New frequencies and geometries for plasmonics and metamaterials

The manipulation of light at the nanoscale has become a fascinating research field called nanophotonics. It brings together a wide range of topics such as semiconductor quantum dots or molecular optoelectronics and the study of metal optics, or plasmonics, on one hand and the development of finely designed structures with specifically engineered optical properties called metamaterials on the other. As is often the case, it is at the boundary of these two domains that most novel effects can be observed. Plasmonics has for instance enabled the detection of single molecules due to the large field enhancement which exists in the vicinity of nanostructured metals. Thanks to the confinement of electromagnetic waves below the diffraction limit plasmonic systems are also foreseen as ideal conduits connecting electronic and photonic systems. On another hand, when a material is patterned on a scale smaller than the wavelength, its optical properties are reflections of the structure of the patterned material rather than the material itself, a concept known as metamaterial. This has allowed researchers to obtain exotic optical properties such as negative refractive indices and can be implemented in devices acting like invisibility cloaks or perfect lenses. While the prospects for nanophotonics are far-reaching, real-life applications are severely limited by the intrinsic absorption of metals and the current fabrication methods mostly based on electron-beam lithography which is slow and costly. In this thesis, we investigate these issues by considering the potentials of other polaritonic materials such as semiconductors, silicon carbide and graphene for field confinement applications. This is achieved through the combination of both numerical studies and sample fabrication and testing with the help of international collaborators. Our results show much improvement over the metallic structures typically used, with an operating range covering the near- and mid-infrared as well as the terahertz. The field compression can also be much greater compared to conventional plasmonic materials, with near-field enhancements reaching four orders of magnitude. Furthermore, we analyse theoretically the optical properties of metallic gyroids which are obtained by self-assembly - a promising chemical route for fabricating large-scale 3D structures with molecular sized resolution. These materials exhibit unexpected properties such as negative refraction and could in consequence be used as thin lenses or wave-plates. Last, we develop and apply a theoretical formulation of Fano theory for the case of plasmonics. It allows a clear and simple physical understanding of the interference spectra which are commonly encountered in nanooptics.Open Acces

MEMS tunable infrared metamaterial and mechanical sensors

Sub-wavelength resonant structures open the path for fine controlling the near-field at the nanoscale dimension. They constitute into macroscopic “metamaterials” with macroscale properties such as transmission, reflection, and absorption being tailored to exhibit a particular electromagnetic response. The properties of the resonators are often fixed at the time of fabrication wherein the tunability is demanding to overcome fabrication tolerances and afford fast signal processing. Hybridizing dynamic components such as optically active medium into the device makes tunable devices. Microelectromechanical systems (MEMS) compatible integrated circuit fabrication process is a promising platform that can be merged with photonics or novel 2D materials. The prospect of enormous freedom in integrating nanophotonics, MEMS actuators and sensors, and microelectronics into a single platform has driven the rapid development of MEMS-based sensing devices. This thesis describes the design and development of four tunable plasmonic structures based on active media or MEMS, two graphene-based MEMS sensors and a novel tape-based cost-effective nanotransfer printing techniques. First of all, we present two tunable plasmonic devices with the use of two active medium, which are electrically controlled liquid crystals and temperature-responsive hydrogels, respectively. By incorporating a nematic liquid crystal layer into quasi-3D mushroom plasmonic nanostructures and thanks to the unique coupling between surface plasmon polariton and Rayleigh anomaly, we have achieved the electrical tuning of the properties of plasmonic crystal at a low operating electric field. We also present another tunable plasmonic device with the capability to sense environmental temperature variations. The device is bowtie nanoantenna arrays coated with a submicron-thick, thermos-responsive hydrogel. The favorable scaling of plasmonic dimers at the nanometer scale and ionic diffusion at the submicron scale is leveraged to achieve strong optical resonance and rapid hydrogel response, respectively. Secondly, we present two MEMS -based tunable near-to-mid infrared metamaterials on a silicon-on-insulator wafer via electrically and thermally actuating the freestanding nanocantilevers. The two devices are developed on the basis of the same fabrication process and are easy-to-implement. The electrostatically driven metamaterial affords ultrahigh mechanical modulation (several tens of MHz) of an optical signal while the thermo-mechanically tunable metamaterial provides up to 90% optical signal modulation at a wavelength of 3.6 õm. Next, we present MEMS graphene-based pressure and gas flow sensors realized by transferring a large area and few-layered graphene onto a suspended silicon nitride thin membrane perforated with micro-through-holes. Due to the increased strain in the through-holes, the pressure sensor exhibits a very high sensitivty outperformed than most existing MEMS-based pressure sensors using graphene, silicon, and carbon nanotubes. An air flow sensor is also demonstrated via patterning graphene sheets with flow-through microholes. The flow rate of the air is measured by converting the mechanically deflection of the membrane into the electrical readout due to the graphene piezeroresistors. Finally, we present a tape-based multifunctional nanotransfer printing process based on a simple stick-and-peel procedure. It affords fast production of large-area metallic and dielectric nanophotonic sensing devices and metamaterials using Scotch tape

