Cette thèse est porté sur l'étude du transport électronique dans différents matériaux organiques semi-conducteurs, considérés comme candidats potentiels pour des applications en Electronique de Spin Organique. Pour rendre possible la diffusion d'un courant polarisée en spin à l'intérieur d'un semi-conducteur (injection-transport-détection), le mécanisme de transport et la mobilité des porteurs de charge, ainsi que la nature et la valeur de la résistance de contact de l'interface séparant matériau organique et électrodes métalliques ferromagnétiques, doivent répondre à des critères très stricts. Tous les dispositifs sont en géométrie latérale. Nous étudions trois matériaux organiques différents: des fibres supramoléculaires auto-assemblées, une encre de nana-flocons de graphene exfolié en phase liquide et un polymère semi-conducteur fortement dopé en forme de couche mince. Nos résultats montrent que les conditions sont partiellement respectées, mais que des défis demeurent. / In this thesis, we study the electronic charge transport properties in different high mobility organic semiconductors considered as possible candidates for applications in Organic Spintronics. Stringent conditions are needed to make possible the diffusive transport of a spin-polarized current through an organic spacer (injection-transport-detection): the mechanism of charge transport and the carriers mobility, as well as the interface between the organic semiconductor and the ferromagnetic metallic electrodes, should meet special criteria. Our devices are in lateral geometry. We investigate three organic materials, all compatible with wet processing of organic electronics: supramolecular fibers self-assembled by light irradiation, an ink of liquid-phase exfoliated graphene nano-sheets and a conjugated polymer semiconductor thin film exposed to strong electrochemical doping. We observe that the criteria are partially matched, but some challenges are still present.

La combinaison de la spintronique et de I' électronique organique est censée conduire à une nouvelle gamme d'applications en la domaine de spintronique organique. Ce travail se concentre sur la physique des molécules organiques adsorbées sur des surfaces métalliques, en mettant I' accent sur les changements de leurs structures électroniques en raison de I' effet important du substrat métallique. Nous avons étudié le complexe Ni2 adsorbé sur le Cu qui montre un effet Kondo à basses températures. Nous avons ensuite étudié des chaînes d'oligoacènes (anneaux de benzène fusionnè) qui présentent une propriété prédite: une oscillation de la bande interdite d' énergies en fonction de la longueur de la molécule. Cette propriété peut survivre même lorsque la molécule est adsorbée sur une surface, comme I' Au ou le Si02. Pour terminer, nous avons étudié des petites molécules, telles que l'éthane ou I'éthylène, adsorbées sur un subtrat de Cu et de Co. La différence d' énergie entre I' orbitale vide la plus basse (LUMO) et I' orbitale moléculaire occupée la plus élevée (HOMO) est étudiée dans les approximations de la théorie de la fonctionnelle de la densité (DFT) et la méthode GW. / The combination of spintronics and organic electronics, is believed to lead to a new generation of spin based devices, which would likely open a new broad range of applications in the field of organic spintronics. ln this context, this work focuses on organic molecules adsorbed on metallic surfaces and their electronic structure changes due to the important screening of the metallic environment. We have studied different systems, starting with a Ni2 complex adsorbed on Cu (001), where Kondo effect sets in. This study is followed by oligoacene chains (fused benzene rings) where an extraordinary property is seen: an oscillation of the energy band gap with respect to the molecular length. This property is proved to survive under the screening of surfaces such as Au(111) and Si02. We finally focused on small molecules, like ethane and ethylene, adsorbed on Cu and Co. The difference of energy between the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO) is studied using density functional theory (DFT)and GW methodologies.

