Miniaturization is a key technological approach in current times. The most prominent examples of miniaturization are personal computers and mobile phones, but we observe miniaturization in other aspects of life, with the most recent example being small portable corona test kits. In science a big part of miniaturization focuses on detectors: to make them portable, to make them integrable into bigger, multi-function systems or to enable detection of smaller and smaller samples. For many experimental techniques highly sensitive and compact devices are already available, one of the extreme examples being single photon detectors. Compared to that, miniaturization of nuclear magnetic resonance (NMR) has still a long way to go in terms of both size and sensitivity. Recently, the successful miniaturization of an NMR coil was presented: on top of a flat polymeric bilayer a metallic layout is patterned. In an aqueous solution, one polymer layer absorbs water and swells, which induces strain between the two polymeric layers. This strain is released by a self-rolling-up of the bilayer, and the metal layer transforms into a microcoil. Such microcoils were successfully used for impedimetric measurements, as antennas, and as mentioned for NMR, but their performance in the latter was far from optimal. This thesis focuses on the optimization of rolled-up microcoils (RUMs) for NMR spectroscopy, with the goal to produce high-resolution and, most importantly, high-sensitivity microcoils. The performance of the microcoil can be expressed in three parameters, namely the spectral linewidth, the (normalized) limit of detection and the damping of a nutation curve, which was not a key parameter for this thesis. Both the microcoil design and the roll-up process have an influence on the quality of a RUM. For an optimal roll-up process, the polymeric bilayer layout needed some adjustment. The rolling process itself was improved through an addition of supporting structures on top of the bilayer, which resulted in tightly rolled tubes with a well-defined diameter. The coil layout was selected from several simple layouts. This layout was then optimized with the help of experiments and simulations. For example, an improvement in resolution was achieved through a reduction of the susceptibility of the metal. Finally, the coil was embedded into a microfluidic chip. This chip allows an easy sample supply into the coil interior and protects the coil from damage. As a side effect, the chip has a positive influence on the resolution of the detector. The best RUMs have a volume of only 1.5 nl, show a linewidth of only 8 ppb and a normalized limit of detection of 0.6 nmol√Hz at 600 MHz. The achieved resolution and sensitivity allow to resolve a 1H ethanol spectrum fully in a single measurement of 6 s duration. Compared to a standard shimmed NMR detector, where the linewidth is 0.65 ppb and the nLOD 10 nmol√Hz, the RUMs linewidth still needs some improvement, but the limit of detection is already an order of magnitude smaller. Combined with the fact that the limit of detection improves with linewidth, this shows the far superior sensitivity of RUMs compared to standard setups. A comparison with literature is also very promising, where optimized RUMs compete with the best published microcoils. Additionally, RUMs can be produced en masse, with, at the moment, four coils fitting on a single 50 x 50 mm2 glass substrate, while the best other microcoils were all made for single, specific experiments one at a time. And finally, the here presented recipe for self-assembled, RUMs is easily adaptable to even smaller sample volumes and to other coil layouts. It can be used to produce matching gradient coil systems and is a guideline on how to combine NMR and other techniques while maintaining a high NMR performance.:Introduction Nuclear magnetic resonance 1 NMR principle 1.1 A single nucleus in a magnetic field 1.2 Multiple spins in external field 1.3 Spins in natura 1.4 Typical liquid state spectrum 1.5 Typical NMR setup 2 Properties of an NMR detector 2.1 Quality of rf-field 2.2 Resolution 2.3 Signal-to-noise ratio 2.4 How to optimize a microcoil 3 Existing microdetectors 3.1 Solenoids 3.2 Saddle coils 3.3 Flat coils 3.4 Striplines/Microslots 4 Comparing microdetectors 4.1 The limit of detection 4.2 Performance of published microcoils Self-assembly 5 What is self-assembly? 6 Self-assembly in microfabrication 6.1 Macroscopic self-assembly 6.2 Self-rolled tubes 7 Self-assembly of rolled-up microcoils 7.1 Working principle 7.2 Experimental methods for self-assembly 8 Encapsulating rolled-up tubes 8.1 Microfluidics 8.2 Microfluidic chip 8.3 Experimental methods for encapsulation Rolled-up microcoils 9 Fabrication 9.1 Bilayer 9.2 Coil geometry 9.3 Metal stack 9.4 Supporting elements 9.5 Rolling process 9.6 Final layout 9.7 Microfluidic integration 10 Reducing susceptibility-induced field distortions 10.1 Simulating field distortions 10.2 Influence of the coil shape 10.3 Susceptibility matching 11 NMR performance 11.1 Measurement setup 11.2 Quality of rf-field 11.3 Resolution and sensitivity 11.4 Comparison to published microcoils 12 Outlook 12.1 Further improvements to rf-field, FWHM and nLOD 12.2 New coil shapes 12.3 New applications Summary Appendix A Simulation and maths A.1 Filling factor and rf-homogeneity A.2 Nutation and rf-homogeneity A.3 FT of one-sided exponential A.4 DFT A.5 Programs B Protocols B.1 Polymeric platform B.2 Metal layers C Test protocols C.1 Wet etching D Calculations for nLODs

