Diese Arbeit behandelt elektronische und strukturelle Eigenschaften dünner Schichten aus konjugierten organischen Molekülen (COMs), aufgebracht auf Metalloberflächen per Vakuum-Sublimation. Diese Eigenschaften sind essenziell für Funktionsrealisierung und -optimierung organischer Elektronikbauteile. Teil 1 diskutiert zwei Ansätze zur Energieniveauanpassung (ELA) an Organik-Metall-Grenzflächen zur Einstellung der dortigen Löcherinjektionsbarrieren (HIBs) durch (Über-)Kompensation des abträglichen "Push-back"-Effekts: - Ausnutzung der besonderen ELA bei Chalkogen-Metall-Bindungen, hier gezeigt mit Hilfe von Röntgen- und Ultraviolettphotoelektronenspektroskopie (UPS/XPS) für ein Seleno-funktionalisiertes COM - Einfügen von COMs mit ausgeprägtem Elektronen-Akzeptorcharakter vor dem Aufbringen der aktiven Schicht. UPS-Messungen zeigen, dass beide Ansätze HIBs von ca. 0.3 eV ermöglichen. Teil 2 untersucht ausgewählte organische Heterostrukturen auf Metallen. Die Untersuchungen identifizieren einen Ladungstransfer vom Metall zur Überschicht (MOCT) als verantwortlich dafür, das System bei Ferminiveau-Pinning in den Gleichgewichtszustand zu überführen. Detaillierte Untersuchungen gestatten die Identifikaton von ganzzahligem Ladungstransfer zu einem Teil der Moleküle in der ersten Überschichtlage und den Einfluss der Dipol-Abstoßung in der Überschicht. In Teil 3 dienen Metalloberflächen als Auflage für supramolekulare Architekturen mit dipolaren Bausteinen. Rastertunnelmikroskopie (STM) an einer Serie von teils partiell fluorierten, stäbchenförmigen COMs mit unterschiedlich großen Dipolmomenten ermöglicht die Entflechtung von Dipol-Dipol- und konkurierenden Wechselwirkungen physisorbierter Submonolagen auf Ag(111). Ein anderes, stark dipolares COM bildet bei Monolagenbedeckung auf Au(111) sechs Phasen, alle mit antiferroelektrischer Einheitszellen. UPS-Messungen ergeben eine bevorzugte Ausrichtung der Moleküle in Multilagen. / In this thesis, the electronic and structural properties of thin films of conjugated organic molecules (COMs) vacuum-deposited on metal surfaces are studied. These properties are essential for realization and optimization of device functionalities in the field of organic electronics. Part 1 discusses two approaches for engineering the energy-level alignment (ELA), and, thereby, optimizing hole injection barriers (HIBs), at organic/metal interfaces via (over)compensation of the detrimental "push-back": - Exploiting the peculiar ELA at chalcogen-metal bonds, shown here (with X-ray and ultraviolet photoelectron spectroscopy, UPS/XPS) for a seleno-functionalized COM - inserting electron-accepting COMs prior to deposition of active layers. UPS shows that both approaches realize HIBs into the active COM as low as 0.3 eV. Part 2 studies selected organic/organic heterostructures on metal surfaces. These studies allow to propose that metal to overlayer charge transfer (MOCT), is responsible for achieving electronic equilibrium when such systems are Fermi-level pinned. Detailed investigations allowed identifying integer charge transfer to a fraction of the molecules in the first overlayer and the influence of the dipole-repulsion on the overlayer. In Part 3, metal surfaces are used as support for supramolecular architecture with polar building blocks. Scanning tunneling microscopy (STM) of a series of rod-like COMs with and without partial fluorination and with different dipole moments help disentangling the delicate balance dipole-dipole and competing interactions for sub-monolayer films physisorbed on Ag(111). For another, highly-polar COM at ca. monolayer coverage on Au(111), STM identifies six phases. All phases are found to exhibit anti-ferroelectric unit cells. UPS evidences a preferential alignment of multilayer molecules.

