Organic molecules such as porphyrins and alkanethiols are currently being investigated for applications such as sensors, light-emitting diodes and single electron transistors. Porphyrins are stable, highly conjugated compounds and the choice of metal ion and substituents bound to the macrocycle as well as other effects such as chemical surrounding and cluster size modulate the electronic and photonic properties of the molecule. Porphyrins and their derivatives are relatively non-toxic and their very rich photo- and electro-chemistry, and small HOMO-LUMO gaps make them outstanding candidates for use in molecularly-enhanced electronic applications. For these studies, self-assembled tri-pyridyl porphyrin thiol derivatives have been fully characterized on Au(111) surfaces. A variety of surface characterization techniques such as Atomic Force Microscopy (AFM), Scanning Tunneling Microscopy (STM), FT-IR spectroscopy and X-ray photoelectron spectroscopy (XPS) have been implemented in order to obtain information regarding the attachment orientation based on the angle and physical height of the molecule, conductivity which is determined based on the apparent height and current-voltage (I-V) measurements of the molecule, conductance switching behavior due to conformational or other effects as well as the stability of the molecular ensembles. Specifically, the transport properties of free base and zinc coordinated tri-pyridyl porphyrin thiol molecular islands inserted into a dodecanethiol matrix on Au(111) were investigated using STM and cross-wire inelastic electron tunneling spectroscopy (IETS). The zinc porphyrin thiol islands observed by STM exhibited reversible bias induced switching at high surface coverage due to the formation of Coulomb islands of ca. 10 nm diameter driven by porphyrin aggregation. Low temperature measurements (~ 4 K) from crossed-wire junctions verified the appearance of a Coulomb staircase and blockade which was not observed for single molecules of this compound or for the analogous free base. Scanning probe lithography via nanografting has been implemented to directly assemble nanoscale patterns of zinc porphyrin thiols and 16-mercapotohexadecanoic acid on Au surfaces. Matrix effects during nanopatterning including solvent and background SAMs have been investigated and ultimately ~ 10 nm islands of zinc porphyrins have been fabricated which is the optimal size for the observed switching effect.

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The Complementary Metal-Oxide-Semiconductor (CMOS) industry has seen tremendous developments over the past several decades and state-of-the-art fabrication technology has likewise been developed. This fabrication technology develops Photonic Integrate Circuits (PIC) which can guide, split, and modulate photonic waves within a small chip scale. On-chip optical phased arrayed waveguides that operate at high power overcome the current limitations of some conventional applications. This paper discusses two applications of on-chip optical waveguide systems: optical phased array (OPA)-based Light Detection and Range (LiDAR) and waveguide array Dielectric Laser Accelerator (DLA). Both the LiDAR and DLA structures require similar properties to achieve optimized performance. These properties are as follows: capability to handle high power, the ability to split the high power evenly through several waveguide branches and distribute the same degree of optical phase on each branch at specific spatial locations, efficient designs of active phase-tuning structures, and the ability to re-combine several waveguide branches into the sub-wavelength pitch spacing array without crosstalk. Additionally, both structures must resolve specific fabrication challenges on each waveguide component. To address these issues, this paper discusses the theoretical reviews of OPA, the Laser-Induced Damage Threshold (LIDT) of optical waveguide materials, and techniques to