In this thesis, I present a comprehensive study of the interfacial electronic structure and thin film growth of two types of dipolar organic semiconductors on noble metals by employing a surface science approach, which underlines the critical role of surface electronic states in determining the interfacial electronic structure and self-assembly of organic semiconductors. I show that the electronic structure at organic/metal interfaces is complex and depends on important factors such as molecular adsorption configuration, surface/molecule coupling strength, reactivity of the substrate, molecular electrostatics, and local film structure. I demonstrate the fundamental capability of the image potential states and resonances in probing the local film environment, especially in systems consisting of inhomogeneous film structure. I also show that the presence of adsorbates on a surface allows one to investigate quantum mechanical interference effects otherwise not accessible on the bare surface. The dipolar organic semiconductors studied here are vanadyl naphthalocyanine (VONc) and chloroboron-subphthalocyanine (ClB-SubPc). The single crystals of gold and copper with hexagonal surface symmetry (111) were used to investigate the interfacial properties of VONc and ClB-SubPc, respectively. The fundamental understanding of self-assembly of large π-conjugated organic semiconductors on metals is a crucial step in controlling fabrication of supramolecular structures. Here, I provide a first step in this direction with a detailed and quantitative analysis of molecular nearest-neighbor distances that unravels the fundamental intermolecular interactions of organic semiconductors on transition metal surfaces. I additionally investigated the interfacial electronic structure of these organic semiconductors to examine the relation between molecular adsorption orientation and charge transfer across the interface.

We report the controlled formation of organic/inorganic Schottky diodes by depositing poly(3,4- ethylenedioxythiophene) (PEDOT) on n-doped ZnO layers using oxidative chemical vapor deposition (oCVD). Current-voltage measurements reveal the formation of Schottky diodes that show good thermal and temporal stability with rectification ratios of 10 7 and ideality factors of ∼1.2. In the frame of a Schottky model, we identify a mean barrier height at the hybrid inorganic-organic interface of 1.28 eV, which is consistent with the difference between the work function of PEDOT and the electron affinity of ZnO. The findings highlight the strength of oCVD to design high-quality hybrid PEDOT/ ZnO heterojunctions with possible applications in electronic and optoelectronic devices.

J'ai étudié les interfaces semi-conducteur organiques/ferromagnétique par la diffusion des électrons et la photoémission résolue en spin. Dans la première partie, un comportement inattendu de la réflexion d'électrons dépendante de spin à ces interfaces est observé. En fait, une couverture sous-monocouche des molécules organiques rend l’amplitude de réflexion d’électrons indépendante de spin, c.à.d. que la réflectivité ainsi que la phase de réflexion devient indépendante de l'orientation du spin des électrons incidents. Bien que je ne sois pas en mesure d'identifier la cause de ce phénomène, je montre qu'il s'agit d'un phénomène très général qui est indépendante de l'énergie des électrons primaires, du choix du substrat ferromagnétique, du choix de la molécule organique, et de l'orientation de la polarisation initiale. Il n'est pas du à un changement de l’aimantation de surface, à une dépolarisation des électrons primaires, ou à une interaction directe des molécules avec le substrat ferromagnétique. En outre, la théorie ne prédit pas les résultats expérimentaux et d'autres recherches sont donc nécessaires pour dévoiler la physique derrière ces observations. Dans la seconde partie de ma thèse, les expériences de photoémission résolue en spin sont réalisées au synchrotron SOLEIL. Le résultat principal est l'observation d'un état électronique induite par les molécules organiques près du niveau de Fermi qui est hautement polarisé en spin. Des mesures en fonction de l’épaisseur de la couche organique permettent d’identifier le caractère interfacial de cet état électronique. Enfin, ces résultats sont comparés avec des calculs théoriques effectués à l'institut. / I studied organic semiconductor/ferromagnet interfaces by characterizing them by spin-polarized electron scattering and photoemission spectroscopy experiments. In the first part, a completely unexpected behaviour of the spin-dependent electron reflection properties of these interfaces is observed. In fact, sub-monolayer coverage of the organic molecules makes the electron reflection amplitude independent of the spin, i.e. both the reflectivity and the reflection phase become independent of the spin orientation of the incident electrons. Although I am not able at the moment to identify the cause of this phenomenon, I show that it is a very general phenomenon which is independent of the energy of the primary electrons, the choice of the ferromagnetic substrate, the choice of the organic molecule, and of the orientation of the initial spin polarization. It is not due to a change of the surface magnetization, a depolarization of the primary electrons, or a direct interaction of the molecules with the ferromagnetic substrate. Moreover, theory does not predict so far the experimental results and further research is required to unveil the physics behind these observations. In the second part of my thesis, spin-resolved photoemission experiments have been performed at the synchrotron SOLEIL. The main result is the observation of a highly spin-polarized molecule-induced electronic state close to the Fermi level. Measurements as a function of the organic layer thickness allow us to determine the interfacial character of this electronic state. Finally, these results are compared with theoretical calculations performed at the institute.

