Thesis (Ph. D.)--University of Missouri--Rolla, 2007. / Vita. The entire thesis text is included in file. Title from title screen of thesis/dissertation PDF file (viewed December 6, 2007) Includes bibliographical references.

Thesis (M.S.)--State University of New York at Binghamton, Department of Mechanical Engineering, 2006. / Includes bibliographical references.

Advanced optical technologies profoundly impact countless aspects of modern life. At the heart of these technologies is the manipulation of light using optical materials. Currently, optical technologies are created using naturally occurring materials. However, a new and exciting approach is to use nanomaterials for technology development. Nanomaterials are artificially constructed material systems with precisely engineered nanostructures. Many technological revolutions await the development of new nanoscale fabrication methods that must provide the ability to control, enhance, and engineer the optical properties of these artificial constructs. This thesis responds to the challenges of nanofabrication by examining glancing angle deposition (GLAD) and improving its optical-nanomaterial fabrication capabilities. GLAD is a bottom-up nanotechnology fabrication method, recognized for its flexibility and precision. The GLAD technique provides the ability to controllably fabricate high-surface-area porous materials, to create structurally induced optical-anisotropy in isotropic materials, and to tailor the refractive index of a single material. These three advantages allow GLAD to assemble optical nanomaterials into a range of complex one-dimensional photonic crystals (PCs). This thesis improves upon previous GLAD optical results in a number of important areas. Multiple optical measurement and modeling techniques were developed for GLAD-fabricated TiO2 nanomaterials. The successful characterization of these nanomaterials was extended to engineer PC structures with great precision and a superior degree of control. The high surface area of basic PC structures was exploited to fabricate an optimized colourimetric sensor with excellent performance. This colourimetric sensor required no power source and no read-out system other than the human eye, making it a highly attractive sensing approach. Incorporating engineered defects into GLAD-fabricated PCs established a new level of design sophistication. Several PC defect structures were examined in detail, including spacing layers and index profile phase-shifts. Remarkable control over defect properties was achieved and intriguing polarization-sensitive optical effects were investigated in anisotropic defect layers. The success of these results demonstrates the precision and flexibilty of the GLAD technique in fabricating optical nanomaterials and advanced photonic devices. / Micro-Electro-Mechanical Systems (MEMS) and Nanosystems

Nanotechnology is a term used to describe nanometer scaled systems. This thesis presents various nanomaterials and systems for the investigation of biologically relevant analytes in general, and in particular for their detection, decontamination, or destruction. The validation of short peptide fragments as models for protein aggregation is initially discussed through applying spectroscopic and microscopic techniques to Langmuir monolayer surface chemistry. Following this validation, the use of nanogold as a photoablative material for the destruction of aggregated protein is investigated. Subsequently, the versatility of nanotechnology is shown by investigating a different form of nanogold; namely, gold quantum dots and the interesting phenomenon that arise when dealing with materials on a nanoscale. Experiments involving a complex between these gold quantum dots and an antibody are performed for the detection of an immunoglobulin in solution. The power of this analytical technique is highlighted by the capability of detecting the analyte at nanomolar concentrations. Finally, a limitation-the multiple synthetic steps necessary for imparting biological activity-- of quantum dots is addressed: a single step reaction is studied that allows for direct stabilization and conjugation of quantum dots with proteins and enzymes. As a representative application of the above mentioned procedure, the detection and decontamination of an organophosphorus compound is explored. In general, methods for overcoming limitations of nanoparticles and nanocrystals are discussed.

Thesis (Ph. D.)--University of Texas at Austin, 2006. / Vita. Includes bibliographical references.

