The studies presented here address the characterization of the electronic structure of various self-assembled monolayers (SAMs) of peptide nucleic acid (PNA) and tetraphenylporphyrin (TPP) SAMs and arrays, formed on gold substrates. PNA is a promising alternative to DNA for bio-sensing applications, as well as for strategies for self-assembly based on nucleic acid hybridization. In recent years charge transfer through PNA molecules was a focus of research due to possible applications in self-assembled molecular circuits and molecular tools. In light of this research it is interesting to investigate the electronic structure of PNA interfaces to gold, a potential electrode material. TPP is, due to its electronic structure, an organic p-type molecular semiconductor. Such a material can provide an alternative to standard micro- and optoelectronic devices and in recent years more attention was paid to semiconducting polymers and organic compounds offering these low-cost and flexible alternatives. Therefore, it is of high importance to investigate the prospect of using modified TPP molecules for the formation of interconnected molecular networks on metallic surfaces. All investigated monolayers were formed from solution in a nitrogen atmosphere inside a homemade glove box. This process allowed for PNA SAM and TPP SAM and array formation on clean Au substrates without the exposure to the ambient atmosphere. Ultraviolet and X-ray photoemission spectroscopy (UPS and XPS) measurements on the resulting PNA SAMs and TPP SAMs and arrays, which were performed in a to the glove box attached vacuum chamber containing a photoemission spectrometer, revealed the hole injection barriers at the interfaces and the interface dipoles. In addition to the UPS and XPS measurements on PNA, electronic structure calculations based on molecular dynamics sampling of the PNA structure were obtained, yielding the HOMO-LUMO gap and the electronic density of states for PNA. Combined with the UPS data, the theoretical calculations enabled estimation of the charge injection barriers for the PNA SAMs at the interface, as well as the assignment of individual UP-spectral features to specific molecular orbitals. The orbital line-up at the interface between the Au substrate and the PNA indicated a significant interface dipole resulting in the alignment of the Au Fermi level near the center of the PNA HOMO-LUMO gap. This alignment causes large charge injection barriers for both holes and electrons, and thus impedes charge transfer from Au into the PNA SAM. The study of PNA molecules with ferrocene termini showed that this hole injection barrier is shifted to lower energies at the PNA/ferrocene interface. This shift was explained with a molecular orbital reconfiguration through the presence of the ferrocene terminus. The further investigation of the dependence of the electronic structure of PNA SAMs, based on their orientation, showed that incomplete films containing flat lying molecules can have a significant impact on the charge injection barriers. The close proximity of the nucleobases to the Au surface offers new ways for charge transfer between the substrate and the PNA molecule through its nitrogen sites, leading to a lowering of the hole injection barrier at the interface. The TPP arrays were formed by depositing AgNO3 on the Au substrate prior to TPP incubation using the electrospray technique. The interaction of AgNO3 with the TPP promoted the formation of an interconnected thin film forming a network on the Au substrate. The line-up at the Au/TPP interface without AgNO3 exposure showed an interface dipole formation with injection barriers that would potentially obstruct charge injection into the molecule. However, the addition of AgNO3 to the process resulted in the formation of fine structures, and lead to a lower hole injection barrier due to an induced dipole, which would ultimately improve charge transfer between the substrate and the thin film. A separate thiolated TPP derivative was used to form SAMs on a gold substrate. The SAM exhibited an even lower injection barrier than the mentioned TPP thin film with AgNO3 exposure, leading to the conclusion that a mix of both TPP derivatives could potentially lead to a SAM with long range interconnectivity and a low hole injection barrier towards the substrate.

L'introduction du SiGe dans les pMOS (Bulk et FDSOI) exige un bon contrôle de la tension de seuil (VT). Ceci nécessite une extraction précise des paramètres électriques ainsi qu'une compréhension des effets électriques du Ge dans de tels dispositifs. Dans cette thèse, nous avons d'abord proposé des méthodes pour une identification précise des paramètres électriques du « gate stack »: VT, la tension de bande plate (VFB) et l'épaisseur équivalente d'oxyde (EOT). Ces méthodes ont été validées avec des simulations Poisson-Schrödinger (PS) et appliquées avec succès aux mesures. Dans un second temps, nous avons étudié les effets électriques du Ge sur les paramètres du « gate stack » des pMOS. La comparaison des caractérisations électriques (C-V) avec les simulations PS a montré un décalage supplémentaire du travail de sortie effectif qui croit avec le Ge. Des caractérisations STEM, EELS et SIMS ont prouvé que ce décalage est due à la présence de dipôles à l'interface SiGe/oxyde. / Maintaining good threshold voltage (VT) centering is a paramount challenge for CMOS technology. The SiGe introduction in bulk and FDSOI pFETs requires VT control for such devices. To this end, we have to extract accurately electrical parameters and to understand Ge integration effects in SiGe based pFETs. In this thesis, first, we have proposed extraction methods to determine VT, flat band voltage (VFB) and equivalent oxide thickness (EOT) parameters in bulk and FDSOI transistors. The extraction methods have been validated via Poisson-Schrodinger (PS) simulations and successfully applied to measurements. Second, we have highlighted and explained electric effects of Ge on pMOS gate stack parameters. Electrical characterizations compared with PS simulations have evidenced an additional effective work function increase, induced by Ge, related to interfacial dipoles. STEM, EELS and SIMS characterizations have demonstrated that dipoles are located at SiGe/IL interface.

