In HIOS-Strukturen, die auf einem Quantengraben und einer angrenzenden organischen Deckschicht basieren, wurde eine effiziente Umwandlung von Wannier-Exzitonen in Frenkel-Exzitonen mittels resonantem Förster Energietransfer (FRET) demonstriert. Das hier verwendete Design besteht aus einem spiro-annulierten Quarter-phenyl (L4P-SP3), das auf einen ZnO-Quantengraben (SQW) aufgewachsen wurde, um inkohärente Kopplung zu erreichen. Mittels optischer Spektroskopie haben wir demonstriert, dass diese hybriden Strukturen Energietransfer vom SQW zu den organischen Molekülen mit einer Effizienz von bis zu 77% zeigen. Allerdings zeigen UPS-Messungen eine typ-II-artige Energieniveau-Anpassung zwischen ZnO und der molekularen Schicht, die zu einem sehr effizienten Ladungstrennungsvorgang (ηCT=0.9) führt, der die molekulare Emission unterdrückt. Die erste beruht auf einer schnellen und hocheffizienten Energietransfer-Kaskade: nach der ersten Transferstufe wird die Anregungsenergie von der hybriden Grenzfläche weggeleitet, indem eine zweite Energietransferstufe eingeführt wird, bevor die Dissoziation der Exzitonen an der Grenzfläche statt-finden kann. Wir verwenden Sexiphenyl, L6P als endgültigen Akzeptor. In solch einer Struktur können wir eine Wiederherstellung der molekularen Emission um einen Faktor acht demonstrieren und zeigen, dass der Energietransferprozess zwischen L4P-SP3 und L6P den Ladungstrennungsprozess fast vollständig überholt. Als andere Option haben wir die Energieniveaus angepasst, indem eine organometallische Donor-Monolage [RuCp*mes] ergänzt wird. Diese Zwischenschicht senkt die Austrittsarbeit von ZnO deutlich ab und führt so zu einer Anpassung der Niveaus zwischen die zwei Halbleiter. Während die Effizienz des Energietransfers unverändert bleibt, steigen die Emission von L4P-SP3 sowie die Lebenszeit der molekularen Photoluminescenz um einen Faktor sieben verglichen mit entsprechenden Strukturen ohne Zwischenlage. / In HIOS structures based on a quantum well and an adjacent organic overlayer, efficient conversion of Wannier excitons into Frenkel excitons via Förster-type resonant energy transfer (FRET) has been demonstrated. The design here in use consists of a spiro-annulated ladder-type quarter-phenyl (L4P-SP3), deposited on ZnO-based single quantum wells (SQW) to obtain incoherent electronic coupling. The SQWs we use are grown with extremely thin (2 nm) capping layer. With photoluminescence excitation and time-resolved spectroscopy, we demonstrate that these hybrid structures exhibit energy transfer from the inorganic material to the organic molecules with an efficiency up to 77%. However, UPS measurements show a type-II energy level alignment between ZnO and the molecular layer, resulting in a very efficient charge separation process (ηCT=0.9) that suppresses the molecular emission. The first idea relies on a fast and highly efficient cascade FRET: following the primary transfer step from the QW, the excitation is conveyed away from the hybrid interface by a secondary transfer-step within the organic layer. As final acceptor we select ladder-type sexiphenyl (L6P). In such a structure, we demonstrate a recovery of the molecular emission by a factor eight, showing that the intermolecular FRET outpaced almost entirely the charge separation process. As alternative option, we tune the energy levels at the interface by introducing an organometallic donor monolayer [RuCp*mes]. The interlayer reduces substantially the ZnO work function, aligning the frontier levels of the inorganic and organic semiconductor. Optical experiments show the benefits of the interlayer: while the FRET efficiency is unaffected, the L4P-SP3 emission and its photoluminescence lifetime increase by a factor of seven, when compared to the same structure without interlayer.

