Die Etablierung der Telemedizin stellt neue Herausforderungen an die Aufbau- und Verbindungstechnik der Elektronik. Neue medizintechnische Anwendungen für die breite Gesellschaft erfordern biokompatible, flexible und dehnbare Elektronik, die zugleich kostengünstig und individuell hergestellt werden kann. Einen vielversprechenden Ansatz bietet die Verwendung additiver Herstellungsverfahren. Gegenstand dieser Arbeit ist die Materialauswahl für flexible und dehnbare Mikrosysteme vor dem Hintergrund der Anforderungen für zukünftige biomedizinische Anwendungen und unter Verwendung ausschließlich additiver Verfahren. Der grundlegende Aufbau gedruckter Elektronik, bestehend aus Leiterzügen verschiedener Nanopartikeltinten und polymeren Substraten, wird hinsichtlich biologischer und mechanischer Eigenschaften untersucht. Diese Charakterisierung beinhaltet die Evaluation der Zytotoxizität, Haftfestigkeit, Biegebelastung und Dehnungsbelastung der Materialkombinationen. Im Fokus steht der Inkjetdruck von Platintinte auf flexiblen Polyimid- und dehnbaren Polyurethansubstraten. Aufgrund der Inkompatibilität zwischen der erforderlichen Sintertemperatur der Platintinte und der Erweichungstemperatur des Polyurethans, wird das photonische Sintern untersucht. Dafür kommen Lasersintern und Blitzlampensintern zum Einsatz. Die Platintinte zeigt ausgezeichnete Eigenschaften im Zytotoxizitätstest durch 98 %ige Zellvitalität im Vergleich zur biokompatiblen Referenz. Die bestimmten Haftfestigkeiten liegen zwischen 0,5N/mm2 und 2,5N/mm2 und entsprechen damit aktuellen Literaturwerten. Weiterhin zeigt das Ergebnis von Biegetests vielversprechende flexible Eigenschaften. Der Widerstand nach 180 000 Biegezyklen erhöht sich bei einem Biegeradius von 5mm um maximal 9,5% und bei 2mm um maximal 42 %. Die Dehnungstests mit Horseshoestrukturen aus Silbertinte zeigen ca. 400 Dehnungszyklen bei 10% Dehnung und ca. 400 Zyklen bei 20% Dehnung bis zur vollständiger Leiterzugunterbrechung. Zwei Demonstratoren validieren das Potential der ausschließlichen Nutzung von additiven Prozessen zur Herstellung biomedizinischer Mikrosysteme. Der erste Demonstrator ist eine Hautelektrode, welche sich durch temporären Elektroden-Hautkontakt zur Hautleitwertmessung eignet. Der zweite Demonstrator beinhaltet eine miniaturisierte, gedruckte Interdigitalelektrode, die durch die Anwendung von Nanosekundenimpulsen in der Lage ist, Zellen zu manipulieren. Die Erkenntnisse aus dieser Arbeit zeigen das große Potential der Nutzung additiver Prozesse für die Herstellung von Medizinprodukten.

During past years, organic-based electronic devices revealed high promise to supplement the ubiquitous silicon-based electronic devices and enable new fields of applications. At the center of this development is the considerable progress regarding π-conjugated polymer semiconductors (PSCs): Due to their processability from solution, light-weight, as well as low-cost, PSCs are now evolving towards production-scale of new technologies, e.g., in organic solar cells (OSCs), organic field-effect transistors (OFETs), and organic light emitting diodes (OLEDs). Especially OFETs are of fundamental importance, as they constitute the switching units in all logic circuits and display technologies. However, the future world is expected to be full with smart electronics and communication devices integrated in clothes, tools and even interacting with the human body, e.g., as on-skin wearable sensors. For this the electrically-active material, just as a human tissue, requires to combine several properties in addition to being charge conducting: They need to show (i) mechanical softness, (ii) capacity to repair, (iii) multimodal sensitivity, as well as (iv) biodegradability. Here, PSCs still face challenges as they are brittle and break upon applying a mechanical stress. When trying to address this issue, the existing knowledge on mechanical properties of well-established polymeric plastics, e.g., polystyrene, cannot be directly applied for several reasons, e.g., (i) the bulkiness of monomers (including long side-chains), (ii) the rigid π-conjugated backbone, (iii) the low degree of polymerization, (iv) the small quantities in which PSCs are available, etc. Moreover, these kinds of materials should not only be mechanically compliant and stretchable, but furthermore retain their charge mobility upon stretching, and withstand numerous of mechanical stretching cycles. Considering this complex