In dieser Arbeit wurde untersucht, wie gut bestimmte aliphatische Verbindungen, die selbstorganisierende Monolagen bilden, als Dielektrikum für organische Transistoren geeignet sind. Die auf Silicium- und Aluminiumoberflächen adsorbierten Verbindungen wurden mittels Ellipsometrie, AFM, STM und XPS charakterisiert, und die Packungsdichte, Ordnung und Oberflächenbelegung der Monolagen ermittelt. Zwischen den experimentellen Ergebnissen und denen von Computersimulationen der räumlichen Anordnung der Moleküle ergab sich eine gute Übereinstimmung. Alle untersuchten Monolagen zeigen keine Fernordnung. Der Grad der Nahordnung hängt von der Wahl der Anker- und Endgruppe ab. Die größte Packungsdichte wurde für die Verbindungen mit Phosphonsäure-Ankergruppe und Methyl-Endgruppe festgestellt. Für Monolagen der Verbindung n-Octadecylphosphonsäure auf Aluminium wurde ein Molekülabstand von 0.35 nm ermittelt. Mit dieser Verbindung als Gate-Dielektrikum wurden funktionsfähige organische Transistoren und integrierte Schaltungen demonstriert.

Organic transistors have attracted significant research interest in recent years due to their promises of mechanical flexibility and low-cost fabrication. Possible innovative applications include wearable electronic sensor systems, as well as mass-produced, inexpensive localization tags for logistics. However, the limited charge carrier mobility in organic semiconductor materials, contact resistance at the organic-metal interface and comparably long transistor channel lengths result low-speed organic transistors and low current densities compared with conventional inorganic transistors. The organic permeable base transistor (OPBT) is a disruptive transistor architecture that overcomes some of these drawbacks by providing a vertical transistor channel, which is much shorter than in lateral channel organic transistor devices. Consequently, it has been shown to be the fastest organic transistor to date with a transition frequency of 40 MHz, driving currents up to the kA/cm^2 regime. Nevertheless, the OPBT has not yet reached the application stage and its production has been limited to lab-scale devices deposited onto rigid glass substrates. Issues include low yield, large leakage currents, and unknown reliability of the devices. This work addresses these problems by transferring OPBTs to flexible polymer substrates and introducing a controlled and easily reproducible manufacturing technique for the crucial base oxide layer by electrochemical anodization. The anodization technique allows the creation of defined insulating layers, leading to devices with significantly reduced leakage currents and consequently very large transmission factors of 99.9996%. An investigation into the electrical stability of OPBTs shows that the devices are suitable as switching transistors in active matrix organic light emitting displays (AMOLED). In this application, the OPBT demonstrates its strengths particularly well, because fast operation and high current densities are needed. With this thesis a series of milestones on the path to commercial viability of the OPBT have been reached, making the device fit for large-scale production and integration into flexible electronic circuits, allowing it to drive the bendable organic displays of the future.:1 Introduction 2 Fundamentals 3 Experimental 4 Results – Flexible Devices 5 Results – Anodization of the Base Layer 6 Results – TEM Investigations 7 Results – Electrical Stress Measurements 8 Conclusion and Outlook / Durch die Aussicht auf mechanische Flexibilität und kostengünstige Herstellung haben Organische Transistoren in den vergangenen Jahren erhebliches Forschungsinteresse geweckt. Innovative Anwendungsideen umfassen tragbare elektronische Sensorsysteme und massenproduzierte, preiswerte Ortungsetiketten für die Logistik. Leider führen die geringe Ladungsträgermobilität in organischen Halbleitermaterialien, Kontaktwiderstände am Organik-Metall-Übergang und vergleichsweise große Kanallängen der Transistoren dazu, dass organische Transistoren langsamer sind und geringere Stromdichten aufweisen als anorganische Transistoren. Der Organic Permeable Base Transistor (Organischer Transistor mit durchlässiger Basis, OPBT) stellt eine bahnbrechende Transistorarchitektur dar, die mithilfe eines vertikalen Transistorkanals