This essay presents a study into the domain of architecture meeting new interaction design principles. The paper discusses future transparent surfaces to become programmable kinetic user interfaces, usable as information and communication channels to simplify our everyday environment. Based on the approach of using the five methodologies: Cultural Probes, Research Through Design, Grounded Theory, Star Life Cycle Model and Wizard of Oz; consistent data was collected to design and iterate on a visionary interface prototype to bridge the use of freehand gestures through motion sensing and moreover supported by RFID in a building structure on a see-through background. The objective of this paper is to unravel the main research question of how can people through kinetic interaction use organic interfaces on transparent surfaces?Several possible uses were ideated such as multiple shared user access, collaborative interaction on both sides. The primary research was answered through a final presented prototype combining a CV system with RFID for multiple and collaborative usages. User experiences and feedback makes an array of applications possible how a transparent interfaces with kinetic interaction can be applied to the interior and exterior such as fridge, mirror, doors, glass panels, alarm systems, games and the home entertainment.In today’s norm screens in the shape of a square are obsolete and support of new patterns, forms and materials are needed. Fieldwork concluded that kinetic interaction could flawlessly unite real world conditions with computer-generated substance, and become the design environment for future interactions to communicate with the user. We no longer seek to be bound to stiff shaped Graphical User Interfaces. Adding a transparent surface as background for such kinetic motion is underlying paradigm for the content to be projected into any ambience and surroundings.

I studied organic semiconductor/ferromagnet interfaces by characterizing them by spin-polarized electron scattering and photoemission spectroscopy experiments. In the first part, a completely unexpected behaviour of the spin-dependent electron reflection properties of these interfaces is observed. In fact, sub-monolayer coverage of the organic molecules makes the electron reflection amplitude independent of the spin, i.e. both the reflectivity and the reflection phase become independent of the spin orientation of the incident electrons. Although I am not able at the moment to identify the cause of this phenomenon, I show that it is a very general phenomenon which is independent of the energy of the primary electrons, the choice of the ferromagnetic substrate, the choice of the organic molecule, and of the orientation of the initial spin polarization. It is not due to a change of the surface magnetization, a depolarization of the primary electrons, or a direct interaction of the molecules with the ferromagnetic substrate. Moreover, theory does not predict so far the experimental results and further research is required to unveil the physics behind these observations. In the second part of my thesis, spin-resolved photoemission experiments have been performed at the synchrotron SOLEIL. The main result is the observation of a highly spin-polarized molecule-induced electronic state close to the Fermi level. Measurements as a function of the organic layer thickness allow us to determine the interfacial character of this electronic state. Finally, these results are compared with theoretical calculations performed at the institute.

[pt] Espectroscopia de ressonância plasmônica de superfície (SPR) é uma técnica óptica amplamente utilizada para monitorizar as alterações físicas ou químicas que ocorrem em uma interface metal - dielétrico. A medição simultânea da espessura e do índice de refração de filmes finos orgânicos, adsorvidos ou depositados sobre a superfície plana de um metal, requer duas medições independentes seguindo uma metodologia designada na literatura como método de duas cores ou método de dois meios. Na primeira, as duas medições são realizadas utilizando diferentes comprimentos de onda da radiação eletromagnética interagindo com a amostra. Na segunda, o índice de refração do meio externo (gás, líquido) é alterado entre as duas medições. Enquanto o primeiro método implica no conhecimento da função de dispersão da fase orgânica, o segundo só produz resultados precisos quando as moléculas orgânicas não interagem quimicamente com o fluido externo. Ambos os métodos apresentam dificuldades quando são aplicados à caracterização de materiais luminescentes orgânicos, os quais são na maior parte do tempo altamente reativos à umidade e ao contato com solventes orgânicos. Neste trabalho foi montado um espectrômetro de SPR automatizado. Primeiramente, ele foi testado na caracterização de amostras feitas no laboratório em termos do valor absoluto, e da homogeneidade das constantes ópticas da deposição metálica que suporta a onda de plasma. Nós demonstramos que medições precisas de constantes ópticas permitem a determinação do índice de refração de filmes finos orgânicos luminescentes, evaporados termicamente utilizando o método de substrato com dois metais. Este método, que até onde sabemos é apenas teorizado na literatura, foi aplicado a uma amostra encapsulada com um filme fino de Alq3 comercial. Além disso, a interface metal/Alq3 foi exposta a ar, e a degradação foi monitorada em tempo real, indicando uma diminuição progressiva do ângulo de ressonância da amostra. / [en] Surface Plasmon Resonance Spectroscopy (SPR) is an optical technique widely used to monitor the physical or chemical changes occurring at a metal-dielectric interface. The simultaneous measurement of the thickness and the index of refraction of organic thin films adsorbed or deposited on the metal flat surface require two independent measurements following a methodology commonly named in literature as Two-Colors Method or Two-Medium Method. In the first one, the two measurements are performed using different wavelength of the electromagnetic radiation interacting with the sample. In the second one the index of refraction of the external medium (gas, liquid) is changed between the two measurements.While the first method implies the knowledge of the dispersion function of the organic layer, the second one gives accurate results only when the organic molecules don t interact chemically with the external fluid. Both of these methods present difficulties when applied to the characterization of luminescent organic materials, most of the time highly reactive to humidity and to the contact with organic solvents. In this work an automated SPR spectrometer was assembled and first tested on the characterization of home-made samples in terms of the absolute value and homogeneity of the optical constants of the metal deposition supporting the plasma wave. We demonstrate that accurate measurements of such optical constants allow the determination of the index of refraction of thermally evaporated luminescent organic thin films using a Two-Metal Substrate Method. This method, to our knowledge only theorized up to now in literature, has been applied to an encapsulated sample containing a thin film of commercial Alq3. Further, the degradation of the metal/Alq3 interface exposed to air has been real time monitored indicating a progressive drop in the angle of resonance of the sample.