Diese Arbeit stellt eine eingehende Studie des sogenannten Vertikalen Organischen Feld-Effekt-Transistors (VOFET) dar, einer neuen Transistor-Geometrie, welche dem stetig wachsenden Bereich der organischen Elektronik entspringt. Dieses neuartige Bauteil hat bereits bewiesen, dass es in der Lage ist, eine der fundamentalen Einschränkungen herkömmlicher organischer Feld-Effekt-Transistoren (OFETs) zu überwinden: Die für Schaltfrequenz und An-Strom wichtige Kanallänge des Transistors kann im VOFET stark reduziert werden, ohne dass teure und komplexe Strukturierungsmethoden genutzt werden müssen. Das genaue Funktionsprinzip des VOFET ist bisher jedoch weitgehend unerforscht. Durch den Vergleich von experimentellen Daten mit Simulationsdaten des erwarteten Bauteil-Verhaltens wird hier ein erstes, grundlegendes Verständnis des VOFETs erarbeitet. Die so gewonnenen Erkenntnisse werden im Folgenden genutzt, um bestimmte Parameter des VOFETs kontrolliert zu manipulieren. So wird beispielsweise gezeigt, dass die Morphologie des organischen Halbleiters, und damit seine Abscheidungsparameter, sowohl für die VOFET-Herstellung als auch für den Ladungsträgertransport im fertigen Bauteil eine wichtige Rolle spielen. Weiterhin wird gezeigt, dass der VOFET, genau wie der konventionelle OFET, durch das Einbringen von Kontaktdotierung deutlich verbessert werden kann. Mit Hilfe dieser Ergebnisse kann gezeigt werden, dass das Funktionsprinzip des VOFETs mit dem eines konventionellen OFETs nahezu identisch ist, wenn man von geringen Abweichungen aufgrund der unterschiedlichen Geometrien absieht. Basierend auf dieser Erkenntnis wird schließlich ein VOFET präsentiert, welcher im Inversionsmodus betrieben werden kann und so die Lücke zur konventionellen MOSFET-Technologie schließt. Dieser Inversions-VOFET stellt folglich einen vielversprechenden Ansatz für leistungsfähige organische Transistoren dar, welche als Grundbausteine für komplexe Elektronikanwendungen auf flexiblen Substraten genutzt werden können. / This work represents a comprehensive study of the so-called vertical organic field-effect transistor (VOFET), a novel transistor geometry originating from the fast-growing field of organic electronics. This device has already demonstrated its potential to overcome one of the fundamental limitations met in conventional organic transistor architectures (OFETs): In the VOFET, it is possible to reduce the channel length and thus increase On-state current and switching frequency without using expensive and complex structuring methods. Yet the VOFET's operational principles are presently not understood in full detail. By simulating the expected device behaviour and correlating it with experimental findings, a basic understanding of the charge transport in VOFETs is established and this knowledge is subsequently applied in order to manipulate certain parameters and materials in the VOFET. In particular, it is found that the morphology, and thus the deposition parameters, of the organic semiconductor play an important role, both for a successful VOFET fabrication and for the charge transport in the finished device. Furthermore, it is shown that VOFETs, just like their conventional counterparts, are greatly improved by the application of contact doping. This result, in turn, is used to demonstrate that the VOFET essentially works in almost exactly the same way as a conventional OFET, with only minor changes due to the altered contact arrangement. Working from this realisation, a vertical organic transistor is developed which operates in the inversion regime, thus closing the gap to conventional MOSFET technology and providing a truly promising candidate for high-performance organic transistors as the building blocks for advanced, flexible electronics applications.

Functional heterojunctions in organic electronic devices are interfaces formed either between a conducting electrode and an organic semiconductor or between two different organic semiconductors in blended and multilayered structures. This thesis is primarily concerned with the energy level alignment and the interfacial electronic structures at functional heterojunctions encountered in electronic devices made with solution-processable semiconducting polymers. Investigations on the electronic structures across these heterointerfaces are performed with the combined use of electromodulation and photoemission spectroscopic techniques. Electromodulation and ultraviolet photoemission spectroscopic techniques enable direct determination of the surface work functions of electrodes at the electrode/semiconducting polymer interfaces. We overcame the inherent problems faced by electromodulation spectroscopy, which undermine accurate determination of interfacial electronic structures, by performing electroabsorption (EA) measurements at reduced temperatures. We showed in this thesis that low-temperature EA spectroscopy is a surface sensitive technique that can determine the interface electronic structures in electrode/polymer semiconductor/electrode diodes. Using this technique, we demonstrated that the energy level alignments in these solution-processed organic electronic devices are determined by the surface work functions of passivated metals rather than by those of clean metals encountered in ultrahigh vacuum. This thesis also discloses our studies on the electronic structures in polymeric diodes with type II donor-acceptor heterojunctions using the EA spectroscopy. We showed that minimising meausurement temperature and attenuating EA illumination intensity enable accurate determinations of the electronic structures in these devices. We demonstrated that the electronic structures and the performance characteristics of multilayered polymer light-emitting diodes are also determined by the surface work functions of passivated metals. Our investigations confirm that electronic doping of the organic active layers, rather than minimisation of the Schottky barriers at electrode/polymer contacts, holds the key in realising high-performance organic light-emitting devices.