In the quest for reliable, repeatable and stable field electron emission that has commercial potential, whilst many attempts have been made, none yet has been truly distinguishable as being successful. Whilst I do not claim within this thesis to have uncovered the secret to success, fundamental issues have been addressed that concern the future directions towards achieving its full potential. An exhaustive comparison is made across the diverse range of materials that have, over the past 40-50 years, been postulated and indeed tested as field emitters. This has not previously been attempted. The materials are assessed according to the important metrics of turn on voltage, Eon, and maximum current density, Jmax, where low Eon and high Jmax are seen as desirable. The nano-carbons, carbon nanotubes (CNTs), in particular, perform well in both these metrics. No dependency was seen between the material work function and its performance as an emitter, which might have been suggested by the Fowler Nordheim equations. To address the issues underlying the definition of the local enhancement factor, β, a number of variations of surface geometry using CNTs were fabricated. The field emission of these emitters was measured using two different approaches. The first is a Scanning Electrode Field Emission Microscope, SAFEM, which maps the emission at individual locations across the surface of the emitter, and the parallel plate that is more commonly encountered in field emission measurements. Finally, an observed hysteretic behaviour in CNT field emission was explored. The field emitters were subjected to a number of tests. These included; in-situ residual gas analysis of the gas species in the emitter environment, a stability study in which the emitters were exposed to a continuing voltage loop for 50 cycles, differing applied voltage times to analyse the effects on the emitted current, and varying maximums of applied field in a search for hysteresis onset information. These studies revealed the candidate in causing the hysteresis is likely to be water vapour that adsorbs on the CNT surface. A six step model if the emission process was made that details how and when the hysteresis is caused.

Les oxydes transparents conducteurs (TCO) ont la rare propriété de concilier haute transparence et conductivité élevée, ce qui en fait des matériaux-clés pour de nombreuses applications requérant des électrodes transparentes comme les cellules photovoltaïques, les diodes organiques et les écrans plats. Avec une résistivité de l'ordre de 10^(-4) ohm.cm et une transmittance de 85% dans le domaine visible, l'oxyde d'indium dopé à l'étain (ITO) est le matériau privilégié. Toutefois, sa fragilité, son instabilité aux procédés plasma et son coût croissant du fait de sa haute teneur en indium sont autant de raisons de rechercher des matériaux alternatifs. Cette thèse a pour but de comprendre les points clefs permettant d'améliorer les performances d'une électrode transparente en oxyde de zinc dopé à l'aluminium (AZO) sur les plans optique, électrique et au niveau des interfaces ; des cellules photovoltaïques en silicium amorphe hydrogéné (a-Si:H) servent de dispositif-test à cette étude. Réalisées par pulvérisation cathodique magnétron sous des conditions de dépôt variées, les couches minces d'AZO obtenues ont une structure microcristalline et, pour des paramètres déterminés, des performances optoélectroniques approchant celles de l'ITO. Un modèle adapté d'après la théorie de Drude a permis de rendre compte du lien entre transparence et conduction et de confirmer la saturation en porteurs du matériau. L'efficacité d'une électrode au sein d'un dispositif dépend également très fortement de l'interface entre celle-ci et l'absorbeur, les porteurs devant être extraits rapidement pour ne pas se recombiner. Quelques voies ont été explorées pour réduire la barrière de potentiel entre le silicium amorphe et l'électrode tout en favorisant l'efficacité optique des cellules. Il ressort que l'insertion d'une couche tampon d'oxyde de titane ou de tungstène permet d'obtenir un gain notable dans les performances des cellules. / Because of their unique ability to reconcile high transparency with good electrical conductivity, transparent conductive oxides (TCOs) are key materials in many applications such as organic light-emitting diodes, photovoltaic solar cells or flat displays. With its resistivity of a few 10^(-4)$ ohm.cm and its 85% transmittance in the visible range, Indium Tin Oxide (ITO) dominates the TCO market. Yet, it is brittle, unstable to plasma processes and its cost is rising due to its high indium content, encouraging research on alternative materials. This thesis aims at understanding key points to improve the performance of an aluminum-doped zinc oxide (AZO) transparent electrode on the optical, electrical and interface levels; hydrogenated amorphous silicon (a-Si:H) photovoltaic solar cells serve as a test device in this study. We obtain microcrystalline AZO thin films by magnetron sputtering under various deposition conditions ; for certain parameters, performances are close to ITO. An adapted model after the Drude theory allowed to account for the link between transparency and conduction and to confirm that the material is saturated by charge carriers. The effectiveness of an electrode within a device also strongly depends on its interface with the absorber layer, since the charge carriers have to be rapidely extracted in order to avoid recombination. Some ways have been explored to reduce the potentiel barrier between amorphous silicon and the electrode, still favoring optical efficiency of the cells. It appears that the insertion of a buffer layer of titanium or tungsten oxide enables a sensible improvement in the cells' efficiencies.