Functional colloidal surface assemblies: Classical optics meets template-assisted self-assembly

Abstract: When noble metals particles are synthesized with progressively smaller dimensions, strikingly novel optical properties arise. For nanoscale particles, collective disturbances of the electron density known as localized surface plasmons resonances can arise, and these resonances are utilized in a variety of applications ranging from surface-enhanced molecular spectroscopy and sensing to photothermal cancer therapy to plasmon-driven photochemistry. Central to all of these studies is the plasmon’s remarkable ability to process light, capturing and converting it into intense near fields, heat, and even energetic carriers at the nanoscale. In the past decade, we have witnessed major advances in plasmonics which is directly linked with the much broader field of (colloidal) nanotechnology. These breakthroughs span from plasmon lasing and waveguides, plasmonic photochemistry and solar cells to active plasmonics, plasmonics nanocomposites and semiconductor plasmons. All the above-mentioned phenomena rely on precise spatial placement and distinct control over the dimensions and orientation of the individual plasmonic building blocks within complex one-, two- or three-dimensional complex arrangements. For the nanofabrication of metal nanostructures at surfaces, most often lithographic approaches, e.g. e-beam lithography or ion-beam milling are generally applied, due to their versatility and precision. However, these techniques come along with several drawbacks such as limited scalability, limited resolution, limited compatibility with silicon manufacturing techniques, damping effects due to the polycrystalline nature of the metal nanostructures and low sample throughput. Thus, there is a great demand for alternative approaches for the fabrication of metal nanostructures to overcome the above-mentioned limitations. But why colloids? True three-dimensionality, lower damping, high quality modes due to mono-dispersity, and the absence of grain boundaries make the colloidal assembly an especially competitive method for high quality large-scale fabrication. On top of that, colloids provide a versatile platform in terms of size, shape, composition and surface modification and dispersion media. 540The combination of directed self-assembly and laser interference lithography is a versatile admixture of bottom-up and top-down approaches that represents a compelling alternative to commonly used nanofabrication methods. The objective of this thesis is to focus on large area fabrication of emergent spectroscopic properties with high structural and optical quality via colloidal self-assembly. We focus on synergy between optical and plasmonic effects such as: (i) coupling between localized surface plasmon resonance and Bragg diffraction leading to surface lattice resonance; (ii) strong light matter interaction between guided mode resonance and collective plasmonic chain modes leading to hybrid guided plasmon modes, which can further be used to boost the hot-electron efficiency in a semiconducting material; (iii) similarly, bilayer nanoparticle chains leading to chiro-optical effects. Following this scope, this thesis introduces a real-time tuning of such exclusive plasmonic-photonic (hybrid) modes via flexible template fabrication. Mechanical stimuli such as tensile strain facilitate the dynamic tuning of surface lattice resonance and chiro-optical effects respectively. This expands the scope to curb the rigidity in optical systems and ease the integration of such systems with flexible electronics or circuits.:Contents Abstract Kurzfassung Abbreviations 1. Introduction and scope of the thesis 1.1. Introduction 1.1.1. Classical optics concepts 1.1.2. Top down fabrication methods and their challenges 1.1.3. Template-assisted self-assembly 1.1.4. Functional colloidal surface assemblies 1.2. Scope of the thesis 2. Results and Discussion 2.1. Mechanotunable Surface Lattice Resonances in the Visible Optical Range by Soft Lithography Templates and Directed Self-Assembly 2.1.1. Fabrication of flexible 2D plasmonic lattice 2.1.2. Investigation of the influence of particle size distribution on SLR quality 2.1.3. Band diagram analysis of 2D plasmonic lattice 2.1.4. Strain induced tuning of SLR 2.1.5. SEM and force transfer analysis in 2D plasmonic lattice under various strain 2.2. Hybridized Guided-Mode Resonances via Colloidal Plasmonic Self-Assembled Grating 2.2.1. Fabrication of hybrid opto-plasmonic structure via template assisted self-assembly 2.2.2. Comparison of optical band diagram of three (plasmonic, photonic and hybrid) different structures in TE and TM modes 2.2.3. Simulative comparison of optical properties of hybrid opto-plasmonic NP chains with a grating of metallic gold bars 2.2.4. Effect of cover index variation with water as a cover medium 2.3. Hot electron generation via guided hybrid modes 2.3.1. Fabrication of the hybrid GMR structure via LIL and lift-off process 2.3.2. Spectroscopic and simulative analysis of hybrid opto-plasmonic structures of different periodicities 2.3.3. Comparative study of photocurrent generation in different plasmonic structures 2.3.4. Polarization dependent response at higher wavelength 2.3.5. Directed self-assembly of gold nanoparticles within grating channels of a dielectric GMR structure supported by titanium dioxide film 2.4. Active Chiral Plasmonics Based on Geometrical Reconfiguration 2.4.1. Chiral 3D assemblies by macroscopic stacking of achiral chain substrates 3. Conclusion 4. Zusammenfassung 5. Bibliography 6. Appendix 6.1. laser interference lithography 6.2. Soft molding 6.3. Determine fill factor of plasmonic lattice 6.4. 2D plasmonic lattice of Au_BSA under strain 6.5. Characterizing order inside a 2D lattice 6.6. Template-assisted colloidal self-assembly 6.7. Out of plane lattice resonance in 1D and 2D lattices 6.8. E-Field distribution at out of plane SLR mode for 1D lattices of various periodicity with AOI 20° 6.9. Refractive index of PDMS and UV-PDMS 6.10. Refractive index measurement for sensing 6.11. Optical constants of TiO2, ma-N 405 photoresist and glass substrate measured from spectroscopic ellipsometry Acknowledgement/ Danksagung Erklärung & Versicherung List of Publication