einige der vorgenannten Nachteile überwindet. Dadurch ist die Kanallänge deutlich kleiner, als das bei lateralen organischen Transistorbauteilen der Fall ist. Infolgedessen kann er sich als der bisher schnellste organische Transistor mit einer Transitfrequenz von 40 MHz behaupten und Stromdichten bis in den kA/cm^2 Bereich treiben. Nichtsdestotrotz hat der OPBT bislang keine Anwendungsreife erreicht und wird derzeit nur im Labormaßstab auf starren Glassubstraten hergestellt. Hindernisse sind die geringe Produktionsausbeute, große Leckströme und die unklare Zuverlässigkeit der Bauteile. Diese Arbeit nimmt die eben genannten Herausforderungen in Angriff. Es werden OPBTs auf flexible Polymersubstrate übertragen, sowie eine kontrollierte und einfach reproduzierbare Herstellungsmethode für das wichtige Basisoxid durch elektrochemische Anodisierung eingeführt. Die Anodisierungsmethode lässt definierte Isolationsschichten entstehen, was zu stark reduzierten Leckströmen und folglich zu sehr großen Transmissionsfaktoren von 99,9996% führt. Die Untersuchung der elektrischen Stabilität von OPBTs zeigt, dass die Bauteile als Schalttransistoren in organischen Aktiv-Matrix-Displays geeignet sind. Für diese Anwendung sind die Stärken von OPBTs besonders relevant, weil kurze Schaltzeiten und hohe Stromdichten benötigt werden. Mit der vorliegenden Arbeit wird eine Reihe von Meilensteinen auf dem Weg zur kommerziellen Anwendbarkeit von OPBTs erreicht. Damit ist das Bauteil reif für die großtechnische Produktion und die Integration in flexible elektronische Schaltkreise, die die biegsamen organischen Displays der Zukunft ansteuern werden.:1 Introduction 2 Fundamentals 3 Experimental 4 Results – Flexible Devices 5 Results – Anodization of the Base Layer 6 Results – TEM Investigations 7 Results – Electrical Stress Measurements 8 Conclusion and Outlook

In dieser Arbeit wurde untersucht, wie gut bestimmte aliphatische Verbindungen, die selbstorganisierende Monolagen bilden, als Dielektrikum für organische Transistoren geeignet sind. Die auf Silicium- und Aluminiumoberflächen adsorbierten Verbindungen wurden mittels Ellipsometrie, AFM, STM und XPS charakterisiert, und die Packungsdichte, Ordnung und Oberflächenbelegung der Monolagen ermittelt. Zwischen den experimentellen Ergebnissen und denen von Computersimulationen der räumlichen Anordnung der Moleküle ergab sich eine gute Übereinstimmung. Alle untersuchten Monolagen zeigen keine Fernordnung. Der Grad der Nahordnung hängt von der Wahl der Anker- und Endgruppe ab. Die größte Packungsdichte wurde für die Verbindungen mit Phosphonsäure-Ankergruppe und Methyl-Endgruppe festgestellt. Für Monolagen der Verbindung n-Octadecylphosphonsäure auf Aluminium wurde ein Molekülabstand von 0.35 nm ermittelt. Mit dieser Verbindung als Gate-Dielektrikum wurden funktionsfähige organische Transistoren und integrierte Schaltungen demonstriert.

I) Introduction p-Conjugated polymers inherently combine electronic properties of inorganic semiconductor crystals and material characteristics of organic plastics due to their special molecular design. This unique combination has led to developing new unconventional optoelectronic technologies and, further, resulted in the evolution of semiconducting polymers (SCPs) as fundamental components for novel electronic devices, such as organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs) and organic solar cells (OSCs).[1–5] Moreover, the material flexibility, capability for thin-film formation, and solution processibility additionally allow utilizing modern printing technologies for the large-scale fabrication of flexible, light-weight organic electronics. This especially enables to significantly increase the production speed and, moreover, to drastically reduce the costs per unit.[6, 7] In particular, transistors are the most important elements in modern functional electronic devices because of acting as electronic switches in logic circuits or in displays to control pixels. However, due to molecular arrangement and interactions, the electronic performance of SCPs cannot compete with the one of monocrystalline silicon which is used in state-of-the-art high-performance microtechnology.