Le présent travail a pour objectif d’étudier la synergie entre la déformation plastique et les processus d’adsorption et d’absorption de l’hydrogène en surface et en subsurface du nickel monocristallin. La Réaction d’Evolution de l’Hydrogène (REH) et l’absorption de l’hydrogène en subsurface (RAH)partagent le plus souvent l’intermédiaire commun : l’hydrogène adsorbé (Hads). Le chemin réactionnel de la REH sur des surfaces de nickel (100) en milieu acide sulfurique peut être présenté par un mécanisme de Volmer-Heyrovsky. Les paramètres cinétiques élémentaires correspondants comme les coefficients de symétrie, les enthalpies d'activation, le nombre de sites actifs, ont été simulés via un modèle thermocinétique en utilisant les données expérimentales. Ces paramètres peuvent être affectés par la déformation plastique. Cette dernière modifie la densité et la distribution des dislocations stockées affectant la rugosité de surface à l'échelle atomique et engendrant des sites actifs supplémentaires d'adsorption. En revanche, l’émergence de ligne de glissement à la surface conduit à un phénomène de désactivation associé la formation de plan plus compact (111). L’entrée d’atomes d’hydrogène associée à l’étape de transfert surface-Subsurface peut être mesurée à l’aide d’une méthode potentiostatique de type pulsé. Cette dernière a permis de caractériser la diffusion et le piégeage de l'hydrogène en subsurface. Deux zones peuvent être distinguées, l’une proche de la surface (subsurface) et l’autre au coeur de l'échantillon. Dans ce cas, le coefficient de diffusion associé à la subsurface semble être beaucoup plus élevé que celui obtenu au coeur du métal. En revanche,l’application d’une contrainte mécanique conduit à une augmentation de la densité de pièges. Cette dernière, développée au voisinage de la surface : « subsurface », est plus faible que celle à coeur du matériau, ce qui suggère un effet adoucissant en subsurface. / The present work has for objective to study the synergy between the plastic strain and the processes of adsorption and absorption of hydrogen on the surface and the subsurface of nickel single crystal.Hydrogen Evolution Reaction (HER) and Hydrogen Absorption in subsurface (HAR) share mostly the common intermediate: the adsorbed hydrogen (Hads). The HER pathway on nickel (100) single crystal surfaces in sulphuric acid medium can be related by a Volmer-Heyrovsky mechanism. The corresponding elementary kinetic parameters as symmetry coefficients, activation enthalpies, number of active sites, have been identified via a thermokinetic model using experimental data. These parameters can be affected by defects associted with plastic strain. Irreversible plastic strain modifies the density and the distribution of storage dislocations affecting the surface roughness at atomic scale and generating additional active adsorption sites. Further more, surface emergence of mobile dislocations induces the formation of slip bands, which modify the surface roughness and the electronic state of the surface and increases the (111) surface density. The entry of hydrogen atoms associated to the transfer step surface-Subsurface can be measured using a potentiostatic double-Steptechnique (pulse method). This last allowed to characterizing the diffusion and trapping of hydrogen in the subsurface. Two domains can be distinguished, that of the subsurface and that of the bulk of the sample. In this case, the diffusion coefficient near the surface (subsurface) seems to be much higher than that obtained in the bulk of the metal. On the other hand, the application of mechanical stressleads to an increase of traps density. This last, developed near the surface: « subsurface », is lower than that at the bulk of material, which suggest a softening effect in the subsurface.