problem, researchers have been developing and investigating several approaches to combine good electrical properties and mechanical compliance within one material. These approaches include (i) stress-accommodating engineering, (ii) blending of PSCs into elastic matrix, as well as (iii) molecular engineering approach. The latter seeks to interlink mechanical and electrical properties on the molecular level, i.e., synthesize polymers that are charge conducting and stretchable. Different strategies were tested, from the modification of side chains, to the introduction of conjugation breakings spacers into the backbone. Selected works sought to incorporate stretchability and conductivity by utilizing block copolymers, i.e., covalently linking a conjugated and a non-conjugated polymer chain, resulting in a phase separation of both constituents and preserving their respective properties. The ultimate goal of this work is to achieve an intrinsically stretchable and electrically high-performing PSC via the block copolymer approach. This is done by connecting organosilicone, namely the polydimethylsiloxane (PDMS) elastomer – possessing outstanding mechanical properties, as well as good environmental and air stability – with a conjugated diketopyrrolopyrrole (DPP)-based donor-acceptor copolymer. The final obtained structure of this polymer is a tri-block copolymer (TBC) consisting of an inner DPP-based polymer block and two outer soft PDMS polymer blocks. The content of PDMS block can be controlled and be very high (up to 67 wt%), and easy processing, e.g., via shear coating, is possible. Relatively high charge carrier mobilities – in the same range as the reference DPP-based copolymer (i.e., without outer PDMS blocks) – are retained, and the block copolymers withstands numerous stretching cycles (up to 1500 cycles) without losing electrical functionality. Finally, one of the block copolymers was successfully incorporated into a biosensor for COVID-19 antibodies and antigens detection. Overall, the findings of this work show that the block copolymer is a highly versatile approach to obtain functional and stretchable semiconductors with high charge carrier mobilities. Block copolymers consisting of a high-performing donor-acceptor PSC and a biocompatible elastomer could contribute towards one of the long-term goals of organic electronics – the realization of mechanically compliant materials for applications in stretchable electronics (e.g., wearable sensors, electronic skin, etc.).

In this work, stretchable magnetic sensorics is successfully established by combining metallic thin films revealing a giant magnetoresistance effect with elastomeric materials. Stretchability of the magnetic nanomembranes is achieved by specific morphologic features (e.g. wrinkles), which accommodate the applied tensile deformation while maintaining the electrical and magnetic integrity of the sensor device. The entire development, from the demonstration of the world-wide first elastically stretchable magnetic sensor to the realization of a technology platform for robust, ready-to-use elastic magnetoelectronics with fully strain invariant properties, is described. The prepared soft giant magnetoresistive devices exhibit the same sensing performance as on conventional rigid supports, but can be stretched uniaxially or biaxially reaching strains of up to 270% and endure over 1,000 stretching cycles without fatigue. The comprehensive magnetoelectrical characterization upon tensile deformation is correlated with in-depth structural investigations of the sensor morphology transitions during stretching. With their unique mechanical properties, the elastic magnetoresistive sensor elements readily conform to ubiquitous objects of arbitrary shapes including the human skin. This feature leads electronic skin systems beyond imitating the characteristics of its natural archetype and extends their cognition to static and dynamic magnetic fields that by no means can be perceived by human beings naturally. Various application fields of stretchable magnetoelectronics are proposed and realized throughout this work. The developed sensor platform can equip soft electronic systems with navigation, orientation, motion tracking and touchless control capabilities. A variety of novel technologies, like smart textiles, soft robotics and actuators, active medical implants and soft consumer electronics will benefit from these new magnetic functionalities.