L’électronique organique connaît depuis ces dernières années un fort développement. Le CEA LITEN dispose d’une technologie d’impression par sérigraphie de transistors de type N et de type P sur une même plaque, permettant de créer des circuits complémentaires. Les performances et les limitations de cette technologie ont été étudiées, l’un des objectifs principaux de cette thèse étant de réaliser une étude concernant la faisabilité d’une étiquette RFID entièrement réalisée en technologie organique imprimée. Une telle étiquette, en plus d’être flexible, possèderait un coût de fabrication extrêmement bas.Des blocs entiers couramment utilisés dans les circuits RFID et comportant jusqu’à 50 transistors sont conçus et testés, montrant des performances supérieures ou au niveau de l’état de l’art dans ce domaine. La technologie organique imprimée n’étant pas aussi mature que celle utilisée dans la filière semi-conductrice classique, une étude est également menée concernant les effets de la dispersion du procédé de fabrication et du vieillissement sur les performances des circuits. Des pistes seront ainsi définies sur les paramètres (fiabilité, mobilité dans les semi-conducteurs organiques, taille des dispositifs…) à améliorer pour permettre à l’électronique organique de venir concurrencer l’industrie du silicium. / During the past few years, the field of organic electronics has known an important development. The CEA LITEN is able to manufacture N-type and P-type screen-printed transistors on a same plastic sheet, enabling the design of complementary circuits. The performances and limitations of this technology are studied since one of this thesis’ main objectives is to determine the feasibility of a fully-printed organic RFID tag. Such a tag would be flexible and could be manufactured at an extremely low-cost. Some circuits commonly used in the RFID tags, and using up to 50 transistors, are designed and tested, showing some performances equivalent or above the reported latest developments. The organic electronics manufacturing process is not as mature as the one used in the classical silicon industry. Therefore, a study is performed concerning the effects of this process scattering, as well as the ageing, on the circuits’ performances. The main improvements (in terms of reliability, organic semi-conductor mobility, size) that can help the organic electronics in order to compete, one day, with the silicon industry, are discussed.

Les diodes organiques électroluminescentes (OLEDs) représentent une évolution de la technologie des diodes électroluminescentes (LED) dans lesquelles l'émission de couleur provient de molécules organiques. Ce travail porte sur la synthèse et l'étude de nouvelles molécules dans le but de leur utilisation (i) comme couche active dans les OLED fluorescentes ou (ii) comme matériau hôte dans les OLEDs phosphorescentes (PhOLEDs). Tout d'abord, une introduction à ce domaine important de l'électronique organique est présentée et suivie de la synthèse de nouveaux semi-conducteurs organiques dérivés d'oligophénylènes d'architecture 3π-2spiro ou 2π-1spiro. L'analyse détaillée de leurs propriétés physico-chimiques est ensuite présentée. Les performances des OLEDs et/ou PhOLEDs bleues utilisant ces nouvelles matrices sont alors décrites et montrent l'intérêt des designs choisis pour les molécules. / Organic light emitting diodes (OLEDs) represent an evolution of the light emitting diode (LED) technology in which light is emitted from an organic molecule. This work is focused on the synthesis and the study of new molecules, which will be used (i) as emissive layer in fluorescent OLEDs, or (ii) as host material in phosphorescent OLED (PhOLED). First of all an introduction of the important field of organic electronics is presented, followed by the presentation of the synthesis of new organic semi-conductors (3π-2spiro or 2π-1spiro hydrocarbons). A detailed analysis of their properties was performed and after incorporation in the devices, the performances of blue OLEDs and PhOLEDs are compared. The performances recorded attests that this molecular design is of great interest.