In der heutigen Zeit sind optoelektronische Bauelemente allgegenwärtig. Sie finden Anwendung für Beleuchtungszwecke, in Anzeigen und für die Telekommunikation. Die Entwicklung dieser Anwendungen wurde lange Zeit von anorganischen Halbleitern getragen, in jüngerer Vergangenheit auch von der organischen Elektronik. Neuerdings werden verstärkt Konzepte entwickelt, um die spezifischen Vorteile der jeweiligen komplementären Materialklassen auszunutzen. Für diese Hybridisierung müssen die Eigenschaften der verschiedenen Materialien, insbesondere die elektronische Struktur, genau auf einander abgestimmt sein. In dieser Arbeit werden Leiter-para-phenylene auf spektrale Überlagerung und angepasste Orbitalenergien mit ZnO, auf chemische Inertheit und auf die Bildung von dünnen Schichten über vakuumbasierte Verarbeitungsmethoden optimiert. Dazu konzentriert sich der synthetische Gesichtspunkt auf die selektive Funktionalisierung der verschiedenen Methylenbrücken mit Alkyl-, Aryl- und Fluorsubstituenten. Die finalen Stufen werden bezüglich ihrer optischen Eigenschaften mittels Absorption und Fluoreszenz, bezüglich ihrer elektrochemischen Eigenschaften und bezüglich ihrer Festkörperstruktur mittels Röntgenstrukturanalyse von Einkristallen charakterisiert. Außerdem widmet sich ein erheblicher Teil dieser Arbeit der Erforschung des photochemischen Abbaus von fluorenbasierten Strukturen. Es werden neue Erkenntnisse zum Abbaumechanismus und der Ursache der grünen Emission gewonnen. Weiterhin werden die Abbauraten von Fluorenstrukturen mit verschiedenen Brückensubstituenten verglichen. Dabei konnten auch verschiedene Reaktionsprodukte und Mechanismen nachgewiesen werden. Letztendlich wird auch die Anwendung einzelner Derivate in Hybridstrukturen diskutiert. / Nowadays optoelectronic devices are ubiquitous for illumination purposes, in telecommunication and displays. For a long time, the development for these devices was driven by inorganic semiconductors, later organic semiconductors contributed, as well. Recently concepts have been developed to combine both complementary material classes to exploit the specific advantages of each one. For the hybridization, the properties of the materials, especially the electronic structure, have to match very well. In this work the optimization of ladder-type p-phenylenes towards spectral overlap and energy level alignment with ZnO, vacuum-processability, inertness, as well as layer formation is described. In terms of molecular design the different properties are addressed by site-selective functionalization of the methylene bridges with alkyl, aryl, and fluoro groups. The final products are characterized regarding their optical properties by absorption and fluorescence, their electrochemical properties, as well as their solid-state structure by single crystal X-ray diffraction. Apart from that, a large part of the work is devoted to investigations of the photochemical degradation of fluorene-type structures. New insights are gained into the mechanism of degradation, as well as the origin of the green emission in ladder-type structures The dependence of the rate of degradation is described semi-quantitatively with respect to the substitution pattern. By that, different reaction mechanisms for different substituents are found. Finally, the integration of some products in hybrid structures is discussed.

Résumé : Cette recherche analyse l'impact des technologies numériques sur l'efficacité de l'innovation des formations professionnelles d'ingénieur, des apprentissages et la flexibilité des dispositifs pédagogiques, ainsi que sur la professionnalisation des enseignants tuteurs universitaires. Ceci, au regard des modèles d'organisation managériale et d’usages pédagogiques des TIC. Les résultats de l’axe 1 indiquent que, les dispositifs de Master présentent un modèle d’organisation bi modale hybride qui impacte directement le déséquilibre de répartition des charges entre distance/présence. L’impact indirect sur les actions managériales favorise la flexibilité des dispositifs en termes de gestion des contraintes professionnelles/distance géographique et l’adaptation horaire, l’ouverture aux projets communs, le libre choix des méthodes et outils de communication collaborative médiatisée, accentués par l’émergence de changements de comportement, et une forte dynamique d’esprit d’équipe acceptant les différences constructives. En revanche, il suscite chez l’étudiant l’expression d’un mal-être se traduisant par la nécessité de souplesse structurelle, un besoin de télé laboratoire et plus de travaux pratiques professionnels en présence. L’axe 2 indique un impact direct sur l’usage pédagogique intensif du groupe d’outils incitatifs et interactifs (Emails, chat, forum, simulations, exerciseurs, conception/modèle graphe), et un usage médiocre du groupe (vidéo/visioconférence, audioconférence), l’absence d’usage du groupe (blog, wiki). En outre, il apparaît que le groupe d’outils (chat, forum, simulation, exerciseur) à usage intensif (presque à tous les UE), sont peu efficaces, contrairement aux outils (vidéo/visioconférence, téléconférence) à usage médiocre (rare à l’UE), qui sont plutôt assez efficace. La structuration des forums a un impact significatif sur l’efficacité d’apprentissage. Les forums de type 2 (assez structurés, 3 ≥ fn < 6), présentent une forte intensité de messages référentiels cognitifs et un comportement initia tif et réactif, assez prononcé. A L’inverse, les