The present work is focused on the nucleation and growth mechanism of carbon nanotubes (CNT) that we have studied through different field emission techniques (FEM, FIM and atom-probe (PFDMS)). Reaction conditions associated with the CVD synthesis method were modeled inside the microscope aiming at studying nucleation phenomena at high resolution. The interaction between different metals (Fe, Co, Ni, conditioned as sharp tips) and gases (acetylene, ethylene and ethanol) was analyzed operando at high temperatures (500–900K), with the aim of reproducing growth conditions during the imaging process. Ni was, in the end, the only metal studied, due to the poor quality of images acquired from Co and Fe. Aimed at reproducing the conditioning step of the catalyst often observed in CVD protocols, a first study showed that the crystal adopts a polyhedral morphology at the working temperature (873K) in an hydrogen atmosphere or under Ultra-High-Vacuum conditions, by the extension of dense crystal planes like {111} or {100}. The presence of hydrogen in the chamber does not seem to present any influence on the final crystal morphology at temperatures above 600K. When exposed to a carbon-containing gas, nickel crystals present two distinct behaviors following the temperature region that is explored. At temperatures below ~623K, exposing Ni to ethylene or acetylene leads to the formation of a stable and poorly structured nickel carbide layer. The superficiality of this carbide is proven by the ease of its physical (by increasing the electrical field) or chemical (exposure to hydrogen or oxygen) evacuation. These three treatments initiate a clean-off phenomenon that evacuates the carbide layer. Reproducing these experiments in the atom-probe confirmed the carbidic nature of the surface as NiCy compounds were collected. At temperatures above 623K, the carbide layer (formed by exposing Ni to the same gases) becomes unstable. Its formation is related to a transition period that precedes the nucleation of graphenes on the surface. The Ni crystal undergoes a massive morphological transformation when acetylene is introduced in the chamber at 873K. This phenomenon is induced by the presence of carbon on the surface which adsorbs so strongly on step sites that it provokes their creation. Carbon also induces a considerable enhancement of Ni atoms mobility that allows for this transition to occur. Once the new morphology is attained, nucleation of graphenes is observed to start on the extended and carbon-enriched step-containing crystal planes. By reproducing these experiments in the atom-probe, a high surface concentration of carbon dimers and trimers was observed. A kinetic study of their formation was thus achieved and showed that they were formed on the surface by the recombination of Cad. Their potential role as building-blocks of the CNT growth process (which had previously been proposed following theoretical considerations) is thus suggested on the basis of experimental results for the first time. Two critical surface concentrations are highlighted in the present work. The first one is needed for the formation of carbon dimers and trimers and the second one has to be attained, during the morphological transformation, before the onset of graphene nucleation, probably providing a sufficient growth rate of the graphitic nuclei and allowing them to attain their critical size before their decomposition. Finally, the observation of rotational circular patterns, most probably related to carbon nanotubes, suggests that CNT growth (and not only graphene nucleation) occurred episodically in our conditions, confirming the validity of our model.

