abstract: III-Nitride nanostructures have been an active area of research recently due to their ability to tune their optoelectronic properties. Thus far work has been done on InGaN quantum dots, nanowires, nanopillars, amongst other structures, but this research reports the creation of a new type of InGaN nanostructure, nanorings. Hexagonal InGaN nanorings were formed using Metal Organic Chemical Vapor Deposition through droplet epitaxy. The nanorings were thoroughly analyzed using x-ray diffraction, photoluminescence, electron microscopy, electron diffraction, and atomic force microscopy. Nanorings with high indium incorporation were achieved with indium content up to 50% that was then controlled using the growth time, temperature, In/Ga ratio and III/N ratio. The analysis showed that the nanoring shape is able to incorporate more indium than other nanostructures, due to the relaxing mechanism involved in the formation of the nanoring. The ideal conditions were determined to be growth of 30 second droplets with a growth time of 1 minute 30 seconds at 770 C to achieve the most well developed rings with the highest indium concentration. / Dissertation/Thesis / M.S. Materials Science and Engineering 2012

Les oligophénylènes constituent une classe de molécules centrale dans la conception de semi-conducteurs organiques pour des applications optoélectroniques. Ces travaux portent sur la synthèse et l’étude approfondie de dérivés linéaires et cycliques du fluorène (un biphényle rigidifié par un pont méthylène), fragment constitutif essentiel dans l’électronique organique. Nous nous intéressons en particulier aux relations structure-propriétés de ces systèmes π-conjugués. Dans une première partie, avec comme cadre le développement de matériaux hôtes pour diodes électroluminescentes (PhOLEDs), nous présentons une étude de la régioisomérie de phényl-fluorènes et de phényl-spirobifluorènes. Ses résultats ont permis la préparation de quatre matériaux hôtes purs hydrocarbures, dimères de spirobifluorène, intégrés dans des PhOLEDs bleues à hautes performances. Dans une seconde partie, nous nous intéressons au domaine récent des nano-anneaux moléculaires, objets cycliques présentant une conjugaison π de nature singulière. Après une revue bibliographique portant sur les cycloparaphénylènes et leurs propriétés, nous présentons nos études concernant plusieurs exemples de leurs analogues pontés : les cycloparafluorènes. / Oligophenylenes constitute a major class of molecules in the design of organic semiconductors for optoelectronics applications. This work involves the synthesis and in-depth study of linear and cyclic derivatives of fluorene (a biphenyl rigidified by a methylene bridge), an essential building block in organic electronics. We focus our attention on the structure-property relationships of these π-conjugated systems. In a first part, within the framework of host materials for phosphorescent organic light-emitting diodes (PhOLEDs), we present a regioisomerism study of phenyl-fluorenes and phenyl-spirobifluorenes. Its results enabled the preparation of four pure hydrocarbon host materials, spirobifluorene dimers, used in high-performance blue PhOLEDs. In a second part, we take interest in the emerging field of molecular nanorings, cyclic objects presenting a singular nature of π-conjugation. After a bibliographical review covering cycloparaphenylenes and their properties, we present our studies regarding several examples of their bridged analogues: cycloparafluorenes.

In the pursuit of economical and rapid fabrication solutions on the micro and nano scale, polymer replication has proven itself to be a formidable technique, which despite zealous development by the research community, remains full of promise. This thesis explores the potential of elastomers in what is a distinctly multidisciplinary field. The focus is on developing innovative fabrication solutions for planar photonic devices and for nanoscale devices in general. Innovations are derived from treatments of master structures, imprintable substrates and device applications. Major contributions made by this work include fully replicated planar integrated optical devices, nanoscale applications for photolithographic standing wave corrugations (SWC), and a biologically templated, optical fiber based, surface-enhanced Raman scattering (SERS) sensor. The planar devices take the form of dielectric rib waveguides which for the first time, have been integrated with long-period gratings by replication. The heretofore unemployed SWC is used to demonstrate two innovations. The first is a novel demonstration of elastomeric sidewall photolithographic mask, which exploits the capacity of elastomers to cast undercut structures. The second demonstrates that the corrugations themselves in the absence of elastomers, can be employed as shadow masks in a directional flux to produce vertical stacks of straight lines and circles of nanowires and nanoribbons. The thesis then closes by conceptually combining the preceding demonstrations of waveguides and nanostructures. An optical fiber endface is em ployed for the first time as a substrate for patterning by replication, wherein the pattern is a nanostructure derived from a biological template. This replicated nanostructure is used to impart a SERS capability to the optical fiber, demonstrating an ultra-sensitive, integrated photonic device realized at great economy of both time and money, with very real potential for mass fabrication.