reduce crosstalk in sub-wavelength pitch size arrays, such as extreme skin-depth (e-skid) waveguides and propagation constant mismatched waveguides. We propose optimized designs for both OPA-based LiDAR and waveguide array DLA with passive and active devices, respectively, and explain the optimized parameters and its simulation results for each component from the full layout of devices. Furthermore, we discuss the fabrication process of the devices and show the resolutions of fabrication challenges, such as trapping void gaps in an e-skid array structure, writing errors of electron beam lithography of large dense patterns, and silicon nitride to silicon hybrid waveguide pattern alignments. Next, we show the experimental setups and the measurement results from the fabricated OPA devices and analyze the results. Finally, this paper concludes the research of the proposed devices and proposes more designs for both OPA-based LiDAR and waveguide arrayed DLA structures that can further increase increase its performance.<br>

Diese Arbeit befasst sich mit der Nanostrukturierung von magnetischen Schichtsystemen mit Tunnelmagnetowiderstandseffekt (TMR-Effekt), welche in der Form von Nanosäulen in magnetoresistiven Speichern (MRAM) eingesetzt werden. Solche Nanosäulen können zukünftig ebenfalls als Nanoemitter von Mikrowellensignalen eine Rolle spielen. Dabei wird von der Auswahl eines geeigneten TMR-Schichtsystems mit einer MgO-Tunnelbarriere über die Präparation der Nanosäulen mit Seitenisolierung bis hin zum Aufbringen der elektrischen Zuleitungen eine komplette Prozesskette entwickelt und optimiert. Die Strukturen werden mittels optischer Lithographie und Elektronenstrahllithographie definiert, die anschließende Strukturübertragung erfolgt durch Ionenstrahlätzen (teilweise reaktiv) sowie durch Lift-off. Rückmeldung über Erfolg oder Probleme bei der Strukturierung geben Transmissionselektronenmikroskopie (teilweise mit Zielpräparation per Ionenfeinstrahl, FIB), Rasterelektronenmikroskopie sowie die Lichtmikroskopie. Es können so TMR-Nanosäulen mit minimalen Abmessungen von bis zu 69 nm x 71 nm hergestellt werden, von denen Nanosäulen mit Abmessungen von 65 nm x 87 nm grundlegend magneto-elektrisch charakterisiert worden sind. Dies umfasst die Bestimmung des TMR-Effektes und des Widerstandes der Tunnelbarriere (RA-Produkt). Weiterhin wurde das Verhalten der magnetischen Schichten bei größeren Magnetfeldern bis +-200mT sowie das Umschaltverhalten der magnetisch freien Schicht bei verändertem Winkel zwischen magnetischer Vorzugsachse des TMR-Elementes und dem äußeren Magnetfeld untersucht. Der Nachweis des Spin-Transfer-Torque Effektes an den präparierten TMR-Nanosäulen ist im Rahmen dieser Arbeit nicht gelungen, was mit dem zu hohen elektrischen Widerstand der verwendeten Tunnelbarriere erklärt werden kann. Mit dünneren Barrieren konnte der Widerstand gesenkt werden, allerdings führt ein Stromfluss durch diese Barrieren schnell zur Degradation der Barrieren. Weiterführende Arbeiten sollten das Ziel haben, niederohmige und gleichzeitig elektrisch belastbare Tunnelbarrieren in einem entsprechenden TMR-Schichtsystem abzuscheiden. Eine erste Auswahl an Ansatzpunkten dafür aus der Literatur wird im Ausblick gegeben.:Einleitung I Grundlagen 1 Spinelektronik und Magnetowiderstand 1.1 Der Elektronenspin – Grundlage des Magnetismus 1.2 Magnetoresistive Effekte 1.2.1 AnisotroperMagnetowiderstand 1.2.2 Riesenmagnetowiderstand 1.2.3 Tunnelmagnetowiderstand 1.3 Spin-Transfer-Torque 1.4 Anwendungen 1.4.1 Festplattenleseköpfe 1.4.2 Magnetoresistive Random AccessMemory (MRAM) 1.4.3 Nanooszillatoren für drahtlose Kommunikation 2 Grundlagen der Mikro- und Nanostrukturierung 2.1 Belacken 2.2 Belichten 2.2.1 Optische Lithographie 2.2.2 Elektronenstrahllithographie 2.3 Entwickeln 2.4 Strukturübertragung 2.4.1 Die Lift-off Technik 2.4.2 Ätzen 2.5 Entfernen der Lackmaske 2.6 Reinigung 2.6.1 Quellen von Verunreinigungen 2.6.2 