In recent years, the aim of supramolecular syntheses is not only the creation of particular structures but also the introduction of specific functions in these supramolecules. The present work describes the use of the ionic self-assembly (ISA) route to generate nanostructured materials with integrated functionality. Since the ISA strategy has proved to be a facile method for the production of liquid-crystalline materials, we investigated the phase behaviour, physical properties and function of a variety of ISA materials comprising a perylene derivative as the employed oligoelectrolyte. Functionality was introduced into the materials through the use of functional surfactants. <br><br> In order to meet the requirements to produce functional ISA materials through the use of functional surfactants, we designed and synthesized pyrrole-derived monomers as surfactant building blocks. Owing to the presence of the pyrrole moiety, these surfactants are not only polymerizable but are also potentially conductive when polymerized. We adopted single-tailed and double-tailed N-substituted pyrrole monomers as target molecules. Since routine characterization analysis of the double-tailed pyrrole-containing surfactant indicated very interesting, complex phase behaviour, a comprehensive investigation of its interfacial properties and mesophase behavior was conducted. The synthesized pyrrole-derived surfactants were then employed in the synthesis of ISA complexes. The self-assembled materials were characterized and subsequently polymerized by both chemical and electrochemical methods. The changes in the structure and properties of the materials caused by the in-situ polymerization were addressed.<br><br> In the second part of this work, the motif investigated was a property rather than a function. Since chiral superstructures have obtained much attention during the last few years, we investigated the possibility of chiral ISA materials through the use of chiral surfactants. Thus, the work involved synthesis of novel chiral surfactants and their incorporation in ISA materials with the aim of obtaining ionically self-assembled chiral superstructures. <br><br> The results and insights presented here suggest that the presented synthesis strategy can be easily extended to incorporate any kind of charged tectonic unit with desired optical, electrical, or magnetic properties into supramolecular assemblies for practical applications. / Supramolekulare Chemie zielt auf den Aufbau großer Moleküle und neuer Materialien aus kleineren Einheiten. Durch supramolekulare Wechselwirkungen d.h. nicht-kovalente Bindungen, können definierte Ordnungen von Molekülverbänden in Größen von mehreren 100 Mikrometern hergestellt werden. Diese Wechselwirkungen und die daraus resultierenden Anordnungen von Molekülen bestimmen die für Anwendungen relevanten makroskopischen Materialeigenschaften. <br><br> Es gibt viele verschiedene Wechselwirkungen, die in der Supramolekularen Chemie angewendet werden können. Eine davon ist die ionische Wechselwirkung, die in dieser Arbeit als Triebkraft für die Herstellung supramolekularer Materialien verwendet wird. Diese Strategie wurde vor kurzem ISA (Ionic-Self-Assembly, d.h. Ionische Selbsorganisation) genannt. <br><br> Die vorliegende Arbeit beschäftigt sich mit der Herstellung funktioneller Nanomaterialen durch die Anwendung der ISA-Strategie. Da sich die ISA-Strategie als einfache Methode für die Produktion von Flüssigkristallen herausstellte, untersuchten wir die Eigenschaften vieler ISA-Materialen, die einen Farbstoffbaustein integriert haben. Die Funktion der Materialien wurde hierbei durch die Verwendung funktioneller Tenside geschaffen. Um die Anforderungen für die Produktion funktioneller ISA-Materialen durch die Nutzung funktioneller Tenside sicherzustellen, wurden Pyrrol-Monomere als Tenside hergestellt. Durch die Pyrrol-Einheiten sind die Tenside polymerisierbar und zeigen danach Potential für Leitfähigkeit. <br><br> Es wurden Pyrrol-Tenside sowohl mit Einzel- als auch mit Doppelketten synthetisiert. Da die Standardcharakterisierung des Doppelketten-Tensids ein interessantes Phasenverhalten zeigte, wurden umfassende Untersuchungen der Grenzflächeneigenschaften und des mesophasen Verhaltens durchgeführt. Beide Tenside wurden dann in der Produktion von ISA-Materialien verwendet. Die hergestellten Materialen wurden charakterisiert und konnten durch die Pyrrol-Einheit sowohl chemisch als auch elektrochemisch polymerisiert werden. Die aus dieser Polymerisierung resultierenden Änderungen der Eigenschaften, Struktur und Function der Materialen wurden ebenfalls untersucht. <br><br> Der zweite Teil dieser Arbeit klärt Nutzungsmöglichkeiten chiraler Tenside für die Herstellung chiraler ISA-Strukturen. Obwohl Chiralität keine eigentliche Funktion sondern eine Eigenschaft ist, haben chirale Strukturen in den letzten Jahren viel Aufmerksamkeit bekommen. Deshalb wurden, mit dem Ziel chirale ISA-Strukturen zu erhalten, neue chirale Tenside hergestellt und diese als Bausteine in ISA-Materialien benutzt.<br><br> Die mit dieser Arbeit gewonnenen Ergebnisse und neuen Einsichten zeigen, dass die ISA-Strategie leicht erweitert werden kann, um jede Art von Bausteine zu integrieren. Dadurch können nanostukturierte Materialien mit gewünschten spezifischen optischen, elektrischen oder elektromagnetischen Eigenschaften für praktische Anwendungen geschaffen werden.

The functional properties of nanoparticles highly depend on the surface morphology of the particles, so precise measurements of a particle's morphology enable reliable characterizing of the nanoparticle's properties. Obtaining the measurements requires image analysis of electron microscopic pictures of nanoparticles. Today's labor-intensive image analysis of electron micrographs of nanoparticles is a significant bottleneck for efficient material characterization. The objective of this dissertation is to develop automated morphology analysis methods. Morphology analysis is comprised of three tasks: separate individual particles from an agglomerate of overlapping nano-objects (image segmentation); infer the particle's missing contours (shape inference); and ultimately, classify the particles by shape based on their complete contours (shape classification). Two approaches are proposed in this dissertation: the divide-and-conquer approach and the convex shape analysis approach. The divide-and-conquer approach solves each task separately, taking less than one minute to complete the required analysis, even for the largest-sized micrograph. However, its separating capability of particle overlaps is limited, meaning that it is able to split only touching particles. The convex shape analysis approach solves shape inference and classification simultaneously for better accuracy, but it requires more computation time, ten minutes for the biggest-sized electron micrograph. However, with a little sacrifice of time efficiency, the second approach achieves far superior separation than the divide-and-conquer approach, and it handles the chain-linked structure of particle overlaps well. The capabilities of the two proposed methods cannot be substituted by generic image processing and bio-imaging methods. This is due to the unique features that the electron microscopic pictures of nanoparticles have, including special particle overlap structures, and large number of particles to be processed. The application of the proposed methods to real electron microscopic pictures showed that the two proposed methods were more capable of extracting the morphology information than the state-of-the-art methods. When nanoparticles do not have many overlaps, the divide-and-conquer approach performed adequately. When nanoparticles have many overlaps, forming chain-linked clusters, the convex shape analysis approach performed much better than the state-of-the-art alternatives in bio-imaging. The author believes that the capabilities of the proposed methods expedite the morphology characterization process of nanoparticles. The author further conjectures that the technical generality of the proposed methods could even be a competent alternative to the current methods analyzing general overlapping convex-shaped objects other than nanoparticles.