L'eau joue un rôle fondamental dans la photochimie du milieu interstellaire (MIS), à travers la formation d'espèces très réactives comme OH. Les radicaux OH peuvent par la suite interagir avec d'autres molécules hydrogénées pour reformer H2O par abstraction d'hydrogène: R-H + OH → R* + H2O. Dans le cadre de ce travail de thèse, nous avons étudié l'influence des photons VUV sur des analogues de glace interstellaire. Nous montrons que l'incorporation d'une petite quantité d'eau dans NH3 et CH4 glaces augmente considérablement la formation de radicaux réactifs comme NH2 et CH3 pendant le processus de photolyse et que le chauffage des glaces binaires irradiées telles que NH3-H2O et CH4-H2O conduit à la formation de NH2OH et d'espèces alcooliques plus complexes comme le propanol et le métoxyméthanol. Nous avons également entamé d'autres études en parallèle sur le l'évolution thermique des glaces de NH2OH d'une part et la formation de propanol par voies énergétiques (irradiation VUV) et non énergétique (réaction d'addition H) d'autre part afin de tenter d'expliquer la non-détection des ces espèces organiques dans le milieu interstellaire. L'étude des glaces mixtes irradiées NH3-CH4-H2O a montré la formation à basse température d'espèces plus exotiques en combinant les spectrométries IR et de masse. Nous avons réussi à identifier des composés organiques très complexes déjà détectés ou activement recherchés dans le MIS. / Water plays a fundamental role in the photochemistry of the interstellar medium (ISM), through OH radical formation. OH radicals can interact with other H-containing species to form H2O through a hydrogen abstraction reaction: R-H + OH → R* + H2O. In this work, we have investigated the VUV processing on different interstellar ice analogs. We show that the incorporation of small amount of water in NH3 and CH4 ices greatly increases the formation of reactive NH2 and CH3 radicals during the photolysis processing. Thermal treatments of irradiated NH3-H2O and CH4-H2O ices lead to the formation of NH2OH and larger alcoholic species such as propanol and metoxymethanol. Further studies of thermal processing of NH2OH ice and formation of propanol through energetic (VUV irradiation) and non-energetic (surface H-addition reaction) processing were carried out in the context of this thesis in order to try explaining their non-detection in the interstellar medium. The study of the irradiated mixed NH3-CH4-H2O ices showed the formation of more exotic species by combining the IR and mass spectrometries. We managed to identify very large complex organic compounds already detected or tensively sought in the ISM.

Le premier chapitre de cette thèse présente l’intérêt et la problématique de la fonctionnalisation du graphène. L’état de l’art actuel de cette thématique est présenté. Dans un deuxième chapitre, nous discutons de façon détaillée des techniques expérimentales. Le chapitre 3 est centré sur la modification du graphène par réaction de cycloaddition par molécules dérivées de maleimides. Dans cette étude, nous démontrons le greffage covalent de molécules sur graphène épitaxié sans défaut sur SiC, ainsi qu’une tendance d’ouverture de bande interdite à l’aide de caractérisations par spectroscopie Raman, XPS, ARPS et STM. L’augmentation du rapport ID /IG des pics Raman et des liaisons sp3 sur l’échantillon en fonction de la durée de réaction chimique confirme le greffage. Par analogie avec les bords de marche de type « zigzag » ou « armchair », l’étude des ondes de densité de charge générées sur le graphène par les molécules permet de déterminer la nature des sous-réseaux mis en jeu lors du greffage. Dans le chapitre 4, nous étudions l’intercalation du terbium dans le graphène épitaxié. Après intercalation, l’ARPES montre une structure de bande complexe dont une composante correspond à une monocouche de graphène fortement dopée n. Nous avons pu isoler cette composante et montrer qu’elle provient du découplage de la couche tampon du substrat par le Terbium. Ces résultats sont confirmés par les données XPS. Le graphène avec Terbium intercalé produit également un réseau de lignes visibles par imagerie STM, qui a l’échelle atomique à basse tension montrent les 6 atomes de carbone de la structure en nid d’abeille, confirmant ainsi la transformation de la couche tampon en graphène. / The first chapter of this thesis explains the general motivation and problematic of graphene functionalization. It presents the state of the art of current research in this field. In the second chapter we discuss the experimental techniques in detail. Chapter 3 of this thesis work focuses on covalent modification of graphene by cycloaddition reaction of maleimide derivative