This diploma thesis describes synthetic approach and characterization of advanced molecules with implemented adamantane skeleton and perspective use in attractive field of organic electronics. Three of four prepared molecules based on para-bis(2-thienyl)phenylene are original and totally new, and there were performed different synthetic approaches with comparison of yield, ecological and financial impact. Study of microwave synthetic approach was provided for cross-coupling reactions on para-bis(2-thienyl)phenylene skeleton. For all molecules were used ethyladamantyl and methyladamantyl substituents. Also, two completely new molecules based on 2,2':5',2''-terthiophene with ethyladamantyl and methyladamantyl substituents were prepared. In the next part were prepared new dimer structures of adamantane with possible application on field of polymers as bridge molecules. In the thesis were also made series of experiments for preparation of tetrasubstituted adamantane molecules, and for optimisation of preparation of spiroadamantane systems.

Organic electronic biosensors are developed as suitable devices that can transform electrochemical processes within the cell membrane into an electronic signal and enable to measure electrical activity of excitable cells and tissues both in vitro and in vivo and thus represent valuable alternative to current cell monitoring methods. In this work we focus on the fabrication of electrophysiological sensors based on organic semiconductors printed by the material printing method. Microelectrode arrays (MEAs) are active components of the device, which can monitore cellular activity and above that stimulating cells with electrical pulses. The proposed platform should be used for cytotoxicity of potential drugs especially on cardiac cells (cardiomyocytes). The experimental part focus on specific production processes of platforms, which were prepared in the laboraty with emphasis on biocompatibility and conductivity of device.

The development of synthetic life once envisioned by Feynman and Flynn many decades ago has stimulated significant research in materials science, biology, neuroscience, robotics, and computer science. The cross-disciplinary effort and advanced technologies in soft miniature robotics have addressed some of the significant challenges of actuation, sensing, and subsystem integration. An ideal Soft motile miniaturised robot (SMMRs) has innovative applications on a small scale, for instance, drug delivery to environmental remediation. Such a system demands smart integration of micro/nano components such as engines, actuators, sensors, controllers, and power supplies, making it possible to implement complex missions controlled wirelessly. Such an autonomous SMMR spans over multiple science and technology disciplines and requires innovative microsystem design and materials. Over the past decade, tremendous efforts have been made towards mastering one of such a SMMR's essential components: micro-engine. Chemical fuels and magnetic fields have been employed to power the micro-engines. However, it was realized seven years ago in work of TU-Chemnitz Professorship of Material Systems in Nanoelectronics and institute of investigative Nanosciences Leibniz IFW Dresden including Chemnitz side. Write explicitly that it is essential to combine the micro-engine with other functional microelectronic components to create an individually addressable smart and motile microsystem. This PhD work summarises the progress in designing and developing a novel flexible and motile soft micro autonomous robotic tubular systems (SMARTS) different from the well-studied single-tube catalytic micro-engines and other reported micromotors. Our systems incorporate polymeric nanomembranes fabricated by photolithography and rolled-up nanotechnology, which provide twin-tube structures and a spacious platform between the engines used to integrate onboard electronics. Energy can be wirelessly transferred to the catalytic tubular engine, allowing control over the SMARTS direction. Furthermore, to have more functionality onboard, a micro-robotic arm was integrated with remote triggering ability by inductive heating. To make the entire system smart, it is necessary to develop an onboard processor. However, the use of conventional Si technology is technically challenging due to the high thermal processes. We developed complex integrated circuits (IC) using novel single crystal-like organic and ZnO-based transistors to overcome this