No description available.

No description available.

In this thesis, atomic force microscopy (AFM), transmission electron microscopy (TEM) and optical microscopy techniques were used to investigate systematically the self-assembled nanostructure behaviour of two different types of spin-cast polymer thin films: poly(isoprene-b-ethylene oxide), PI-b-PEO diblock copolymers and [poly(9,9-dioctylfluorene-co-benzothiadiazole)]:poly[9,9- dioctyfluorene-co-N-(4-butylphenyl)-diphenylamine], F8BT:TFB conjugated polymer blends. In the particular case of the polymer blend thin films, the morphology of their composites with cadmium selenide (CdSe) quantum dot (QD) nanoparticles was also investigated. For the diblock copolymer thin films, the behaviour of the nanostructures formed and the wetting behaviour on mica, varying the volume fraction of the PEO block (fPEO) and the average film thickness was explored. For the polymer blend films, the effect of the F8BT/TFB blend ratio (per weight), spin-coating parameters and solution concentration on the phase-separated nanodomains was investigated. The influence of the quantum dots on the phase separation when these were embedded in the F8BT:TFB thin films was also examined. It was found that in the case of PI-b-PEO copolymer thin films, robust nanostructures, which remained unchanged after heating/annealing and/or ageing, were obtained immediately after spin coating on hydrophilic mica substrates from aqueous solutions. The competition and coupling of the PEO crystallisation and the phase separation between the PEO and PI blocks determined the ultimate morphology of the thin films. Due to the great biocompatible properties of the PEO block (protein resistance), robust PEO-based nanostructures find important applications in the development of micro/nano patterns for biological and biomedical applications. It was also found that sub-micrometre length-scale phase-separated domains were formed in F8BT:TFB spin cast thin films. The nanophase-separated domains of F8BT-rich and TFB-rich areas were close to one order of magnitude smaller (in the lateral direction) than those reported in the literature. When the quantum dot nanoparticles were added to the blend thin films, it was found that the QDs prefer to lie in the F8BT areas alone. Furthermore, adding quantum dots to the system, purer F8BT and TFB nano-phase separated domains were obtained. Conjugated polymer blend thin films are excellent candidates for alternatives to the inorganic semiconductor materials for use in applications such as light emitting diodes and photovoltaic cells, mainly due to the ease of processing, low-cost fabrication and mechanical flexibility. The rather limited optoelectronic efficiency of the organic thin films can be significantly improved by adding inorganic semiconducting nanoparticles.

Precessional dynamics are exploited in the operation of high frequency magnetic devices such as magnetic disk drives, non reciprocal microwave devices and spin transfer oscillators. The trajectory of the precession and its damping are of crucial importance. This thesis presents the characterisation of a variety of magnetic thin film structures performed with a range of phase sensitive techniques. It is possible to obtain new insight by utilising the chemical and site specificity of X-ray Magnetic Circular Dichroism (XMCD) to isolate the precession in different chemical species or at distinct sites in the crystal structure of a chosen material. X-ray Ferromagnetic Resonance (XFMR) combines XMCD and Ferromagnetic Resonance (FMR) phenomena in a technique capable of measuring the FMR response of an alloy or multilayer with both chemical and site specificity. To complement the XFMR technique a low temperature Time-Resolved Magneto Optical Kerr Effect (TR-MOKE) setup has been developed. This allowed for the characterisation of samples at temperatures in the range 4 K to room temperature. A frequency swept Vector Network Analyser FMR (VNA-FMR) setup was developed to allow for a fast method for determining the resonance condition and damping of a range of ferromagnetic thin film samples. In addition a TR-X-ray Photoemission Electron Microscopy (TR-XPEEM) setup has been established which allows images to be obtained with magnetic contrast. The combination of the above techniques has lead to studies on rare earth capped spin valve free layers and the measurement of spin pumping in industrially relevant spin valves.

Carbon-based thin films are a vast group of materials of great technological importance. Thanks to the different bonding options for carbon, a large variety of structures (from amorphous to nanostructured) can be achieved in the process of film synthesis. The structural diversity increases even more if carbon is combined with relatively small quantities of atoms of other elements. This results in a set of materials with many different interesting properties for a wide range of technological applications. This doctoral thesis is about nanostructured carbon-based thin films. In particular, the focus is set on theoretical modeling, prediction of structural features and design of sulfo carbide (CSx) and carbon fluoride (CFx) thin films. The theoretical approach follows the synthetic growth concept (SGC) which is based on the density functional theory. The SGC departure point is the fact that the nanostructured films of interest can be modeled as assemblies of low dimensional units (e.g., finite graphene-like model systems), similarly to modeling graphite as stacks of graphene sheets. Moreover, the SGC includes a description of the groups of atoms that act as building blocks (i.e., precursors) during film deposition, as well as their interaction with the growing film. This thesis consists of two main parts: Prediction: In this work, I show that nanostructured CSx thin films can be expected for sulfur contents up to 20 atomic % with structural characteristics that go from graphite-like to fullerene-like (FL). In the case of CFx thin films, a diversity of structures are predicted depending on the fluorine concentration. Short range ordered structures, such as FL structure, can be expected for low concentrations (up to 5 atomic %). For increasing fluorine concentration, diamond-like and polymeric structures should predominate. As a special case, I also studied the ternary system CSxFy. The calculations show that CSxFy thin films with nanostructured features should be possible to synthesize at low sulfur and fluorine concentrations and the structural characteristics can be described and explained in terms of the binaries CSx and CFx. Design: The carbon-based thin films predicted in this thesis were synthesized by magnetron sputtering. The results from my calculations regarding structure and composition, and analysis of precursors (availability and role during deposition process) were successfully combined with the experimental techniques in the quest of obtaining films with desired structural features and understanding their properties.