molecules. In these studies we have confirmed the grafting of molecules on epitaxial defect free graphene on SiC and a tendency to open a gap with the help of Raman spectroscopy, XPS, ARPES and STM studies. An increase in the ID /IG ratio for Raman signature and sp3 bonding on the sample with increasing reaction time confirmed the reaction of molecules. By drawing an analogy with the standing waves obtained on armchair step edges of graphene and standing waves generated by molecules it was possible to determine the location of grafted molecules on the graphene lattice. In chapter 4, studies on terbium intercalation of epitaxial graphene are discussed. After intercalation a complex band structure was observed by ARPES with one spectra corresponding to highly n-doped graphene monolayer. We were able to isolate this highly n-doped graphene and confirmed its origin from decoupling of buffer layer and making it graphene like. These results are also supported by the XPS data. STM images on Terbium intercalated on buffer layer samples showed an interesting pattern of lines, atomic resolution scans at low bias voltage on these lines showed 6 atoms of hexagon confirming the transformation of buffer layer into graphene layer.

Zentrales Thema dieser Dissertation ist die Untersuchung anorganisch/organischer Hybridsysteme (HIOS) mit besonderem Fokus auf den speziellen Prozessen an der Grenzfläche beider Materialklassen. Organische Moleküle, in Verbindung mit anorganischen Halbleitern haben ein großes Potenzial für Anwendungen in zukünftigen optoelektronischen Hybridbauteilen, indem sie Vorteile zweier unterschiedlicher Welten kombinieren. Entscheidend für die Herstellung von hybriden Strukturen ist das Verständnis der Wechselwirkungen an der Grenzfläche zwischen organischem und anorganischem Material. In dieser Arbeit werden diese Wechselwirkungen analysiert, um eine Wachstumskontrolle an der Grenzfläche zwischen konjugierten organischen Molekül und anorganischem Halbleiter zu ermöglichen. Hierfür werden unterschiedliche Ansätze verfolgt: Im ersten Teil der Arbeit wird die Wechselwirkung des Modellsystems Sexiphenyl (6P) an der Grenzfläche zu ZnO untersucht, sowie das Wachstum des Moleküls mittels verschiedener Methoden kontrolliert. Das daraus gewonnene Wissen kann im zweiten Teil dazu verwendet werden einen hybriden ZnO/6P/ZnO-Stapel zu realisieren, bei dem die organische Schicht ohne Beeinträchtigung der Kristallstruktur, mit definierten Grenzflächen bis hin zur atomaren/molekularen Ebene, überwachsen werden kann. Der letzte Teil der Arbeit befasst sich mit der optischen Echtzeit-Beobachtung während des organischen Wachstums verschiedener Moleküle. Dadurch ist es möglich Veränderungen von Struktureigenschaften und Wechselwirkungen zwischen Molekülen und dem Substrat zerstörungsfrei zu bestimmen, während diese aufgewachsen werden. Hierdurch können schlussendlich mögliche Mechanismen aufgezeigt werden, um elektronische und optische Wechselwirkung an der Grenzfläche zwischen organischem Molekül und anorganischen Halbleitern zu analysieren, sowie Wachstumsprozesse weiter zu verstehen und kontrollieren. / The central subject of this thesis are hybrid inorganic/organic systems (HIOS) with a focus on the specific processes at the interface between the two material classes. Organic molecules used together with inorganic semiconductors, have a great potential for future optoelectronic applications in hybrid components, by combining the advantages of two dissimilar worlds. Decisive for the production of hybrid structures is the understanding of the interactions at the interface between organic and inorganic material. In this thesis, the interactions are analyzed to enable growth control at the interface between conjugated organic molecules and inorganic semiconductors. In the first part of the thesis, the interaction of the model system sexiphenyl (6P) at the interface with ZnO, as well as approaches to control the growth of the molecule are being investigated. The knowledge gained here is used in the second part to realize a hybrid ZnO/6P/ ZnO stack, in which the organic layer can be overgrown without affecting the crystal structure, exhibiting defined interfaces down to the atomic/molecular level. The last part of the thesis deals with real time optical observation during organic growth of different molecules. By this changes in structural properties and interactions between molecules and the substrate can be non-destructively determined as they are growing. Ultimately, a comprehensive insight into the optical and electronic interactions at the interface between organic molecules and inorganic semiconductors can be gained and possible control mechanisms are shown.