Auswirkungen von Verunreinigungen 2.6.3 Entfernung von Verunreinigungen 2.6.4 Spülen und Trocknen der Probenoberfläche 3 Ionenstrahlätzen 3.1 Physikalisches Ätzen – Sputterätzen 3.2 Reaktives Ionenstrahlätzen – RIBE 3.3 Anlagentechnik 3.3.1 Parameter 3.3.2 Homogenität 3.3.3 Endpunktdetektion II Ergebnisse und Diskussion 4 TMR-Schichtsysteme 4.1 Prinzipielle Schichtfolge 4.2 Verwendete TMR-Schichtsysteme 4.3 Rekristallisation von Kupfer 4.4 Formierung der TMR-Schichtsysteme 4.4.1 Antiferromagnetische Kopplung an PtMn 4.4.2 Rekristallisation an der MgO-Barriere 4.5 Anpassung der MgO-Schicht – TMR-Effekt und RA-Produkt 4.6 Magnetische Charakterisierung 5 Probendesign 5.1 Beschreibung der vier lithographischen Ebenen 5.2 Layout für statische und dynamischeMessungen 5.2.1 Geometrie 5.2.2 Anforderungen für die Hochfrequenzmessung 5.3 Layout für Zuverlässigkeitsmessungen 5.3.1 Geometrie 5.3.2 Voraussetzungen für die Funktion 5.4 Chiplayout 5.4.1 Zusatzstrukturen 5.4.2 Anordnung der Elemente 6 Fertigung eines Maskensatzes für die optische Lithographie 6.1 Vorbereitung desMaskenrohlings 6.2 Strukturierung mittels Elektronenstrahllithographie 6.3 Ätzen der Chromschicht 7 Ergebnisse und Diskussion der Probenpräparation 7.1 Definition der Grundelektrode 7.1.1 Freistellen der Grundelektrode 7.1.2 Gratfreiheit der Grundelektrode 7.1.3 Oberflächenqualität nach der Strukturierung 7.2 Präparation der magnetischen Nanosäulen 7.2.1 Aufbringen einer Ätzmaske 7.2.2 Ionenstrahlätzen der TMR-Nanosäule 7.2.3 Abmessungen der präparierten Nanosäulen 7.3 Vertikale Kontaktierung 7.3.1 Seitenwandisolation 7.3.2 Freilegen der Kontakte 7.3.3 Aufbringen der elektrischen Zuleitungen 7.4 Die komplette Prozesskette und Ausbeute 8 Magneto-elektrische Charakterisierung 8.1 Messung des Tunnelmagnetowiderstandes 8.2 Stabilität der magnetischen Konfiguration 8.3 Spin-Transfer-Torque an TMR-Nanosäulen 9 Zusammenfassung und Ausblick Literaturverzeichnis / This thesis deals with the fabrication of nanopillars with tunnel magnetoresistance effect (TMR-effect), which are used in magnetoresistive memory (MRAM) and may be used as nanooscillators for future near field communication devices. Starting with the selection of a suitable TMR-layer stack with MgO-tunnel barrier, the whole process chain covering the fabrication of the nanopillars, sidewall isolation and preparation of the supply lines on top is developed and optimised. The structures are defined by optical and electron beam lithography, the subsequent patterning is done by ion beam etching (partially reactive) and lift-off. Techniques providing feedback on the nanofabrication are transmission electron microscopy (partially with target preparation by focused ion beam, FIB), scanning electron microscopy and optical microscopy. In this way nanopillars with minimal dimensions reaching 69 nm x 71 nm could be fabricated, of which nanopillars with a size of 65 nm x 87 nm were characterized fundamentally with respect to their magnetic and electric properties. This covers the determination of the TMR-effect and the resistance of the tunnel barrier (RA-product). In addition, the behaviour of the magnetic layers under higher magnetic fields (up to +-200mT) and the switching behaviour of the free layer at different angles between the easy axis of the TMR-element and the external magnetic field were investigated. The spin transfer torque effect could not be detected in the fabricated nanopillars due to the high electrical resistance of the tunnel barriers which were used. The resistance could be lowered by using thinner barriers, but this led to a quick degradation of the barrier when a current was applied. Continuative work should focus on the preparation of tunnel barriers in an appropriate TMR-stack being low resistive and electrically robust at the same time. A first selection of concepts and ideas from the literature for this task is given in the outlook.:Einleitung I Grundlagen 1 Spinelektronik und