Photonic crystal enhanced light emitters and their use in improving cancer screening and disease progression monitoring

Screening for and monitoring the progression of cancer remains a complex task in medicine today, further complicated by the variety of both cancer types and treatments. Each patient's response to treatments and cancers is unique, calling for a personalized approach to healthcare. Early detection and correct treatment of cancer are critical for controlling disease progression and improving patient outcomes. This dissertation describes a photonic crystal-based detection and analysis system to improve cancer screening and treatment by increasing sensitivity to low concentrations of cancer biomarkers. There are two main methods of increasing sensitivity: automating detection and analysis to reduce time and user error, and improving coupling efficiency by optimizing photonic crystal design parameters. I address both these methods in this work: the former by increasing sensitivity in the screening for oropharyngeal cancer, and the latter in the design of two new photonic crystals. The first of these photonic crystals is designed for enhanced excitation of multi-colored quantum dots, instead of traditional fluorescent dyes, for the investigation of multiplexed treatment progression monitoring of prostate cancer. The second of these photonic crystals is a design for metamaterial-based photonic crystals that improves coupling efficiency and offers additional design flexibility. This new photonic crystal is interchangeable with the photonic crystal designed to enhance quantum dots but can also be used in a standard microscope setup. The objective is to retain high enhancement while improving coupling to the photonic crystal resonance to increase fluorescent output. This work presents my efforts toward the development of technologies that will enable low-cost, portable screening and disease monitoring to improve outcomes for patients around the world. The ultimate goal is to improve patient access to vital healthcare practices while keeping expenses low and standard of detection high

Porous photonic crystal external cavity laser biosensor

We report the design, fabrication, and testing of a photonic crystal (PhC) biosensor structure that incorporates a porous high refractive index TiO2 dielectric film that enables immobilization of capture proteins within an enhanced surface-area volume that spatially overlaps with the regions of resonant electromagnetic fields where biomolecular binding can produce the greatest shifts in photonic crystal resonant wavelength. Despite the nanoscale porosity of the sensor structure, the PhC slab exhibits narrowband and high efficiency resonant reflection, enabling the structure to serve as a wavelength tunable element of an external cavity laser. In the context of sensing small molecule interactions with much larger immobilized proteins, we demonstrate that the porous structure provides 3.7x larger biosensor signals than an equivalent nonporous structure, while the external cavity laser (ECL) detection method provides capability for sensing picometer-scale shifts in the PhC resonant wavelength caused by small molecule binding. The porous ECL achieves a record high figure of merit for label-free optical biosensors

Active Tuning of LSPR and SLR for Au Nanoring Metasurfaces and Hybrids via Flexible Plasmonics

Recent advances in nanofabrication have stimulated research efforts in the field of flexible plasmonics by integrating functional metasurfaces onto mechanically flexible substrates. In this thesis, we report on the fabrication of flexible metasurfaces composed of gold regular and elliptical nanoring arrays embedded in polydimethylsiloxane (PDMS), using state-of-the-art electron beam lithography and wet-etching transfer techniques. In-situ dark-field reflection spectra are monitored on the flexible systems by implementing a homemade micro-stretcher inside the spectroscope. The feasibility of pattern transfer and reliability of optical measurement are further confirmed by subsequent SEM characterizations on PDMS. The spectral behavior of thin-width nanoring square arrays exhibits a significant shift towards longer wavelengths due to in-situ shape changes under strain. The shape-altering ability is carefully demonstrated through optical/SEM measurements and numerical simulations, which is further understood by a purposed squeezing mechanism. On the other hand, the spectral evolution of elliptical nanorings in square and triangular arrays presents interesting polarization dependence and spectral blueshift under strain. The square array subjected to high strain values exhibits also surface lattice resonances with Fano features due to the coupling between the grating and plasmonic modes. Additionally, we demonstrate Fano resonances in ring-disc-pair hybrid systems on a rigid substrate. The ring-disc-pair system shows significantly enhanced Fano features and surface-enhanced Raman signals with a decreasing gap, predicting well an active spectral tuning once they are transferred onto flexible substrates in future work. In general, this thesis expands the possibilities of conventional gap-altering flexible plasmonics by investigating plasmonic spectral shifts corresponding to NPs shape-altering, surface lattice resonances, and Fano coupling under strain. It provides valuable insights into strain sensing, flexible color displays, and wearable electronics with high sensitivity and selectivity