In the present work a Metal / organic / inorganic semiconductor hybrid heterostructure (Ag / DiMe−PTCDI / GaAs) was built under UHV conditions and characterised in situ. The aim was to investigate the influence of the organic layer in the surface properties of GaAs(100) and in the electrical response of organic−modified Ag / GaAs Schottky diodes. The device was tested by combining surface−sensitive techniques (Photoemission spectroscopy and NEXAFS) with electrical measurements (current−voltage, capacitance−voltage, impedance and charge transient spectroscopies). Core level examination by PES confirms removal of native oxide layers on sulphur passivated (S−GaAs) and hydrogen plasma treated GaAs(100) (H+GaAs) surfaces. Additional deposition of ultrathin layers of DiMe−PTCDI may lead to a reduction of the surface defects density and thereby to an improvement of the electronic properties of GaAs. The energy level alignment through the heterostructure was deduced by combining UPS and I−V measurements. This allows fitting of the I−V characteristics with electron as majority carriers injected over a barrier by thermionic emission as a primary event. For thin organic layers (below 8 nm thickness) several techniques (UPS, I−V, C−V, QTS and AFM) show non homogeneous layer growth, leading to formation of voids. The coverage of the H+GaAs substrate as a function of the nominal thickness of DiMe−PTCDI was assessed via C−V measurements assuming a voltage independent capacitance of the organic layer. The frequency response of the device was evaluated through C−V and impedance measurements in the range 1 kHz−1 MHz. The almost independent behaviour of the capacitance in the measured frequency range confirmed the assumption of a near geometrical capacitor, which was used for modelling the impedance with an equivalent circuit of seven components. From there it was found a predominance of the space charge region impedance, so that A.C. conduction can only takes place through the parallel conductance, with a significant contribution of the back contact. Additionally a non linear behaviour of the organic layer resistance probably due to the presence of traps was deduced. ( ) ω ' R QTS measurements performed on the heterostructure showed the presence of two relaxations induced by deposition of the organic layer. The first one is attributed to the presence of a deep trap probably located at the metal / organic interface, while the second one has very small activation energy ( ~ 20 meV) which are probably due to disorder at the organic film. Those processes with small activation energies proved to be determinant for fitting the I−V characteristics of DiMe−PTCDI organic modified diodes using the expressions of a trapped charge limited current regime TCLC. Such a model was the best analytical approach found for fitting the I−V response. Further improving probably will involve implementation of numerical calculations or additional considerations in the physics of the device.

