germanium nanowires functionalization by core/shell Ge/GeMn heterostructures formation were considered: - magnetization measurements performed on implanted germanium nanowires demonstrate ferromagnetic properties with Curie temperatures above 400K. This result is very promising for the processing of devices using room-temperature ferromagnetic germanium nanowires ; - in order to access Ge/GeMn nanowires magnetic properties, we processed samples to probe nanowires magnetotransport properties. Electrical resistivities of devices show that transport properties are dominated by GeMn shell layer even more at low temperature. Magnetotransport measurements done at 100K indicate magnetoresistance effects linked with nanowires ferromagnetic properties.

In dieser Forschungsarbeit wird das selbstorganisierte Wachstum von InP/InGaP-Quantenpunkten (QP) sowie ihre optischen und strukturellen Eigenschaften untersucht. Die QP wurden auf GaAsgitterangepasstem InGaP gewachsen.Selbstorganisierte InP-QP werden mittels Gasquellen-Molekularstrahlepitaxie gewachsen, wobei die InP-Abscheidungsrate uber einen weiten Bereich variiert wird. Bei besonders geringer Wachstumsratevon rund 0,01 Atomlagen/s wird eine Flachendichte von 1 QP/μm2 erreicht. Die daraus resultierenden InP QP, konnen einzeln charakterisiert werden ohne vorher das Substrat lithografisch behandeln zu mussen. Sowohl exzitonische als auch biexzitonische Emission kann dabei an einzelnen QPn als Doublett mit einer Feinstrukturaufspaltung von 320μeV beobachtet warden. Hanbury-Brown-Twiss Korrelationsmessungen der exzitonischen Emission unter Dauerstrichanregung zeigen Antibunching mit einem Autokorrelationskoeffizienten von g(2)(0)=0.2. Dieses System liee sich beispielsweise als Einzelphotonenquelle in Anwendungsbereichen wie der Quantenkryptographie einsetzen. Daruber hinaus wird die Bildung wohlgeordneter Quantenpunktketten auf GaAs (001)-Substraten unter Ausnutzung einer selbstorganisierten InGaP-Oberflachenwellung demonstriert. Diese Anordnung basiert weder auf gestapelten Quantenpunktschichten noch einem intentionalen Substratschragschnitt. Die Strukturen warden mittels polarisationsabhangiger Photolumineszenzspektroskopie sowie Transmissionselektronenmikroskopie untersucht. Die Lumineszenz der InGaP-Matrix ist in eine kristallografische Richtung polarisiert, bedingt durch anisotrope Verspannung, welche ihrerseits aus der lateralen Variation der Materialzusammensetzung entsteht. Photolumineszenzmessungen der QP zeigen eine lineare Polarisation entlang [-110], der Richtung der Ketten. Der Polarisationsgrad liegt bei 66%. Diese optische Anisotropie wird direkt in einer Heterostruktur hervorgerufen, die lediglich eine Quantenpunktschicht beinhaltet. / In this work the growth of self-assembled InP/InGaP quantum dots, as well as their optical and structural properties are presented and discussed. The QDs were grown on InGaP, lattice matched to GaAs.Self-assembled InP quantum dots are grown using gas-source molecular beam epitaxy over a wide range of InP deposition rates, using an ultra-low growth rate of about 0.01 atomic monolayers/s, a quantum-dot density of 1 dot/μm2 is realized. The resulting isolated InP quantum dots are individually characterized without the need for lithographical patterning and masks on the substrate. Both excitionic and biexcitonic emissions are observed from single dots, appearing as doublets with a fine-structure splitting of 320 μeV. Hanbury Brown-Twiss correlation measurements for the excitonic emission under cw excitation show anti-bunching behavior with an autocorrelation value of g(2)(0)=0.2. This system is applicable as a single-photon source for applications such as quantum cryptography. The formation of well-ordered chains of InP quantum dots on GaAs (001) substrates by using self-organized InGaP surface undulations as a template is also demonstrated. The ordering requires neither stacked layers of quantum dots nor substrate misorientation. The structures are investigated by polarization-dependent photoluminescence together with transmission electron microscopy. Luminescence from the InGaP matrix is polarized in one crystallographic direction due to anisotropic strain arising from a lateral compositional modulation. The photoluminescence measurements show enhanced linear polarization in the alignment direction of quantum dots, [-110]. A polarization degree of 66% is observed. The optical anisotropy is achieved with a straightforward heterostructure, requiring only a single layer of QDs.