Nanoplasmonic surface structures for integrated photonics

Nanoplasmonic surfaces are known to be able to alter the localisation and propagation characteristics of light owing to the subwavelength interactions with the metallic elements. The recent improvements of nanolithography and self-assembly techniques have enabled the design of ever smaller and intricate structures with a high precision, allowing for research into more complex nanoplasmonic structures that control light on the nano-scale. Up until now, plasmonic surfaces are mostly operated with out-of-plane excitation which, although well-established and experimentally convenient to perform, has limited potential for on-chip applications. The integration of surface plasmonic structures with photonic waveguides allows for light to be confined to a guiding layer while being kept in interaction along the surface structure without inducing uncontrolled scattering or excessive dissipative loss. In this work, plasmonic surface structures such as plasmonic antennas and array structures that are integrated with a CMOS compatible platform are explored. In particular, a new class of plasmonic surfaces, plasmonic nanogap tilings, are introduced. Remarkably, these simple periodic structures provide a rich physics characterised by many different regimes of operation, including subwavelength surface enhancement, hybrid plasmonic-photonic resonances, transmission stop-bands, resonant back scattering, coupling to out-of-plane radiation and asymmetric transmission. The ability of the nanogap tiling to concentrate the field on the surface is studied in detail as it allows for sensing changes in the dielectric medium on the accessible surface or the inclusion of nonlinear or gain materials to functionalise the device in an integrated setup.Open Acces

Plasmonics and its Applications

Plasmonics is a rapidly developing field that combines fundamental research and applications ranging from areas such as physics to engineering, chemistry, biology, medicine, food sciences, and the environmental sciences. Plasmonics appeared in the 1950s with the discovery of surface plasmon polaritons. Plasmonics then went through a novel propulsion in the mid-1970s, when surface-enhanced Raman scattering was discovered. Nevertheless, it is in this last decade that a very significant explosion of plasmonics and its applications has occurred. Thus, this book provides a snapshot of the current advances in these various areas of plasmonics and its applications, such as engineering, sensing, surface-enhanced fluorescence, catalysis, and photovoltaic devices

Surface enhanced raman spectroscopy for ultra-sensitive detection of energetic materials

The prospect of ultra-sensitive detection of molecular species, particularly those of energetic materials, has prompted the present research initiative. The combination of metal surface nano-technology and Raman spectroscopy has given rise to ‘Surface Enhanced Raman Spectroscopy’ (SERS). This is a very sensitive technique and has proved to be capable of detecting a single molecule. SERS was demonstrated by recording Raman spectra of the sample molecules adsorbed on various specially prepared SER-active surfaces both in the form of a colloidal suspension and on the solid roughened surfaces. Using a gold colloidal suspension, pyridine has been detected down to 10-11 molar (M) concentration. A silver slab was roughened to a dimension of a nano-scale by etching in nitric acid solution to make SER-active surface. Pentaerythritol Tetranitrate (PETN) explosive was detected using this surface after its 10-2 M solution was dropped, dried and washed (of any residue) from the surface. Lithographically engineered silver structures in the form of nanoarrays having a number of silver structures of approximately 106 in a region of 0.1 mm2 have been used for SERS. The major noise contribution to the scattering from impurities in an ordinary glass substrate has been eliminated by replacing glasses as substrates with pure quartz discs. The headspace vapours from peroxide explosives, Triacetone Triperoxide (TATP) and Hexamethylene Triperoxide Diamine (HMTD), were detected at approximately 70 parts per million (ppm) and 0.3 ppm concentrations respectively using a portable commercial Raman Spectrometer. PETN was also detected from its headspace vapour at about 18 parts per trillion (ppt) in spite of it having a much lower vapour pressure. The possibility of desorption of adsorbed molecules from a nano-structured surface by laser irradiation has been demonstrated experimentally with the aim of reusability of SER-active surfaces. Also demonstrated was the enhancement in Raman intensity through resonance Raman effect spectroscopy for the future use in surface enhanced resonance Raman spectroscopy (SERRS)