Unconventional nanofabrication techniques; both those which have been newly developed and those under development, had brought inexpensive, facile, yet high quality means to fabricate nanostructures that have feature sizes of less than 100 nm in industry and academia. This dissertation focuses on developing unconventional fabrication techniques, building studying platforms, and studying the mechanisms behind them. The studies are divided into two main facets and four chapters. The first facet, in Chapter II and Chapter III, deals with the research and development of different nanofabrication techniques and nanostructures. These techniques include litho-synthesis, colloidal lithography, and photolithography. The nanostructures that were fabricated by these techniques include the metal nanoparticle arrays, and the self-assembled CdSe nanoring arrays. At the same time, the dissertation provides mechanisms and models to describe the physical and chemical nature of these techniques. The second area of this study, in Chapter III to Chapter V, presents the applications of these nanostructures in fundamental studies, i.e. the mechanisms of plasmon enhanced fluorescence and photo-oxidation kinetics of CdSe quantum dots, and applications such as molecular sensing and material fabrication. More specifically, these applications include tuning the optical properties of CdSe quantum dots, biomodification of CdSe quantum dots, and copper ion detection using plasmon and photo enhanced CdSe quantum dots. We have successfully accomplished our research goals in this dissertation. Firstly, we were able to tune the emission wavelength of quantum dots, blue-shifted for up to 45 nm, and their surface functionalization with photo-oxidation. A kinetic model to calculate the photo-oxidation rates was established. Secondly, we established a simple mathematical model to explain the mechanism of plasmon enhanced fluoresce of quantum dots. Our calculation and experimental data support the fluorescence resonance energy transfer (FRET) mechanism between quantum dots and the metal nanoparticles. Thirdly, we successfully pattered the CdSe quantum dots (diameter ~4 nm) into nanorings with tunable diameters and annular sizes on different substrates. We also established a physical model to quantitatively explain the mechanism with the forces that involved in the formation of the nanorings.

This thesis presents a combined experimental and computational evaluation of the physical-organic properties of butadiyne-linked porphyrin oligomers. The principal result from the thesis is the synthesis and characterisation of the largest aromatic and antiaromatic systems to date, in the form of an oxidised [6]-porphyrin nanoring, with diameter 2.4 nm. This large electronically coherent system provides insight into the connection between aromatic ring currents and persistent currents in metal and semiconductor mesoscopic rings. Chapter 1 briefly reviews the concepts used in the remainder of the thesis, with a particular focus on aromaticity. In Chapter 2, the barrier to inter-porphyrin torsional rotation in a butadiyne-linked porphyrin dimer is determined computationally and experimentally to be 3 kJ mol^-1. The barrier height is closely related to the resonance delocalisation energy between the porphyrin subunits. In Chapter 3 we show that by oxidising a butadiyne-linked [6]-porphyrin nanoring to its 4+ and 6+ oxidation states, the nanoring becomes antiaromatic and aromatic respectively. In contrast, the neutral oxidation state exhibits only local aromaticity for the six porphyrin units. The 12+ cation can also be generated, and exhibits local antiaromaticity for each porphyrin unit. The characterisation of (anti)aromaticity employs NMR and computational techniques. In Chapter 4, the properties of cation radicals of linear and cyclic porphyrin oligomers are explored. Cations generated by spectroelectrochemistry are measured by optical spectroscopies, and chemically generated radical monocations are examined by cw/pulsed EPR spectroscopies. EPR and optical spectroscopies agree that the dimer monocation radical is fully delocalised, in Robin-Day Class III, whereas the monocations of longer oligomers are localised over 2-3 porphyrin units (Class II). In Chapter 5, photophysical and computational investigations into excited state aromaticity in porphyrin nanorings are presented. The computational results suggest the presence of aromaticity in the triplet excited states, but experiment fails to convincingly demonstrate the effect. Computational results in Chapter 6 show that a butadiyne linked [6]-porphyrin nanoring in which one butadiyne (C≡C-C≡C) is truncated to an alkyne (C≡C) exhibits a reversal of aromaticity and antiaromaticity in its oxidised states, compared to the all-butadiyne linked nanoring, consistent with Hückel's law.