In this thesis, I have investigated gas phase infrared spectroscopy of environmentally as well as astrophysical important large organic molecules such as naphthalene, methy-lated naphthalene, fluorine, methyalted fluorine etc. which are commonly known as polycyclic aromatic hydrocarbons (PAHs). Depending upon the molecular weight these organic molecules can exist both in gaseous as well as in the particulate state at room temperature hence they are the major environmental pollutants. They are also responsible for the unidentified infrared emission bands in the interstellar medium. Chapter 1 provides a brief introduction to my thesis work. A detailed literature survey on the importance, abundance of the PAHs in the environment as well as various spectroscopic techniques useful for identifying the PAHs has been done. Since the objective of my thesis work is to assign the observed fundamental infrared bands of large organic molecules with the help of high level quantum mechanical calculations, a brief introduction to the various high level quantum mechanical techniques that I have used in assigning the bands have been described in this chapter. In Chapter 2 I have presented the experimental and the theoretical methodologies in details. The chapter begins with a detailed description of the experimental procedure used for recording the infrared spectrum of these molecules followed by the theoretical methodologies used for the assignment of the observed infrared bands as well as for identifying the Fermi resonances. In Chapters 3 and 4, of this thesis I have recorded infrared spectrum of 1-and 2-methylnaphthalene (1-and 2-MN), fluorine (FL), 1-methylfluorene (1-MFL) and 1,8-dimethylfluorene (1,8-DMF) in the gas phase. The observed bands were assigned with the help of scaled harmonic frequency, scaled quantum mechanical harmonic force field (SQMFF) and enharmonic frequency calculations. The first two methods are based on the harmonic approximation, whereas the enharmonic frequency calculation is based on the standard second order perturbation theory. All these calculations gave me a partial fit to the fundamental bands in both aromatic and aliphatic C-H stretching as well as in the non C-H stretching region. At the end of both the chapters an error analysis in fitting the spectrum from all the three different calculations have been presented. Evidently the non linear least square fitting method employed in SQMFF calculation gives much better agreement between the experiment and theory than the other two methods. It has been observed in the experimental spectrum of methylated naphthalene that the band structure near the C-H stretch around 3000 cm−1 is very complicated and many bands and shoulders remain unassigned by the methods described in Chapters 3 and 4. Fermi resonance is one of the potential reason for the complicated band structure in this region. In Chapter 5, I have taken naphthalene and have investigated the Fermi resonance around the C-H stretching region using an effective vibrational hamiltonian (EVH) approach. In this method I have constructed an EVH consisting of 8 C-H stretches and 8 H-C-C in-plane bend overtones and 28 H-C-C in-plane bend combination modes as the basis. Both type 1 (stretch overtone) and type 2 (stretch combination) Fermi resonances were investigated. Calculated frequencies belonging to B1u and B2u irreducible representation were compared with the observed bands. Many bands and shoulders have been assigned as the overtone and combination modes of low frequency H-C-C bend motion obtained from the EVH approach. How-ever some bands remain unassigned in this method. This is perhaps due to the neglect of the carbon framework motion in the construction of the EVH. To improve upon the results obtained from the EVH formalism I included the carbon frame degrees of freedom and have carried out a full variation treatment in curvilinear coordinates. I have considered the 8 C-H stretches and 8 H-C-C in-plane bends of naphthalene as local mode oscillators and 17 coordinates belonging to the carbon framework motion as curvilinear normal mode oscillators. A quartic hamiltonian in a mixed local mode -normal mode basis was constructed including up to three body terms in both kinetic and potential energy part. The hamiltonian was subsequently recast into the ladder operator form and diagonal zed in a symmetry adapted basis with polyad constraints. Frequencies so obtained were compared to the experiment All these findings have been presented in Chapter 6 of this thesis. The concluding remark of the thesis and the future direction is presented in Chapter 7

La recherche de molécules organiques à la surface de Mars est l’un des enjeux majeurs pour caractériser son habitabilité passée et/ou présente. C’est l’un des objectifs de la mission spatiale Mars Science Laboratory (MSL) et en particulier de l’instrument Sample Analysis at Mars (SAM) à bord du robot Curiosity. Cette thèse s’inscrit dans l’aide au traitement et l’interprétation des données de SAM, en vue de détecter et d’effectuer l’inventaire des molécules organiques à la surface de Mars. Ces travaux portent en premier lieu sur les performances analytiques du chromatographe en phase gazeuse (CPG) de SAM et sur l’identification des molécules organiques dans les échantillons solides martiens analysés. A cette fin, j’ai étudié les performances de la chaine d’injection et de séparation du CPG de SAM dans les conditions opératoires de vol reproduites en laboratoire. J’ai également créé une base de données des temps de rétention de molécules présentes, et potentiellement présentes sur Mars, qui sert de référence pour le traitement des données de vol. Ces données ont permis d’identifier des molécules organiques dans les échantillons solides martiens et d’expliquer pourquoi certaines d’entre elles, supposées présentes, ne sont pas