forums de type 1 (peu structurés, fn < 3), accentuent les messages (relationnels, de régulation) et l’attitude évaluative. Il apparaît dans les dispositifs hybrides, que la performance des étudiants ne dépend pas simplement de l’usage diversifié et intensif d’outils numériques, mais aussi des facteurs d’autodétermination, motivationnels, le sentiment de compétences et la valeur ajoutée des dispositifs. L’axe 3, présente un impact significatif des dispositifs sur le développement professionnel des enseignants/tuteurs, au niveau du changement des pratiques innovantes et de leur sentiment d’engagement. Il ressort que l’engagement dépend plus de l’intention personnelle d’explorer de nouvelles méthodes pédagogiques à distance par le numérique, et non pas aux prescriptions institutionnelles, ou actions managériales, perçues comme des injonctions institutionnelles.Mots-clés : Management et organisation, Technologies numériques, Innovation et formation d’ingénieurs, flexibilité et efficacité des stratégies, impact dispositifs hybrides ou FAD/e-Learning, actes de langage, pratiques pédagogiques innovantes, développement professionnel / This research analyzes the impact of the digital technologies on the efficiency of innovation of the vocational engineer’s trainings, and the flexibility of educational devices in distance learning, as well as on the professionalization of the teacher’s university guardians. This, with regard to the models of managerial organization and educational practices of ICTS(INFORMATION AND COMMUNICATION TECHNOLOGIES).With the glance as of results from the axis 1, it arises that, the organization devices as regard mater degree, offer the model type bimodal hybrid with an imbalance in the burden-sharing with charges activities higher as distance involved than presence. The indirect impact of managerial actions favor the flexibility of devices in terms of managing professionals constraints as regard distance geographical and the hourly adaptation, the opening to the common projects, the free choice of methods and communications tools. It accentuated the emergency of the behavioral changes, and a strong dynamics of team spirit accepting the constructive differences. In addition, from de axis 2 of search, the intensive use of the inciting digital tools and interactive tool is not enough to explain their effectiveness or performance durably in supporting quality and evolution of the device’s training. It makes emerge the difficulty in organizing, illustrating and sharing the graphic figures or symbols, in order to explain reasoning during the exchanges with (chat, audio conference, and forum).The use of simulation devices is less effective, because of the digital divide (cost access and low speed Internet, infrastructures decayed to the point). Furthermore, the level of structuring of the forums has a significant impact on the effectiveness of training. Forums of the type 2 (structured enough, 3 ≥ fn ≤ 6), presents a high intensity of cognitive/métacognitive’s messages, an initiative and reactive behavior. It is the reverse with the forums type 1 (little structured, fn ≤ 2), where the evaluative attitude and messages that are not directly related to learning are increase than others. It also appears that the performance of the students does not depend simply on the intensive use of tool of the digital tools, but of their self-determination, resulting in their feeling of new competences, the sources of motivation and the added-value of the devices to develop itself in company. It arises from axis 3 that the devices significantly impact the professional development of the teachers/tutors, with the changes of practices digital and a strong personal intention to explore new teaching practices remotely, and not of a commitment related to the managerial or institutional regulations, perceived like injunctions.Keys words: Impact of digital technologies, hybrid devices or FAD/e-Learning, training of engineers of LMD system, flexibility and effectiveness’s pedagogic, acts of language and training quality, practices innovating, professional development of trainer. Management and organization

This thesis work contains electrical transport and low frequency (1/f) noise measurements in ultrathin graphene and Molybdenum disulphide (MoS2) field effect transistors (FET). From the measurements, We mainly focus on the origin of disorder in both the materials. To address the orgin of disorder in graphene, we study single and bilayer graphene-FET devices on SiO2 substrate. We observe that both conductivity and mobility are mainly determined by substrate induced long range, short range, and polar phonon scattering. For further confirmation, we fabricate suspended graphene devices which show extremely high mobility. We find that, in contrast to substrate-supported graphene, conductivity and mobility in suspended graphene are governed by the longitudinal acoustic phonon scattering at high temperature and the devices reach a ballistic limit at low temperature. We also conduct low frequency 1/f noise measurements, known to be sensitive to disorder dynamics, to extract more information on the nature of disorder. The measurements are carried out both in substrate-supported and suspended graphene devices. We find that 1/f noise in substarted graphene is mainly determined by the trap charges in the SiO2 substrate. On the other hand, noise behaviour in suspended graphene devices can not be