issue. Furthermore, a novel fabrication methodology that combines with six primary components of an autonomous system, namely motion, structure, onboard energy, processor, actuators, and sensors to developing novel SMARTSs, is being pursued and discussed.:List of acronyms 8 Chapter 1. Introduction 12 1.1 Motivation 14 1.2 Objectives 17 1.3 Thesis structure 18 Chapter 2. Building blocks of micro synthetic life 19 2.1 Soft structure 20 2.1.1 Polymorphic adaptability 20 2.1.2 Dynamic reconfigurability 20 2.1.3 Continuous motion 21 2.2 Locomotion 21 2.2.1 Aquatic 22 2.2.2 State-of-the-art aquatic SMMR 24 2.2.3 State-of-the-art terrestrial SMMR 25 2.2.4 State-of-the-art aerial SMMR 27 2.3 Onboard sensing 28 2.3.1 State-of-the-art 3D and flexible sensors systems 28 2.4 Onboard actuation 30 2.4.1 State-of-the-art actuators 30 2.5 Embedded onboard intelligence 32 2.5.1 State-of-the-art flexible integrated circuits 32 2.6 Onboard energy 33 2.6.1 State-of-the-art micro energy storage 34 2.6.2 State-of-the-art onboard energy harvesting SMMR 35 Chapter 3. Technology overview 38 3.1 Structure 38 3.1.1 Self-assembled “swiss-roll” architectures 40 3.1.2 Polymeric “swiss-roll” architectures 41 3.2 Motion: micro tubes as propulsion engines 44 3.2.1 Chemical engines 44 3.3 Embedded onboard intelligence 46 3.3.1 Thin film transistor 46 3.3.2 Basic characteristics of MOSFETs 48 3.4 Growth dynamics of organic single crystal films 51 3.4.1 Thin films growth dynamics 52 3.5 Powering SMARTSs 55 3.5.1 Onboard energy storage 56 3.5.2 Wireless power delivery 59 3.6 Integrable micro-arm 63 3.6.1 Stimuli-responsive actuator 63 3.6.2 Remote activation 64 Chapter 4. Fabrication and characterization 65 4.1 Thin film fabrication technology 65 4.1.1 Photolithography 65 4.1.2 E-beam deposition 68 4.1.3 Sputtering 69 4.1.4 Physical vapour deposition 70 4.1.5 Atomic layer deposition 71 4.1.6 Ion beam etching 72 4.2 Characterization methods 73 4.2.1 Atomic force microscopy 73 4.2.2 Scanning electron microscopy 74 4.2.3 Cyclic voltammetry 75 4.2.4 Galvanic charge discharge 77 4.2.5 Electrochemical impedance spectroscopy 78 Chapter 5. Development of soft micro autonomous robotic tubular systems (SMARTS) 81 5.1 Soft, flexible and robust polymeric platform 82 5.2 Locomotion of SMARTS 84 5.2.1 Assembly of polymeric tubular jet engines 84 5.2.2 Catalytic self-propulsion of soft motile microsystem 85 5.2.3 Propulsion power generated by the catalyst reaction 87 5.3 Onboard energy for SMARTS 89 5.3.1 Onboard wireless energy 90 5.3.2 Onboard ‘zero-pitch’ micro receiver coil 90 5.3.3 Evaluation of the micro receiver coil 91 5.4 Onboard energy storage 92 5.4.1 Fabrication of nano-biosupercapacitors 93 5.4.2 Electrochemical performance of “Swiss-roll” nBSC 97 5.4.3 Self-discharge performance and Bio enhancement: 98 5.4.4 Electrochemical and structural life time performance 100 5.4.5 Performance under physiologically conditions 101 5.4.6 Electrolyte temperature and flow dependent performance 102 5.4.7 Performance under hemodynamic conditions 105 5.4.8 Biocompatibility of nBSCs 105 5.5 Wireless powering and autarkic operation of SMARTS 108 5.5.1 Remote activation of an onboard IR-LED 108 5.5.2 Wireless locomotion of SMARTS 109 5.5.3 Effect of magnetic moment on SMARTS locomotion 111 5.5.4 Full 2D wireless locomotion control of SMARTS 112 5.5.5 Self-powered monolithic pH sensor system 114 5.6 Onboard remote actuation 119 5.6.1 Fabrication of integrable micro-arm 120 5.6.2 Remote actuation of integrable micro-arm 122 5.7 Flexibility of SMARTS 122 5.8 Onboard integrated electronics 123 5.9 Onboard organic electronics 124 5.9.1 Growth of BTBT-T6 as active semiconductor material 125 5.9.2 Confined Growth of BTBT-T6 to form Single-Crystal-Like Domain 128 5.9.3 Fabrication of OFET based on Single-Crystal-Like BTBT-T6 129 5.9.4 Carrier injection optimization 132 5.9.5 Performance of single-crystal-like BTBT-T6-OFET 133 5.10 Onboard flexible metal oxide electronics 136 5.10.1 Fabrication flexible ZnO TFT 138 5.10.2 Performance of ZnO TFT 139 5.10.3 Flexible integrated circuits 140 5.10.4 Logic gates 140 Chapter 6. Summary 142 Chapter 7. Conclusion and outlook 144 References 147 List of Figures & tables 173 Versicherung 177 Acknowledgement 178 Research achievements 180 Research highlight 183 Cover pages 184 Theses 188 Curriculum-vitae 191