détectées. La deuxième partie de l’étude est focalisée sur l’impact des minéraux oxychlorés sur les molécules organiques, lors de la pyrolyse. Pour ce faire, j’ai développé une approche systématique d’étude de la pyrolyse de molécules organiques en présence de minéraux oxydants, ayant tous deux une forte probabilité de se trouver à la surface de Mars. J’ai ainsi pu étudier l’évolution et/ou destruction des molécules organiques, déterminer celles pouvant être à l’origine des composés chlorés détectés sur Mars, évaluer l’impact de la concentration en minéraux oxychlorés et celui du paramètre de température de pyrolyse. Les résultats indiquent que le nombre, la nature, et les abondances relatives des composés formés au cours de la pyrolyse, dépendent de la nature des phases minérales et organiques, de la concentration en minéraux oxychlorés et de la température de pyrolyse. / The search for organic molecules at the Mars’ surface is of primary interest to understand its past and/or present habitability. It is one among the main goals of the Mars Science Laboratory (MSL) space mission and especially of the Sample Analysis at Mars (SAM) experiment onboard the Curiosity rover. This thesis deals with the support to the SAM data treatment and interpretation, which aims to detect and inventory the organic molecules at the Mars’ surface. The first part of this work focuses on the analytical capabilities of the SAM gas chromatograph (GC) and the identification of the organics in the solid samples analysed on Mars with the flight model. To do so, I studied the analytical chain from injection to separation of the SAM GC in the flight operating conditions reproduced in the laboratory. I also created a library of retention times for molecules present or potentially present on Mars, and used as a reference library to treat the flight data. These data allowed to identify the organics in the martian solid samples, and to explain why a few molecules, expected to be present, are not detected. The second part of the thesis focuses on the impact of oxychlorine phases on the organics, during the pyrolysis process. With this aim, I developed a systematic approach to study the pyrolysis of organic molecules on the presence of oxidant minerals that have a high probability of presence at the Mars surface.The evolution and/or destruction of the organics was evaluated. We also looked for the organic and inorganic compounds that can be the precursors of the chlorohydrocarbons detected on Mars with SAM. Finally, we evaluated the influence of the oxychlorines concentration and of the pyrolysis temperature parameter. The results show that the number, the nature and the relative abundances of the compounds formed during the pyrolysis, depend on the nature of the organic and inorganic phases, of the concentration of the oxychlorines phases and of the pyrolysis temperature.

In the present work a Metal / organic / inorganic semiconductor hybrid heterostructure (Ag / DiMe−PTCDI / GaAs) was built under UHV conditions and characterised in situ. The aim was to investigate the influence of the organic layer in the surface properties of GaAs(100) and in the electrical response of organic−modified Ag / GaAs Schottky diodes. The device was tested by combining surface−sensitive techniques (Photoemission spectroscopy and NEXAFS) with electrical measurements (current−voltage, capacitance−voltage, impedance and charge transient spectroscopies). Core level examination by PES confirms removal of native oxide layers on sulphur passivated (S−GaAs) and hydrogen plasma treated GaAs(100) (H+GaAs) surfaces. Additional deposition of ultrathin layers of DiMe−PTCDI may lead to a reduction of the surface defects density and thereby to an improvement of the electronic properties of GaAs. The energy level alignment through the heterostructure was deduced by combining UPS and I−V measurements. This allows fitting of the I−V characteristics with electron as majority carriers injected over a barrier by thermionic emission as a primary event. For thin organic layers (below 8 nm thickness) several techniques (UPS, I−V, C−V, QTS and AFM) show non homogeneous layer growth, leading to formation of voids. The coverage of the H+GaAs substrate as a function of the nominal thickness of DiMe−PTCDI was assessed via C−V measurements assuming a voltage independent capacitance of the organic layer. The frequency response of the device was evaluated through C−V and impedance measurements in the range 1 kHz−1 MHz. The almost independent behaviour of the capacitance in the measured frequency range confirmed the assumption of a near geometrical capacitor, which was used for modelling the impedance with an equivalent circuit of seven components. From there it was found a predominance of the space charge region impedance, so that A.C. conduction can only takes place through the parallel conductance, with a significant contribution of the back contact. Additionally a non linear behaviour of the organic layer resistance probably due to the presence of traps was deduced. ( ) ω ' R QTS measurements performed on the heterostructure showed the presence of two relaxations induced by deposition of the organic layer. The first one is attributed to the presence of a deep trap probably located at the metal / organic interface, while the second one has very small activation energy ( ~ 20 meV) which are probably due to disorder at the organic film. Those processes with small activation energies proved to be determinant for fitting the I−V characteristics of DiMe−PTCDI organic modified diodes using the expressions of a trapped charge limited current regime TCLC. Such a model was the best analytical approach found for fitting the I−V response. Further improving probably will involve implementation of numerical calculations or additional considerations in the physics of the device.