This work is devoted to investigate light confinement in rolled-up microtubular cavities and their optofluidic applications. The microcavities are fabricated by a roll-up mechanism based on releasing pre-strained silicon-oxide nanomembranes. By defining the shape and thickness of the nanomembranes, the geometrical tube structure is well controlled. Micro-photoluminescence spectroscopy at room temperature is employed to study the optical modes and their dependence on the structural characteristics of the microtubes. Finite-difference-time-domain simulations are performed to elucidate the experimental results. In addition, a theoretical model (based on a wave description) is applied to describe the optical modes in the tubular microcavities, supporting quantitatively and qualitatively the experimental findings. Precise spectral tuning of the optical modes is achieved by two post-fabrication methods. One method employs conformal coating of the tube wall with Al2O3 monolayers by atomic-layer-deposition, which permits a mode tuning over a wide spectral range (larger than one free-spectral-range). An average mode tuning to longer wavelengths of 0.11nm/ Al2O3-monolayer is obtained. The other method consists in asymmetric material deposition onto the tube surface. Besides the possibility of mode tuning, this method permits to detect small shape deformations (at the nanometer scale) of an optical microcavity. Controlled confinement of resonant light is demonstrated by using an asymmetric cone-like microtube, which is fabricated by unevenly rolling-up circular-shaped nanomembranes. Localized three-dimensional optical modes are obtained due to an axial confinement mechanism that is defined by the variation of the tube radius and wall windings along the tube axis. Optofluidic functions of the rolled-up microtubes are explored by immersing the tubes or filling their core with a liquid medium. Refractive index sensing of liquids is demonstrated by correlating spectral shift of the optical modes when a liquid interacts with the resonant light of the microtube. In addition, a novel sensing methodology is proposed by monitoring axial mode spacing changes. Lab-on-a-chip methods are employed to fabricate an optofluidic chip device, allowing a high degree of liquid handling. A maximum sensitivity of 880 nm/refractive-index-unit is achieved. The developed optofluidic sensors show high potential for lab-on-a-chip applications, such as real-time bio/chemical analytic systems.

This work is devoted to investigate light confinement in rolled-up microtubular cavities and their optofluidic applications. The microcavities are fabricated by a roll-up mechanism based on releasing pre-strained silicon-oxide nanomembranes. By defining the shape and thickness of the nanomembranes, the geometrical tube structure is well controlled. Micro-photoluminescence spectroscopy at room temperature is employed to study the optical modes and their dependence on the structural characteristics of the microtubes. Finite-difference-time-domain simulations are performed to elucidate the experimental results. In addition, a theoretical model (based on a wave description) is applied to describe the optical modes in the tubular microcavities, supporting quantitatively and qualitatively the experimental findings. Precise spectral tuning of the optical modes is achieved by two post-fabrication methods. One method employs conformal coating of the tube wall with Al2O3 monolayers by atomic-layer-deposition, which permits a mode tuning over a wide spectral range (larger than one free-spectral-range). An average mode tuning to longer wavelengths of 0.11nm/ Al2O3-monolayer is obtained. The other method consists in asymmetric material deposition onto the tube surface. Besides the possibility of mode tuning, this method permits to detect small shape deformations (at the nanometer scale) of an optical microcavity. Controlled confinement of resonant light is demonstrated by using an asymmetric cone-like microtube, which is fabricated by unevenly rolling-up circular-shaped nanomembranes. Localized three-dimensional optical modes are obtained due to an axial confinement mechanism that is defined by the variation of the tube radius and wall windings along the tube axis. Optofluidic functions of the rolled-up microtubes are explored by immersing the tubes or filling their core with a liquid medium. Refractive index sensing of liquids is demonstrated by correlating spectral shift of the optical modes when a liquid interacts with the resonant light of the microtube. In addition, a novel sensing methodology is proposed by monitoring axial mode spacing changes. Lab-on-a-chip methods are employed to fabricate an optofluidic chip device, allowing a high degree of liquid handling. A maximum sensitivity of 880 nm/refractive-index-unit is achieved. The developed optofluidic sensors show high potential for lab-on-a-chip applications, such as real-time bio/chemical analytic systems.