In the present work, the structural, electronic properties, thermodynamic stability and adatom surface movements of oxygen and sulfur adsorption on the Fe surface were studied based on the ab initio method. Firstly, the oxygen adsorbed on the iron (100) surface is investigated at the three adsorption sites top, bridge and hollow sites, respectively. Adsorption energy, work function and surface geometries were calculated, the hollow site was found to be the most stable adsorption site, Which is in agreement with the experiments. In addition, the difference charge density of the different adsorption systems was calculated to analyze the interaction and bonding properties between Fe and O. It can be found out that the charge redistribution was related to the geometry relaxation. Secondly, the sulfur coverage is considered from a quarter of one monolayer (1ML) to a full monolayer. Our calculated results indicate that the most likely site for S adsorption is the hollow site on Fe (100). We find that the work function and its change Df increased with S coverage, in very good agreement with experiments. Due to a recent discussion regarding the influence of charge transfer on Df, we show that the increase in Df can be explained by the increasing surface dipole moment as a function of S coverage. In addition, the Fe-S bonding was analyzed. Finally, the thermodynamic stabilities of the different structures were evaluated as a function the sulfur chemical potential. Finally, a two dimensional (2D) gas model was proposed to simulate the surface active elements, oxygen and sulfur atoms, movement on the Fe (100) surface. The average velocity of oxygen and sulfur atoms was found out to be related to the vibration frequencies and energy barrier in the final expression developed. The calculated results were based on the density function and thermodynamics & statistical physics theories. In addition, this 2D gas model can be used to simulate and give an atomic view of the complex interfacial phenomena in the steelmaking refining process.

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Die Ladungsinjektion (-extraktion) an einer Schnittstelle spielt in der organischen Elektronik eine entscheidende Rolle, da sie die Leistung des Bauelements stark beeinflusst. Eine der effizientesten Methoden zur Optimierung der Energiebarrieren für die Injektion ist die Modifikation der Austrittsarbeit der Elektroden. In dieser Dissertation untersuchen wir die Modifikation der Austrittsarbeit von Au(111) durch dithiol-terminiertes Polyethylenglykol (PEG(thiol)) sowie deren Abhängigkeit von der Anzahl der PEG-Wiederholungseinheiten. In beiden Fällen beobachten wir, dass die Austrittsarbeit des Au(111) durch eine Monoschicht PEG(thiol)-Moleküle reduziert wird. Unsere Berechnungen zeigen, dass diese Änderung der Austrittsarbeit hauptsächlich durch (i) die Ladungsumlagerung aufgrund der Chemisorption und (ii) das intrinsische Dipolmoment der PEG(thiol)-Monoschicht verursacht wird. Die Größe des letzteren Beitrags hängt spürbar von der Anzahl der Wiederholungseinheiten ab und bewirkt somit eine Variation in der Reduktion der Austrittsarbeit. Das oszillatorische Verhalten spiegelt einen ausgeprägten Odd-Even-Effekt wider. Dadurch kann die Austrittsarbeit der Metallelektrode unter Berücksichtigung des Odd-Even-Effekts gesteuert werden. Die Konvergenz der selbstkonsistenten Felditeration für unsere Systeme ist nicht garantiert. Um die Konvergenz zu verbessern, schlagen wir die Verwendung eines speziell auf die FP-LAPW-Methode zugeschnittenen Mischalgorithmus vor. In einem auf Ag(111) basierenden System zeigt sich, dass eine Struktur mit drei Leerstellen in der Substratschicht besonders stabil ist. Dabei ist eine kontinuierliche Abnahme der Austrittsarbeit des Ag(111) feststellbar. Ähnlich wie beim Au(111) manifestiert sich der Odd-Even-Effekt, der auf das Dipolmoment der Molekularschicht zurückzuführen ist. / Charge injection (extraction) at an interface plays a crucial role to organic electronics because this injection (extraction) heavily affects the device performance. One of the most efficient way to optimize energy barriers of the injection (extraction) is modifying the work function of electrodes. In this dissertation, we investigate the modification of work function of Au(111) and Ag(111) induced by the dithiol-terminated polyethylene glycol (PEG(thiol)) as well as a dependence of the work function change on different numbers of PEG repeat units. We find that the work function of the Au(111) is reduced by a monolayer of PEG(thiol) molecules. Overall, our calculations indicate that the work function change is mainly induced by (i) the charge rearrangement due to chemisorption and (ii) the intrinsic dipole moment of the PEG(thiol) monolayer. The magnitude of the latter contribution noticeably depends on the number of repeat units and, thus, causes a variation in the reduction of the work function. The oscillatory behavior reflects a pronounced odd-even effect. As a result, the work function of the metal electrode would be controlled by considering the odd-even effect. Unfortunately, the convergence of the self-consistent field iteration is not guaranteed for our investigated systems. To make the smooth convergence, a mixing algorithm, which is applicable to FP-LAPW method, is devised. We add the Kerker preconditioner as well as further improvements to Pulay’s direct inversion in the iterative subspace. Using this method, one can avoid charge sloshing and noise in the exchange-correlation potential. This method is also implemented in the exciting code. We find the decrease of the work function of the Ag(111) surface is always presented. Similar to the Au(111) case, the odd-even effect is revealed, arising from the dipole moment of the molecular layer.