explained with trap charge dominated noise model. More-over, suspended devices exhibit one order of magnitude less noise compared to graphene on SiO2 substrate. We believe noise in suspended graphene devices probably originate from metal-graphene contact regions. In the second part of our work, We present low temperature electrical transport in ultrathin MoS2 fields effect devices, mechanically exfoliated onto Si/SiO2 substrate. Our experiments reveal that the electronic states in MoS2 are localized well up to the room temperature over the experimentally accessible range of gate voltage. This manifests in two dimensional (2D) variable range hopping (VRH) at high temperatures, while below ~ 30 K the conductivity displays oscillatory structures in gate voltage arising from resonant tunneling at the localized sites. From the correlation energy (T0) of VRH and gate voltage dependence of conductivity, we suggest that the charged impurities are the dominant source of disorder in MoS2. To explore the origin of the disorder, we perform temperature dependent I - V measurements at high source-drain bias. These measurements indicate presence of an exponentially distributed trap states in MoS2 which originate from the structural inhomogeneity. For more detailed investigation, we employ 1/f noise which further confirms possible presence of structural disorder in the system. The origin of the localized states is also investigated by spectroscopic studies, which indicate a possible presence of metallic 1T-patches inside semiconducting 2H phase. From all these evidences, we suggest that the disorder is internal, and achieving high mobility in MoS2 FET requires a greater level of crystalline homogeneity.

Com a crescente complexidade das aplicações e sistemas computacionais, atualmente tem se tornado importante o uso de formalismos de várias naturezas na representação e modelagem de problemas complexos, como os sistemas reativos e concorrentes. Este trabalho apresenta uma contribuição na Tecnologia Adaptativa e uma nova técnica no desenvolvimento de uma aplicação para execução de alguns tipos de jogos, (General Game Playing), cuja característica está associada à capacidade de o sistema tomar conhecimento das regras do jogo apenas em tempo de execução. Com esse trabalho, amplia-se a classe de problemas que podem ser estudados e analisados sob a perspectiva da Tecnologia Adaptativa, através dos Dispositivos Adaptativos Cooperantes. A aplicação desenvolvida como exemplo neste trabalho introduz uma nova ótica no desenvolvimento de aplicações para jogos gerais (GGP) e abre novos horizontes para a aplicação da Tecnologia Adaptativa, como a utilização das regras para extração de informação e inferência. / The complexity of computer applications has grown so much that several formalisms of different kinds became important nowadays. Many systems (e.g. reactive and concurrent ones) employ such formalisms to represent and model actual complex problems. This work contributes to the field of Adaptive Technology, and proposes a new approach for developing general game playing system, whose feature is the capability to play a game by acknowledging the game rules only at run time. This work expands the set of problems that can be studied and analyzed under the Adaptive Technology perspective, by means of cooperating adaptive devices. The developed application used a new approach for general game playing development bringing and widens the application field of Adaptive Technology with subjects related to information extraction and inference based in the devices rules.

Com a crescente complexidade das aplicações e sistemas computacionais, atualmente tem se tornado importante o uso de formalismos de várias naturezas na representação e modelagem de problemas complexos, como os sistemas reativos e concorrentes. Este trabalho apresenta uma contribuição na Tecnologia Adaptativa e uma nova técnica no desenvolvimento de uma aplicação para execução de alguns tipos de jogos, (General Game Playing), cuja característica está associada à capacidade de o sistema tomar conhecimento das regras do jogo apenas em tempo de execução. Com esse trabalho, amplia-se a classe de problemas que podem ser estudados e analisados sob a perspectiva da Tecnologia Adaptativa, através dos Dispositivos Adaptativos Cooperantes. A aplicação desenvolvida como exemplo neste trabalho introduz uma nova ótica no desenvolvimento de aplicações para jogos gerais (GGP) e abre novos horizontes para a aplicação da Tecnologia Adaptativa, como a utilização das regras para extração de informação e inferência. / The complexity of computer applications has grown so much that several formalisms of different kinds became important nowadays. Many systems (e.g. reactive and concurrent ones) employ such formalisms to represent and model actual complex problems. This work contributes to the field of Adaptive Technology, and proposes a new approach for developing general game playing system, whose feature is the capability to play a game by acknowledging the game rules only at run time. This work expands the set of problems that can be studied and analyzed under the Adaptive Technology perspective, by means of cooperating adaptive devices. The developed application used a new approach for general game playing development bringing and widens the application field of Adaptive Technology with subjects related to information extraction and inference based in the devices rules.