[5, 8] Nonetheless, intensive and continuing efforts of scientists focused on improving the performance of OFETs, with the special focus on the charge carrier mobility, by optimizing the polymer structure, processing conditions and OFET device architecture. By this, it was possible to identify crucial relationships between polymer structure, optoelectronic properties, microstructure, and OFET performance.[8] Nowadays, the interdisciplinary scientific success is represented by high-performance SCPs with charge carrier mobilities exceeding the value of amorphous silicon.[3, 9] However, further research is essential to enable developing the next generation of electronic devices for application in healthcare, safety technology, transportation, and communication. II) Objective and Results Within the scope of this doctoral thesis, current high-performance p-conjugated SCPs should be studied comprehensively to improve the present understanding about the interdependency between molecular structure, material properties and charge transport. Therefore, the extensive research approaches focused on different key aspects of high charge carrier mobility polymers for organic transistors. The performed investigations comprised the impact of, first, novel design concepts, second, precise structural modifications and, third, synthetic and processing conditions and led to the major findings listed below. 1. The design concept of tuning the p-conjugation length allows to gradually modulate physical material properties and demonstrates that a strong localization of frontier molecular orbitals in combination with a high degree of thin-film ordering can provide a favorable platform for charge transport in p-conjugated semiconducting polymers.[1] 2. The replacement of thiophene units with thiazoles in naphthalene diimide-based p- conjugated polymers allows to increase interchain interactions and to lower frontier molecular orbitals. This compensates the potentially detrimental enhancement of backbone torsion and drives the charge transport to unipolar electron transport, whereas mobility values are partially comparable with those of the respective thiophene containing analogs. 3. p-Conjugated diketopyrrolo[3,4-c]pyrrole-based copolymers can be synthesized within fifteen minutes what, in combination with avoiding aqueous washings and optimizing processing conditions, allowed an increase in morphological and energetic order and, thus, improved the charge transport properties significantly. III) Conclusion The key findings of this doctoral thesis provide new significant insights into important aspects of designing, synthesizing and processing high charge carrier mobility polymers. By this, they can guide future research to further improve the performance of organic electronic devices - decisive for driving the development and fabrication of smart, functional and wearable next-generation electronics. References [1] T. Erdmann, S. Fabiano, B. Milián-Medina, D. Hanifi, Z. Chen, M. Berggren, J. Gierschner, A. Salleo, A. Kiriy, B. Voit, A. Facchetti, Advanced Materials 2016, 28 (41), 9169–9174, DOI:10.1002/adma.201602923. [2] Y. Karpov, T. Erdmann, I. Raguzin, M. Al-Hussein, M. Binner, U. Lappan, M. Stamm, K. L. Gerasimov, T. Beryozkina, V. Bakulev, D. V. Anokhin, D. A. Ivanov, F. Günther, S. Gemming, G. Seifert, B. Voit, R. Di Pietro, A. Kiriy, Advanced Materials 2016, 28 (28), 6003–6010, DOI:10.1002/adma.201506295. [3] A. Facchetti, Chemistry of Materials 2011, 23 (3), 733–758, DOI:10.1021/cm102419z. [4] A. J. Heeger, Chemical Society Reviews 2010, 39, 2354–2371, DOI:10.1039/B914956M. [5] H. Klauk, Chemical Society Reviews 2010, 39, 2643–2666, DOI:10.1039/B909902F. [6] S. G. Bucella, A. Luzio, E. Gann, L. Thomsen, C. R. McNeill, G. Pace, A. Perinot, Z. Chen, A. Facchetti, M. Caironi, Nature Communications 2015, 6, 8394, DOI:10.1038/ncomms9394. [7] H. Sirringhaus, T. Kawase, R. H. Friend, T. Shimoda, M. Inbasekaran, W. Wu, E. P. Woo, Science 2000, 290 (5499), 2123–2126, DOI:10.1126/science.290.5499.2123. [8] D. Venkateshvaran, M. Nikolka, A. Sadhanala, V. Lemaur, M. Zelazny, M. Kepa, M. Hurhangee, A. J. Kronemeijer, V. Pecunia, I. Nasrallah, I. Romanov, K. Broch, I. McCulloch, D. Emin, Y. Olivier, J. Cornil, D. Beljonne, H. Sirringhaus, Nature 2014, 515 (7527), 384–388, DOI:10.1038/nature13854. [9] S. Holliday, J. E. Donaghey, I. McCulloch, Chemistry of Materials 2014, 26 (1), 647–663, DOI: 10.1021/cm402421p.