La Spectroscopie par Effet Tunnel Inélastique (IETS) avec un Microscope à Effet Tunnel (STM) est une nouvelle technique de spectroscopie vibrationnelle, qui permet de caractériser des propriétés très fines de molécules adsorbées sur des surfaces métalliques. Des règles de selection d’excitation vibrationnelle basées sur la symétrie ont été proposées, cependant, elles ne semblent pas exhaustives pour expliquer la totalité du mécanisme et des facteurs en jeu; elles ne sont pas directement transposables pour les propriétés d'un adsorbat et sont lourdes d'utilisation. Le but de cette thèse est donc d'améliorer ces règles de selection par une étude théorique. Un protocole de simulation de l'IETS a été développé, paramétré, et évalué, puis appliqué pour calculer des spectres IETS pour différentes petites molécules, qui sont systématiquement liées, sur une surface de cuivre. Des principes additifs de l'IETS ont été developpés, notamment concernant l’extension dans le vide de l’état de tunnel, l'activation/ quench sélectif de certains modes du aux propriétés électroniques de certains fragments moléculaires, et l'application de certaines règles d'addition de signaux IETS. De plus, des empreintes vibrationnelles par des signaux IETS ont été determinées pour permettre de différentier entre les orientations des adsorbats, la nature chimique des atomes et les isomères de structures. Une stratégie simple utilisant les propriétés de distribution de la densité électronique de la molécule isolée pour prédire les activités IETS sans des couts importants de calculs a aussi été développée. Cette expertise a été utilisée pour rationaliser et interpréter les mesures expérimentales des spectres IETS pour des métalloporphyrines et métallophtalocyanines adsorbées. Ces études sont les premières études IETS pour des molécules aussi larges et complexes. L'approche expérimentale a permis de déterminer les limitations actuelles des simulations IETS. Les défauts associés à l'identification ont été résolus en faisant des simulations d'images STM complémentaires. / Inelastic Electron Tunneling Spectroscopy (IETS) with the Scanning Tunneling Microscope (STM) is a novel vibrational spectroscopy technique that permits to characterize very subtle properties of molecules adsorbed on metallic surfaces. Its proposed symmetry-based propensity selection rules, however, fail to fully capture its exact mechanism and influencing factors; are not directly retraceable to an adsorbate property and are cumbersome. In this thesis, a theoretical approach was taken to improve them. An IETS simulation protocol has been developed, parameterized and benchmarked, and consequently used to calculate IETS spectra for a set of systematically related small molecules on copper surfaces. Extending IETS principles were deduced that refer to the tunneling state’s vacuum extension, the selective activating/quenching of certain types of modes due to the moieties’ electronic properties, and the applicability of a sum rule of IETS signals. Also, fingerprinting IETS-signals that enable discrimination between adsorbate orientations, the chemical nature of atoms and structural isomers were determined and a strategy using straightforward electronic density distribution properties of the isolated molecule to predict IETS activity without (large) computational cost was developed. This expertise was used to rationalize and interpret experimentally measured IETS spectra for adsorbed metalloporphyrins and metallophthalocyanines, being the first IETS studies of this large size. This experimental approach permitted to determine the current limitations of IETS-simulations. The associated identification shortcomings were resolved by conducting complementary STM-image simulations.