Magnetowiderstand 1.1 Der Elektronenspin – Grundlage des Magnetismus 1.2 Magnetoresistive Effekte 1.2.1 AnisotroperMagnetowiderstand 1.2.2 Riesenmagnetowiderstand 1.2.3 Tunnelmagnetowiderstand 1.3 Spin-Transfer-Torque 1.4 Anwendungen 1.4.1 Festplattenleseköpfe 1.4.2 Magnetoresistive Random AccessMemory (MRAM) 1.4.3 Nanooszillatoren für drahtlose Kommunikation 2 Grundlagen der Mikro- und Nanostrukturierung 2.1 Belacken 2.2 Belichten 2.2.1 Optische Lithographie 2.2.2 Elektronenstrahllithographie 2.3 Entwickeln 2.4 Strukturübertragung 2.4.1 Die Lift-off Technik 2.4.2 Ätzen 2.5 Entfernen der Lackmaske 2.6 Reinigung 2.6.1 Quellen von Verunreinigungen 2.6.2 Auswirkungen von Verunreinigungen 2.6.3 Entfernung von Verunreinigungen 2.6.4 Spülen und Trocknen der Probenoberfläche 3 Ionenstrahlätzen 3.1 Physikalisches Ätzen – Sputterätzen 3.2 Reaktives Ionenstrahlätzen – RIBE 3.3 Anlagentechnik 3.3.1 Parameter 3.3.2 Homogenität 3.3.3 Endpunktdetektion II Ergebnisse und Diskussion 4 TMR-Schichtsysteme 4.1 Prinzipielle Schichtfolge 4.2 Verwendete TMR-Schichtsysteme 4.3 Rekristallisation von Kupfer 4.4 Formierung der TMR-Schichtsysteme 4.4.1 Antiferromagnetische Kopplung an PtMn 4.4.2 Rekristallisation an der MgO-Barriere 4.5 Anpassung der MgO-Schicht – TMR-Effekt und RA-Produkt 4.6 Magnetische Charakterisierung 5 Probendesign 5.1 Beschreibung der vier lithographischen Ebenen 5.2 Layout für statische und dynamischeMessungen 5.2.1 Geometrie 5.2.2 Anforderungen für die Hochfrequenzmessung 5.3 Layout für Zuverlässigkeitsmessungen 5.3.1 Geometrie 5.3.2 Voraussetzungen für die Funktion 5.4 Chiplayout 5.4.1 Zusatzstrukturen 5.4.2 Anordnung der Elemente 6 Fertigung eines Maskensatzes für die optische Lithographie 6.1 Vorbereitung desMaskenrohlings 6.2 Strukturierung mittels Elektronenstrahllithographie 6.3 Ätzen der Chromschicht 7 Ergebnisse und Diskussion der Probenpräparation 7.1 Definition der Grundelektrode 7.1.1 Freistellen der Grundelektrode 7.1.2 Gratfreiheit der Grundelektrode 7.1.3 Oberflächenqualität nach der Strukturierung 7.2 Präparation der magnetischen Nanosäulen 7.2.1 Aufbringen einer Ätzmaske 7.2.2 Ionenstrahlätzen der TMR-Nanosäule 7.2.3 Abmessungen der präparierten Nanosäulen 7.3 Vertikale Kontaktierung 7.3.1 Seitenwandisolation 7.3.2 Freilegen der Kontakte 7.3.3 Aufbringen der elektrischen Zuleitungen 7.4 Die komplette Prozesskette und Ausbeute 8 Magneto-elektrische Charakterisierung 8.1 Messung des Tunnelmagnetowiderstandes 8.2 Stabilität der magnetischen Konfiguration 8.3 Spin-Transfer-Torque an TMR-Nanosäulen 9 Zusammenfassung und Ausblick Literaturverzeichnis

Since its inception, the field of nonlinear optics has only increased in importance as a result of a growing number of applications. The efficiency of all parametric nonlinear optical processes is limited by challenges associated with phase-matching requirements. To address this constraint, a variety of approaches, such as quasi-phase-matching, birefringent phase matching, and higher-order-mode phase matching have historically been used to phase-match interactions. However, the methods demonstrated to date suffer from the inconvenience of only being phase-matched for one specific arrangement of beams, typically co-propagating along the same axis. This stringency of the phase-matching requirement results in cumbersome optical configurations and large footprints for integrated devices. In this thesis, we show that phase-matching requirements in parametric nonlinear optical processes may be satisfied for all orientations of input and output beams when using zero-index media: a condition of omnidirectional phase matching. To validate this theory, we perform experimental demonstrations of phase matching for five separate FWM beam configurations to confirm this phenomenon. Our measurements constitute the first experimental observation of the simultaneous generation of a forward- and backward-propagating signal with respect to the pump beams in a