I) Introduction p-Conjugated polymers inherently combine electronic properties of inorganic semiconductor crystals and material characteristics of organic plastics due to their special molecular design. This unique combination has led to developing new unconventional optoelectronic technologies and, further, resulted in the evolution of semiconducting polymers (SCPs) as fundamental components for novel electronic devices, such as organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs) and organic solar cells (OSCs).[1–5] Moreover, the material flexibility, capability for thin-film formation, and solution processibility additionally allow utilizing modern printing technologies for the large-scale fabrication of flexible, light-weight organic electronics. This especially enables to significantly increase the production speed and, moreover, to drastically reduce the costs per unit.[6, 7] In particular, transistors are the most important elements in modern functional electronic devices because of acting as electronic switches in logic circuits or in displays to control pixels. However, due to molecular arrangement and interactions, the electronic performance of SCPs cannot compete with the one of monocrystalline silicon which is used in state-of-the-art high-performance microtechnology.[5, 8] Nonetheless, intensive and continuing efforts of scientists focused on improving the performance of OFETs, with the special focus on the charge carrier mobility, by optimizing the polymer structure, processing conditions and OFET device architecture. By this, it was possible to identify crucial relationships between polymer structure, optoelectronic properties, microstructure, and OFET performance.[8] Nowadays, the interdisciplinary scientific success is represented by high-performance SCPs with charge carrier mobilities exceeding the value of amorphous silicon.[3, 9] However, further research is essential to enable developing the next generation of electronic devices for application in healthcare, safety technology, transportation, and communication. II) Objective and Results Within the scope of this doctoral thesis, current high-performance p-conjugated SCPs should be studied comprehensively to improve the present understanding about the interdependency between molecular structure, material properties and charge transport. Therefore, the extensive research approaches focused on different key aspects of high charge carrier mobility polymers for organic transistors. The performed investigations comprised the impact of, first, novel design concepts, second, precise structural modifications and, third, synthetic and processing conditions and led to the major findings listed below. 1. The design concept of tuning the p-conjugation length allows to gradually modulate physical material properties and demonstrates that a strong localization of frontier molecular orbitals in combination with a high degree of thin-film ordering can provide a favorable platform for charge transport in p-conjugated semiconducting polymers.[1] 2. The replacement of thiophene units with thiazoles in naphthalene diimide-based p- conjugated polymers allows to increase interchain interactions and to lower frontier molecular orbitals. This compensates the potentially detrimental enhancement of backbone torsion and drives the charge transport to unipolar electron transport, whereas mobility values are partially comparable with those of the respective thiophene containing analogs. 3. p-Conjugated diketopyrrolo[3,4-c]pyrrole-based copolymers can be synthesized within fifteen minutes what, in combination with avoiding aqueous washings and optimizing processing conditions, allowed an increase in morphological and energetic order and, thus, improved the charge transport properties significantly. III) Conclusion The key findings of this doctoral thesis provide new significant insights into important aspects of designing, synthesizing and processing high charge carrier mobility polymers. By this, they can guide future research to further improve the performance of organic electronic devices - decisive for driving the development and fabrication of smart, functional and wearable next-generation electronics. References [1] T. Erdmann, S. Fabiano, B. Milián-Medina, D. Hanifi, Z. Chen, M. Berggren, J. Gierschner, A. Salleo, A. Kiriy, B. Voit, A. Facchetti, Advanced Materials 2016, 28 (41), 9169–9174, DOI:10.1002/adma.201602923. [2] Y. Karpov, T. Erdmann, I. Raguzin, M. Al-Hussein, M. Binner, U. Lappan, M. Stamm, K. L. Gerasimov, T. Beryozkina, V. Bakulev, D. V. Anokhin, D. A. Ivanov, F. Günther, S. Gemming, G. Seifert, B. Voit, R. Di Pietro, A. Kiriy, Advanced Materials 2016, 28 (28), 6003–6010, DOI:10.1002/adma.201506295. [3] A. Facchetti, Chemistry of Materials 2011, 23 (3), 733–758, DOI:10.1021/cm102419z. [4] A. J. Heeger, Chemical Society Reviews 2010, 39, 2354–2371, DOI:10.1039/B914956M. [5] H. Klauk, Chemical Society Reviews 2010, 39, 2643–2666, DOI:10.1039/B909902F. [6] S. G. Bucella, A. Luzio, E. Gann, L. Thomsen, C. R. McNeill, G. Pace, A. Perinot, Z. Chen, A. Facchetti, M. Caironi, Nature Communications 2015, 6, 8394, DOI:10.1038/ncomms9394. [7] H. Sirringhaus, T. Kawase, R. H. Friend, T. Shimoda, M. Inbasekaran, W. Wu, E. P. Woo, Science 2000, 290 (5499), 2123–2126, DOI:10.1126/science.290.5499.2123. [8] D. Venkateshvaran, M. Nikolka, A. Sadhanala, V. Lemaur, M. Zelazny, M. Kepa, M. Hurhangee, A. J. Kronemeijer, V. Pecunia, I. Nasrallah, I. Romanov, K. Broch, I. McCulloch, D. Emin, Y. Olivier, J. Cornil, D. Beljonne, H. Sirringhaus, Nature 2014, 515 (7527), 384–388, DOI:10.1038/nature13854. [9] S. Holliday, J. E. Donaghey, I. McCulloch, Chemistry of Materials 2014, 26 (1), 647–663, DOI: 10.1021/cm402421p.