Cyclooctyne and cycloocten-5-yne undergo, at room temperature, a 1,3-dipolar cycloaddition with dialkyl acetylenedicarboxylates 1a,b to generate furan-derived short-lived intermediates 2, which can be trapped by two additional equivalents of 1a,b or alternatively by methanol, phenol, water or aldehydes to yield polycyclic products 3b–d, orthoesters 4a–c, ketones 5 or epoxides 6a,b, respectively. Treatment of bis(trimethylsilyl) acetylenedicarboxylate (1c) with cyclooctyne leads to the ketone 7 via retro-Brook rearrangement of the dipolar intermediate 2c. In all cases, the products are formed with perfect atom economy.

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.

Cyclooctyne and cycloocten-5-yne undergo, at room temperature, a 1,3-dipolar cycloaddition with dialkyl acetylenedicarboxylates 1a,b to generate furan-derived short-lived intermediates 2, which can be trapped by two additional equivalents of 1a,b or alternatively by methanol, phenol, water or aldehydes to yield polycyclic products 3b–d, orthoesters 4a–c, ketones 5 or epoxides 6a,b, respectively. Treatment of bis(trimethylsilyl) acetylenedicarboxylate (1c) with cyclooctyne leads to the ketone 7 via retro-Brook rearrangement of the dipolar intermediate 2c. In all cases, the products are formed with perfect atom economy.

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