Magnetic nanorings are the object of increasing scientific interest because they possess the vortex (stray field free) state which ensures lower magnetostatic interactions between adjacent ring elements in high packing density memory devices. In addition, they have other potential applications such as single magnetic nanoparticle sensors, microwave-frequency oscillators and data processing. The stabilization of magnetization state, types of domains and domain wall structures depends on the competing energies such as magnetostatic, exchange and anisotropy. The nucleation/ pinning of domain walls depends on the local inhomogeneity in shape such as roughness, notches etc, which play an important role in stabilizing domain configurations that can be controlled by magnetic field/spin polarized current etc. The information gained by the study of magnetization reversal in the nanoring devices could help in understanding the possible stable magnetization states, which can be incorporated into the development of magnetic logic and recording devices in a NR-based architecture. The magnetization reversal and the stable states in the symmetric cobalt nanorings (NRs) attached with nanowires (NWs) (at diametrically opposite points), is studied through magnetoresistance (MR) measurements by application of in-plane magnetic field (H). Here, a strong in-plane shape anisotropy is introduced in cobalt thin films by patterning them into NR and NWs. The presence or absence of a DW in the device is detected utilizing the AMR property of the material, where the presence of DW leads to a decrease in the resistance of the probed section of the device. It is demonstrated that the magnetization reversal of the device with smaller width, proceeds through four distinct magnetization states, one of these is the stabilized vortex state that persists over a field range of 0.730 kOe. The effect of width (from 70 nm to 1 µm) and diameter (from 2 µm to 6 µm) on the switching behavior is demonstrated. The magnetization states observed in the MR measurements are well supported by micromagnetic simulations. A statistical analysis of switching fields in these devices was demonstrated by histogram plot (of switching counts) to understand the repeatability and reproducibility of switching characteristics. In addition, the magnetization reversal of permalloy NR is also studied by MR experiment when two NWs are attached to it in two different configurations. It has been demonstrated that a vortex state can be stabilized if the NWs are attached in a way that they are at an obtuse angle with respect to each other (type-II device) which is not the case if the NWs are attached at diametrically opposite points (type-I device). This occurs because the NWs reverse at different fields as they are asymmetric with respect to applied magnetic field at every angle. The angular dependence study of the magnetization states indicates that the vortex state could be always stabilized in the type-II device irrespective of the direction of in-plane applied magnetic field while it is not the case in type-I device. The experimental observations are in good agreement with micromagnetic simulations performed on similar device structures. Further, in the last part of the thesis, the magnetization reversal of geometrically engineered cobalt NR (of width 80 nm) devices are studied by application of H. Two types of cobalt nanoring devices were fabricated. In type-1 devices the NR is attached with two nanowires (NWs) at diametrically opposite positions. In type-2 devices the NR is attached with one NW, whose other end is attached to a 5 µm x 5 µm square pad. In type-2 device, the pad reverses first, thus causing the generation of a DW at the junction of the nucleation pad and the NW. The device type-2 possesses five distinct magnetization states, one of these is the vortex state. Easy nucleation of domain walls (DWs) results in a decrease of switching field corresponding to the reversal of the nanowire. This leads to an increase in the range of fields, where the vortex state exists. In addition, angular dependence of the switching behavior indicates that the vortex state can be stabilized at all in-plane orientations of H. This occurs because of the fact that symmetry was broken due to the presence of single domain wall pinning center which was the junction of the NR and NW. The results of our micromagnetic simulations are in a good agreement with the experimental results. These results are important to understand the role of NWs which allows the formation of vortex state at every angle of the in-plane H. In type-1 device, the simulation shows that when the field is applied at any angle away from the axis of the NW, the vortex state cannot be stabilized. The width dependent study of switching fields indicates, that the switching fields decrease with increasing the width of NR devices due to a reduction of the demagnetization field.