medium longer than a free-space optical wavelength, allowing us to determine the coherence length of our four-wave-mixing process. Our demonstration includes nonlinear signal generation from spectrally distinct counter-propagating pump and probe beams, as well as the excitation of a parametric process with the probe beam's wave vector orthogonal to the wave vector of the pump beam. By sampling all of these beam configurations, our results explicitly demonstrate that the unique properties of zero-index media relax traditional phase-matching constraints, and provide strong experimental evidence for the existence of omnidirectional phase matching in zero-index media. This property can be exploited to facilitate nonlinear interactions and miniaturize nonlinear devices, and adds to the established exceptional properties of low-index materials.

<p>Plasmonics with the capability to harness electromagnetic waves at a nanoscale can be utilized for multitude of applications in ultra-compact miniature optical devices. Plasmonic metasurfaces which are artificially designed sub-wavelength structures have gained unprecedented interest in being able to engineer and effectively modulate the amplitude and phase of the incident wave. Introducing randomness to such plasmonic metasurfaces can also advance possibilities for extraordinary wave manipulation. Hence, by exploiting the plasmonic response of the ordered and disordered metasurfaces, we can design high performance devices for nanoscale optics.</p> <p>Aiming to provide a holistic solution to the current device limitations and bio-compatibility, my research focuses on non-toxic and environment-friendly coloration using plasmonic disordered metasurfaces. These structures generate a broad range of long-lasting colors in reflection that can be applied to real-life artistic or technological applications with a spatial resolution on the order of 0.3 mm or less. Moreover, my research also deals with the possibility of even concentrating energy in the smallest phase-space volume in optics in the form of coherent radiation through designing nanolasers. The study of carrier dynamics and photophysics of the gain media can be extremely beneficial towards the practicability of these lasers. This work elucidates the evolution of different competing mechanisms for coherent lasing. The dynamic study and experimental demonstration of these devices and respective materials can therefore provide a novel aspect to fundamental and applied research.</p>

Nanomaterials display interesting physical and chemical properties depending on their shape, size and composition. Self assembly is an intriguing route to producing nanomaterials with controllable compositions and morphologies. DNA has been used to guide the self assembly of materials, resulting in: (1) metal nanowires; (2) metal or semiconductor nanorods; (3) carbon nanotubes; and (4) semiconductor, metal or biological nanoparticles. My work expands the range of DNA templated nanomaterials and develops novel ways of using DNA to pattern nanostructures on surfaces. I have performed the first synthesis of silver nanorods on single stranded DNA, an attractive material for localizing DNA coupled nanostructures through hybridization. I have demonstrated an ionic surface masking protocol to reduce ~70% of non specific metal deposition (a pervasive problem) during electroless plating of DNA with silver or copper. I have designed and constructed discrete three branched DNA junctions as scaffolding for self assembling three terminal, individually gateable nanotransistors. I have labeled these DNA structures with single streptavidin molecules, as a model for the placement of semiconductor nanocrystals at the junctions. Moreover, I have shown selective silver and copper plating of branched DNA constructs, with crystallinity that depends on plating conditions. I have fabricated DNA templated nickel nanostructures on surfaces and demonstrated