In this work, stretchable magnetic sensorics is successfully established by combining metallic thin films revealing a giant magnetoresistance effect with elastomeric materials. Stretchability of the magnetic nanomembranes is achieved by specific morphologic features (e.g. wrinkles), which accommodate the applied tensile deformation while maintaining the electrical and magnetic integrity of the sensor device. The entire development, from the demonstration of the world-wide first elastically stretchable magnetic sensor to the realization of a technology platform for robust, ready-to-use elastic magnetoelectronics with fully strain invariant properties, is described. The prepared soft giant magnetoresistive devices exhibit the same sensing performance as on conventional rigid supports, but can be stretched uniaxially or biaxially reaching strains of up to 270% and endure over 1,000 stretching cycles without fatigue. The comprehensive magnetoelectrical characterization upon tensile deformation is correlated with in-depth structural investigations of the sensor morphology transitions during stretching. With their unique mechanical properties, the elastic magnetoresistive sensor elements readily conform to ubiquitous objects of arbitrary shapes including the human skin. This feature leads electronic skin systems beyond imitating the characteristics of its natural archetype and extends their cognition to static and dynamic magnetic fields that by no means can be perceived by human beings naturally. Various application fields of stretchable magnetoelectronics are proposed and realized throughout this work. The developed sensor platform can equip soft electronic systems with navigation, orientation, motion tracking and touchless control capabilities. A variety of novel technologies, like smart textiles, soft robotics and actuators, active medical implants and soft consumer electronics will benefit from these new magnetic functionalities.:Outline List of abbreviations 7 1. INTRODUCTION 1.1 Motivation and scope of this work 8 1.1.1 A brief review on stretchable electronics 8 1.1.2 Stretchable magnetic sensorics 10 1.2 Technological approach 11 1.3 State-of-the-art 12 2. THEORETICAL BACKGROUND 2.1 Magnetic coupling phenomena in layered structures 14 2.1.1 Magnetic interlayer exchange coupling 14 2.1.2 Exchange bias 15 2.1.3 Orange peel coupling 16 2.2 Giant magnetoresistance 17 2.2.1 Electronic transport through ferromagnets 17 2.2.2 The GMR effect 19 2.2.3 GMR multilayers 20 2.2.4 Spin valves 21 2.3 Theory of elasticity 22 2.3.1 Elastomeric materials 22 2.3.2 Stress and strain 23 2.3.3 Rubber elasticity 25 2.3.4 The Poisson effect 26 2.3.5 Viscoelasticity 27 2.3.6 Bending strain in a stiff film on a flexible support 27 2.4 Approaches to stretchable electronic systems 28 2.4.1 Microcrack formation 28 2.4.2 Meanders and compliant patterns 29 2.4.3 Surface wrinkling 30 2.4.4 Rigid islands 32 3. METHODS & MATERIALS 3.1 Sample fabrication 34 3.1.1 Polydimethylsiloxane (PDMS) 34 3.1.2 PDMS film preparation 35 3.1.3 Lithographic structuring on the PDMS surface. 36 3.1.4 Magnetic thin film deposition 38 3.1.5 GMR layer stacks 40 3.1.6 Mechanically induced pre-strain 43 3.1.7 Methods and materials for the direct transfer of GMR sensors 45 3.1.8 Materials used for imperceptible GMR sensors 47 3.2 Characterization 48 3.2.1 GMR characterization setup with in situ stretching capability 48 3.2.2 Sample mounting 50 3.2.3 Electrical contacting of stretchable sensor devices 51 3.2.4 Customized demonstrator electronics 52 3.2.5 Microscopic investigation techniques 53 4. RESULTS & DISCUSSION 4.1 GMR multilayer structures on PDMS 54 4.1.1 Pre-characterization 54 4.1.2 Thermally induced wrinkling 55 4.1.3 Self-healing effect 57 4.1.4 Demonstrator: Magnetic detection on a curved surface 60 4.1.5 Sensitivity enhancement 61 4.1.6 GMR sensors in circumferential geometry 64 4.1.7 Stretchability test 67 4.2 Stretchable spin valves 69 4.2.1 Random wrinkles and periodic fracture 70 4.2.2 GMR characterization 73 4.2.3 Stretching of spin valves 74 4.2.4 Microcrack formation mechanism 76 4.3 Direct transfer printing of GMR sensorics 81 4.3.1 The direct transfer printing process 82 4.3.2 Direct transfer of GMR microsensor arrays 84 4.3.3 Direct transfer of compliant meander shaped GMR sensors 86 4.4 Imperceptible magnetoelectronics 89 4.4.1 GMR multilayers on ultra-thin PET membranes 89 4.4.2 Imperceptible GMR sensor skin 92 4.4.3 Demonstrator: Fingertip magnetic proximity sensor 93 4.4.4 Ultra-stretchable GMR sensors 94 4.4.5 Biaxial stretchability 99 4.4.6 Demonstrator: Dynamic detection of diaphragm inflation 101 5. CONCLUSIONS & OUTLOOK 5.1 Achievements 102 5.2 Outlook 104 5.2.1 Further development steps 104 5.2.2 Prospective applications. 105 5.3 Technological impact: flexible Bi Hall sensorics 106 5.3.1 Application potential 106 5.3.2 Thin and flexible Hall probes 107 5.3.3 Continuative works and improvements 108 5.4 Activities on technology transfer and public relations 108 Appendix References 110 Selbständigkeitserklärung 119 Acknowledgements 120 Curriculum Vitae 121 Scientific publications, contributions, patents, grants & prizes 122