In today’s society many non-renewable and environmentally harming energy sources are used to facilitate people’s everyday energy demands. This causes ecosystems to break down, global temperatures to rise, pollution and many more critical long lasting problems. By replacing non-renewable energy sources and taking advantage of the 100% renewable energy source, light, these problems will diminish. This project has been in collaboration with a company called Epishine who develop indoor organic solar cell devices to be able to replace conventual battery driven electrical devices with solar power harvested from indoor light. Since there is no good existing contacting solution, for Epishine to be able to enter the market, a contact solution between their solar cell device and the electrical devices it will power has to be developed. This thesis focuses on developing, designing, testing and evaluating the performance of new contact solutions for encapsulated flexible organic printed solar cells with the feasibility, viability, scalability and durability in focus. This project was conducted by first performing a literature study, thereafter, establishing a baseline for future referencing of new contact solutions and the main part, developing new concepts and evaluating them. By using the design thinking method, an iterative process could take place, allowing for a constant flow of new ideas whilst testing concepts throughout the project. The baseline tests were successful and the hypothesis of organic materials degrading over time was confirmed. From the many sub-concepts and production methods for a new contacting solution, two concepts showed promising results and were merged into one main concept. Two devices were created with the new concept, one functional device and one showing the design. To conclude, the thesis resulted in a functional solar cell device with a new contact solution which shows great potential and a new production method which enables all organic printed electronics to be design and developed in a more compact and component dense design. This production method is beneficial to not only Epishine, but everywhere where printed electronics are used and need to be optimized due to restrictions such as space and weight. / I dagens samhälle används många icke-förnybara energikällor för att underlätta människans vardagliga behov men skadar samtidigt miljön. Detta leder till att hela ekosystem fallerar, den globala temperaturen stiger, giftiga ämnen släpps fria och flera kritiska, långvariga problem skapas. Genom att byta ut icke-förnybara energikällor och istället dra nytta av den 100 % förnybara energikällan, ljus, kommer dessa ovanstående problem att minska. Detta projekt har varit i samarbete med ett företag vid namn Epishine som utvecklar organiska solcellsenheter för inomhusbruk, för att kunna ersätta konventionella batteridrivna elektriska apparater med solenergi tillvaratagen av inomhusbelysning. I dagsläget finns det ingen bra kontaktlösning mellan solcellsenheten och den apparat den ska driva, vilket är ett av Epishines större problem i nuläget, som hindrar dem från att kunna slå igenom på marknaden. Denna avhandling fokuserar på att utveckla, designa, testa och utvärdera prestandan av nya kontaktlösningar för inkapslade flexibla organiska solceller. Projektet började med en litteraturstudie, därefter etablerades en ”baseline” för att kunna jämföra de nya kontaktlösningarna. Största delen av rapporten handlar om att utveckla och testa nya kontaktlösningar för att sedan utvärdera dem. Genom att använda ”Design thinking” processen, kunde en iterativ process äga rum, vilket möjliggjorde ett konstant flöde med nya idéer som genererades samtidigt som koncept och prototyper utvecklades och utvärderades. Resultaten av ”baseline”-testerna var framgångsrika och hypotesen om att de konduktiva egenskaperna av organiska material försämras med tiden bekräftades. Från alla delkoncept och potentiella produktionsmetoderna för en ny kontaktlösning visade två koncept lovande resultat och slogs därför samman till ett huvudkoncept. Två olika solcellsenheter skapades med den nya kontaktlösningen implementerad. En funktionell enhet skapades och en enhet som visar layouten och designen. Sammanfattningsvis resulterade avhandlingen i en funktionell solcellsenhet med en ny kontaktlösning som visar stor potential samt en ny produktionsmetod som gör att all organisk tryckt elektronik kan designas och tillverkas i en mer kompakt och komponenttät design. Denna produktionsmetod är en fördel inte bara för Epishine utan också överallt där tryckt elektronik används och behöver optimeras i form av utrymme och vikt.