their reversible interaction with a histidine labeled protein, as a model system for patterning histidine tagged nanostructures on surfaces. Previous methods were limited to decorating DNA scaffolds using streptavidin-biotin interactions. Finally, I have developed DNA shadow nanolithography, which uses angled thin film deposition and anisotropic etching to transfer patterns of surface aligned DNA onto substrates as nanoscale trenches with linewidths <30 nm. Nanotrenches can be post processed with microfabrication methods to modify their properties; I have constructed metal lines and nanopores from such trenches. This dissertation summarizes the principles and methods for synthesis and characterization of DNA templated nanomaterials. These biologically templated constructs may be useful in the fabrication of self assembled chemical and electrical sensors, and as structural materials for nanofabrication and nanopatterning on surfaces.

<p dir="ltr">Metamaterials are artificially engineered nanoscale systems with a three-dimensional repetitive arrangement of certain components, and present exceptional optical properties for applications in nanophotonics, solar cells, plasmonic devices, and more. Self-assembled oxide-metal vertically aligned nanocomposites (VANs), with metallic phase as nanopillars embedded in the matrix oxide, have been recently proposed as a promising candidate for metamaterial applications. However, precise microstructural control and the structure-property relationships in VANs are still in high demand. Thus, by employing multiple approaches for structural design, this dissertation attempts to investigate the mechanisms of nanostructure evolutions and the corresponding optical responses.</p><p dir="ltr">In this dissertation, the precise control over the nanostructures has been demonstrated through morphology tuning, nanopillar orderings, and strain engineering. Firstly, Au, a well-known plasmonic mediator, has been selected as the metallic phase that forms nanopillars. Based on the previously proposed strain compensation model which describes the basic formation mechanism of VAN morphology, two oxides were then considered: La_0.7Sr_0.3MnO₃(LSMO) and CeO₂. In the first two chapters of this dissertation, LSMO was considered due to its similar lattice (a_LSMO= 3.87 Å, a_Au= 4.08 Å) and its enormous potential in nanoelectronics and spintronics. Deposited on SrTiO₃ (001) substrate through pulsed laser deposition (PLD), LSMO-Au nanocomposites exhibit ideal VAN morphology as well as promising hyperbolic dispersions in response to the incident illuminations. By substrate surface treatment of annealing at 1000°C, and variation of STO substate orientations from (001), to (111) and (110), the improved and tunable in-plan orderings of Au nanopillars have been successfully achieved. In the third chapter, a new oxide-metal VAN system of <a href="" target="_blank">CeO₂</a>-Au (a_CeO2= 5.411 Å, and a_CeO2/= 3.83 Å) has been deposited. The intriguing 45° rotated in-plan epitaxy presents an unexpected update to the strain compensation model, and tuning of Au morphology from nanopillars, nanoantennas, to nanoparticles also shows an effective modulation of the LSPR responses. COMSOL simulations have been exploited to reveal the relationships between Au morphologies and optical responses. In the last chapter, the two VAN systems of LSMO-Au and CeO₂-Au have been combined to form a complex layered VAN thin film. Investigations into the strain states, the nature of complex interfaces, and the according hybrid properties, show dramatic possibilities for further strain engineering. In summary, this dissertation has provided multiple routes for highly tailorable oxide-metal nanocomposite designs. And the two proposed material systems present great potential in optical metamaterial applications including biosensors, photovoltaics, super lenses, and more.</p>

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