ZnO hat wegen seiner potenziellen Anwendung in elektronischen Geräten und als Katalysator viel Aufmerksamkeit erhalten. Die Struktur und Reaktivität von ZnO-Oberflächen haben eine direkte Bedeutung für die Leistung und Funktionalität dieser Geräte. Daher ist die Definition und das Verständnis der atomistischen Details von ZnO-Oberflächenstrukturen von besonderer Bedeutung. Die atomistischen Details von ZnO-Oberflächen hängen von den Präparationsverfahren ab. Nach der Kristallpräparation ist es notwendig, eine Oberflächencharakterisierung durchzuführen, um eine Verbesserung der Funktionalität und Effizienz von ZnO-basierten opto-elektronischen Bauelementen und Katalysatoren zu erreichen. Die atomistische Wahrnehmung der Reaktion zwischen einem organischen Molekül und ZnO-Oberflächen spielt eine entscheidende Rolle bei der Optimierung der Wasserstoff-on-demand-Lieferung in Brennstoffzellen. Das Verständnis der atomistischen Details von Adsorption, Diffusion und Dissoziation eines organischen Moleküls ebnet den Weg, um die Vorgänge bei der Wasserstofffreisetzung für Brennstoffzellen zu enträtseln. Mit dem Ziel, die Struktur- und Stöchiometriebestimmung mit Hilfe der XPS zu ermöglichen, präsentiere ich in dieser Arbeit die Ergebnisse einer umfassenden theoretischen Studie über die Kernniveauverschiebungen von ZnO-Oberflächenrekonstruktionen. Darüber hinaus biete ich eine gründliche Untersuchung der gemischt-terminierten Oberfläche, indem ich zunächst die Bedingungen untersuche, unter denen sich Methanol-Monolagen auf dieser Kristallfläche bilden können, und dann alle möglichen Wege für deren Reaktion erforsche. Diese Studie liefert ein umfassendes Bild, um die wahrscheinlichsten Reaktionsschritte zu identifizieren, die zur Interpretation der experimentellen Ergebnisse herangezogen werden können. Sie wird zukünftigen theoretischen Studien für ähnliche Reaktionen wie die Dehydrierung und die Kinetik der Monolagenbildung, die hier untersucht wurden, helfen. / Zinc-Oxide (ZnO) has been getting much attention over the past decades because of its potential application in electronic devices and as a catalyst. The structure and reactivity of ZnO surfaces have direct relevance for the performance and functionality of these devices. Therefore, defining and understanding the atomistic details of ZnO surface structures is of particular importance. The atomistic details of ZnO surfaces depend on the preparation procedures. After the crystal preparation, it is necessary to perform a surface characterization, to achieve an improvement in the functionality and efficiency of ZnO-based opto-electronic devices and catalysts. The atomistic perception of the reaction between an organic molecule and ZnO surfaces plays a crucial role in optimizing hydrogen-on-demand delivery in fuel cells, and understanding the atomistic details of adsorption, diffusion, and dissociation of a simple organic molecule paves the way towards unraveling the procedures involved in the hydrogen liberation for fuel cells. In this work, with the aim of enabling structure and stoichiometry determination by using X-ray photoelectron spectroscopy, I present the results of a comprehensive theoretical study on the core-level shifts of ZnO surface reconstructions. Moreover, I provide a thorough investigation of the mixed-terminated (10-10) surface by first examining the conditions under which methanol monolayers can form on this crystal face and by then exploring all possible pathways for its adsorption, diffusion, and initial dehydrogenation. This study provides a comprehensive picture to identify the most probable reaction steps that can be used to interpret experimental findings and will help future theoretical studies for reactions similar to dehydrogenation of organic molecules and monolayer-formation kinetics that were studied here.