Successful operation of Nano-ElectroMechanical Systems (NEMS) critically depends on their working environment and component materials' electromechanical properties. It is equally important that ambient or liquid environment to be seriously considered for NEMS to work as high sensitivity sensors with commercial viabilities. Firstly, to understand interaction between NEMS oscillator and fluid, transfer function of suspended gold nanowire NEMS devices in fluid was calculated. It was found that NEMS's resonance frequency decreased and energy dissipation increased, which constrained its sensitivity. Sensitivity limit of NEMS oscillators was also considered in a statistical framework. Subsequently, suspended gold nanowire NEMS devices were magnetomotively actuated in vacuum and liquid. Secondly, electromechanical properties of gold nanowires were carefully studied and the observed size effect was found to agree with theory, which predicted small changes of electromechanical property compared with bulk gold materials. Finally, it is well recognized that continuous development of new NEMS devices demands novel materials. Mechanical properties of new two-dimensional hexagonal Boron Nitride films with a few atomic layers were studied. Outlook of utilizing ultrathm BN films in next generation NEMS devices was discussed.

Making a robust carbon nanotube-based conductor as a replacement of copper in electricity grids can initiate a paradigm shift in energy transmission. This dissertation identifies four fundamental factors for making carbon nanotube-based conductors as functionalization, dispersion, concentration and processing. These four factors are discussed in detail by studying four separate systems: nanotube/epoxy composites, nanotube/porous medium density polyethylene (MDPE) composites, nanotube/high density polyethylene (HDPE) composites and pure nanotube cables. In nanotube/epoxy composites, homogeneous dispersion of nanotubes and a strong interface between nanotubes and epoxy matrix were simultaneously achieved through the development of a novel nanotube functionalization. While the degree of functionalization was high, the process was non-destructive to the mechanical properties of the nanotubes. In addition, the functional groups constructed covalent bonds with the epoxy matrix and also made dispersing the nanotubes much easier. As a result, the composites reinforced by the functionalized nanotubes had better mechanical properties than the samples reinforced by the raw nanotubes. In nanotube/porous MDPE composites, the degree of nanotube dispersion reached a level of 1 micron for nanotube agglomerate size within the matrix. This successful dispersion was primarily attributed to creating the porous MDPE. The pore size was tuned to be as small as 1 micron so that the sub-micron long HiPco nanotubes could easily penetrate into the matrix. The nanotube/porous MDPE composites obtained enhancement both in mechanical strength and electrical conductivity compared to the control samples. In nanotube/HDPE composites, the nanotube conducting networks were studied. Conductivity of the composites with the loading ratio at the percolation threshold was not sufficiently high for conductor applications. Nanotube/HDPE composite wires with higher loading ratios up to 40 wt% were prepared. Key factors for improving the formation of the conducting networks were identified. Through optimization in processing, maximum conductivity of ∼10 3 S/m was achieved. Pure nanotube cables were prepared by a solid spinning procedure, which showed the potential to make macroscopic cables of various length and thickness. The pure nanotube cables circumvented the bottleneck in improving conductivity for composite systems, in which polymer in-between the nanotubes caused high contact resistance. The pure nanotube cables reached conductivity as high as ∼10 6 S/m. Through iodine doping, conductivity further was enhanced so that the specific conductivity of the doped cables exceeded that of metals such as copper. As a result of applying the knowledge learned from study of the four fundamental factors, a macroscopic carbon-nanotube cable was created. It reached an unprecedented conductivity as high as ∼10 7 S/m. Mechanically it was more robust than steel, but with 1/6 the weight. This advanced nanotube-based conductor can have a wide spectrum of applications such as transmission lines and low dimensional connecting wires.