Micro-technology relies on a highly parallel fabrication of 2D electronic and/or microelectromechanical devices, where in most cases silicon wafers are used as substrates. In contrast 3D fabrication shows unique advantages, such as footprint reduction or the possibility to obtain additional functionalities. For example, in the case of a sensor, knowledge of the acceleration in all possible directions, the surrounding electric or magnetic field among other quantities can help to determine the exact position of an object in 3D space. To do that it is crucial to retrieve all components of a vector field, which requires at least one out of plane component. In other fields like integrated optics three dimensional structures can enhance the coupling efficiency with free space interactions. As such 3D micro-structures will be crucial for upcoming products and devices. A highly parallel fabrication is required to enable mass-adaption, self-assembly is an emerging technology that could deliver this purpose. Examples of 3D structures created by self-assembly include polyhedrons like cubes, pyramids or micro tubular structures such as tubes or spirals. Following a self assembly scheme, 3D devices would be created through the fabrication of standard 2D structures that are reshaped through a self-assembly step into a 3D object. In this thesis a novel dry release protocol was developed to roll-up strained nanomembranes from a silicon sacrificial layer employing dry fluorine chemistry. This way a wet release is totally circumvented thus preventing damage of the created structures due to turbulent flow or capillary forces. Additionally the developed process enabled the use of standard CMOS deposition and processing tools, leading to a high increase in yield and quality, with yields exceeding 99% for microtubes. Building on the developed technology various devices where fabricated, for example rolled-up micro capacitors at a wafer scale with an increased yield and a low spread of electrical characteristics. For the E12 industrial standard more than 90% of devices behaved within the required performance characteristics. Furthermore the yield and Q-factor of roll-up whispering gallery mode resonators was strongly improved, making it possible to self assemble 3D coupled photonic molecules, which showed a mode splitting exceeding the FSR, as well as hybrid supermodes at points of energy degeneracy.:Contents Bibliographic Record i List of Abbreviations vii List of Chemical Substances ix 1 Introduction 1 1.1 Microelectromechanical Systems 1 1.2 Strain Engineering 2 1.3 Rolled - Up Nanotechnology 3 1.4 Objective and Structure of the Thesis 5 2 Materials and Methods 9 2.1 Fabrication Techniques 9 2.1.1 Substrates 9 2.1.2 Plasma Enhanced Chemical Vapor Deposition 9 2.1.3 Dry Etching12 2.1.4 Deep Reactive Ion Etching 18 2.1.5 Atomic Layer Deposition 19 2.1.6 Lithography 20 2.2 Characterization Techniques 22 2.2.1 Strain Measurement 22 2.2.2 Ellipsometry 23 3 Dry Roll-Up of Strained Nanomembranes 25 3.1 Rolled - Up Nanotechnology 25 3.2 Fabrication 26 3.2.1 Release 29 3.3 Conclusions 33 4 Rolled-UpMicro Capacitors 35 4.1 Micro Capacitors 35 4.2 Fabrication 38 4.3 Characterization 39 4.4 Conclusion 41 5 Optical Micro-Cavities 43 5.1 Optical Micro Cavities 43 5.2 Theorectical Background 45 5.2.1 Quality - factor 49 5.2.2 FDTD 52 6 Optical Microtube Resonators 55 6.1 Optical Whispering Gallery Mode Microtube Resonators 55 6.2 Fabrication 57 6.3 Active Characterization 60 6.4 Conclusions 64 7 Photonic Molecules 65 7.1 Coupled Photonic Systems 65 7.2 Fabrication 68 7.3 Device Characterization 71 7.4 Multimode Waveguides 84 7.5 Conclusions 85 8 Conclusions and Outlook 87 8.1 Conclusions 87 8.2 Outlook 88 Bibliography 91 List of Figures 109 List of Tables 117 A Equipment 119 Cover Pages 121 Selbstständigkeitserklärung 123 Acknowledgements 125 List of Publications 127 List of Presentations 129 Curriculum Vitae 131