La métrologie laser basée sur l’analyse de la fluorescence de traceurs moléculaires est devenue l’un des outils clefs pour l’étude expérimentale de la dynamique des fluides réactifs. Une étude spectroscopique des propriétés photophysiques de fluorescence dans le domaine spectral UV-visible de plusieurs molécules fluorescentes appartenant aux cétones aliphatiques et aux aromatiques mono- et bicycliques a permis d’approfondir la compréhension de l’influence de la température, de la pression et de la concentration d’oxygène sur leur fluorescence. Les résultats expérimentaux obtenus ont ensuite permis le développement d’un modèle de simulation du rendement de fluorescence pour les espèces aromatiques (naphtalène et toluène), qui fournit des résultats très proches de ceux mesurés.De ces résultats, le développement de la technique d’imagerie de fluorescence (PLIF) sur la phase vapeur d’un carburant multi-composant a conduit à étendre cette analyse spectrale de fluorescence au cas du kérosène (Jet A-1). La comparaison entre les propriétés de fluorescence du kérosène et des traceurs aromatiques étudiés a notamment permis d’établir une stratégie de mesure de la concentration de la phase vapeur du kérosène dans des environnements où la teneur en oxygène est variable. Les signaux de fluorescence provenant des espèces mono- et di-aromatiques contenues dans le kérosène soulignent des évolutions différentes avec les conditions de température et teneur en oxygène. L’utilisation de filtres optiques appropriés associés à deux caméras ICCD permet alors une mesure bidimensionnelle de la température et de la concentration de kérosène en phase vapeur. La thèse débouche finalement sur l’application de cette technique PLIF-kérosène en combinaison avec la technique PLIF du radical OH en sortie d’un système d’injection industriel multi-point de nouvelle génération intégré dans une chambre de combustion haute pression. / Planar laser-induced fluorescence (PLIF) diagnostic based on the optical excitation of fluorescence tracers has become a key tool for the experimental study of fluid dynamics in reactive flows. A spectroscopic fluorescence study of several organic molecules from aliphatic ketones and mono- and bi-cyclic aromatics in gas-phase was performed in a high-pressure high temperature optical cell. The experimental measurements allowed the understanding of the influence of temperature, pressure and oxygen concentration on the photophysics of these molecules in the UV/visible domain. These results were then used to successfully develop a model of fluorescence yield of the naphthalene and toluene aromatic molecules permitting the simulation of the fluorescence signals with temperature, pressure and species composition in large domains of temperature and pressure.This study has been extended to the case of a multi-component aeronautical fuel (kerosene – jet A1) containing natural aromatics. The comparison of the spectroscopic data recorded in the optical cell to those of the aromatic tracers initially probed has then permitted the definition of a kerosene-PLIF excitation/detection strategy for kerosene vapour concentration measurements in reactive gaseous flowfield containing variable oxygen concentration. Fluorescence signals from mono- and di-aromatic species in kerosene highlight significant differences in evolution with temperature and oxygen concentration. With appropriate optical filters applied to two ICCD cameras, the two-dimensional instantaneous distribution of temperature and concentration of kerosene vapour is then possible to measure in reactive flows. Finally, the kerosene-PLIF diagnostic has been applied at the exit of an innovative multi-point aeronautical injection system integrated to high-pressure kerosene/air combustor test rig. The kerosene-PLIF, combined with the radical OH-PLIF confirmed their implementation in realistic high-pressure flowfields and delivered experimental fruitful experimental information on the effect of the fuel/air mixing on the flame structure in the combustion chamber.