CIVINS / Carbon nanotubes (CNTs) exhibit exceptional electrical, thermal, and mechanical properties that could potentially transform such diverse fields as composites, electronics, cooling, energy storage, and biological sensing. For the United States Navy, composites potentially provide a significant decrease in lifetime maintenance costs of ships by eliminating hull corrosion. A stronger composite could also improve naval ship survivability or increase combat payloads by reducing the hull weight of ships and submarines. Further, cooling requirements of ship borne electronics have grown exponentially and represent a significant weight penalty for advanced ship designs. Any improvement in thermal transport could significantly improve future naval ship designs. In order to realize these benefits, methods must be discovered to fully characterize CNT growth mechanisms, consistently produce CUTs in manufacturable quantities, and to integrate CUTs into macroscale structures which reflect the properties of individual CUTs. While growth of CNTs in laboratory scale chemical vapor deposition (CVD) tube furnaces has shown great promise, existing low cost tube furnace designs limit the researcher's ability to fully separate critical reaction parameter such as temperature and flow profiles and limit the rate of temperature change during the growth process. Conventional tube furnace designs also provide limited mechanical access to the growth Site and prevent optical monitoring of the growth site, removing the ability to observe and interact in situ during growth. This thesis presents the SabreTube, a low-cost desktop cvD apparatus that decouples temperature and flow variables, provides mechanical and optical access to the reaction site during growth, and provides modular fixturing to enable versatile experimentation with and characterization of CUT growth mechanisms. This thesis also presents the Nanosled, a device designed to translate a substrate through a CVD furnace. / Contract number: N62271-97-G-0026. / CIVINS

Phosphorescent organic light emitting diodes (PHOLEDs) based on efficient electrophosphorescent dopant, platinum(II)-pyridyltriazolate complex, bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) (Pt(ptp)2) have been studied and improved with respect to power efficiency, external efficiency, chromacity and efficiency roll-off. By studying the electrical and optical behavior of the doped devices and functionality of the various constituent layers, devices with a maximum EQE of 20.8±0.2 % and power efficiency of 45.1±0.9 lm/W (77lm/W with luminaries) have been engineered. This improvement compares to devices whose emission initially could only be detected by a photomultiplier tube in a darkened environment. These devices consisted of a 65 % bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) (Pt(ptp)2) doped into 4,4'-bis(carbazol-9-yl)triphenylamine (CBP) an EML layer, a hole transporting layer/electron blocker of 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), an electron transport layer of 1,3,5-tris(phenyl-2-benzimidazolyl)-benzene (TPBI), and a LiF/Al cathode. These devices show the acceptable range for warm white light quadrants and qualify to be called "warm white" even w/o adding another emissive layer. Dual EML devices composed of neat Pt(ptp)2 films emitting orange and CBP: Pt(ptp)2 film emitting blue-green produced a color rendering index (CRI) of 59 and color coordinates (CIE) of (0.47,0.49) at 1000Cd/m² with power efficiency of 12.6±0.2 lm/W and EQE of 10.8±0.2 %. Devices with two blue fluorescent emission layers as singlet filters and one broad yellow emission layer from CBP: Pt(ptp)2 displayed a CRI of 78 and CIE of (0.28,0.31) at 100Cd/m² with maximum power efficiency of 6.7±0.3 lm/W and EQE of 5.7±0.2 %.

A fairly general method for studying electromagnetic induction in cases where any lateral variations in conductivity are confined to the near-surface region is developed using the thin-sheet technique. The significant feature is that extended anomalies, subject only to the restriction that well-defined two-dimensional problems are approached at infinity, can be handled. The approximate boundary condition is that gradients parallel to the coordinate axes vanish at infinity. / Graduate

Conducting polymers have emerged as a promising material for optoelectronics and chemical sensing application. Polyaniline (PANI) is a conductive polymer which can be easily functionalized to be specific for various biomolecules and has ideal sensor characteristics. The protonation and deprotonation of the polyaniline’s backbone by derivatization can result in color and conductive change responses. This makes it ideal for the construction of a real time, naked eye sensor. Derivatized polyaniline has previously been reported as a colorimetric sensor in solution. We plan to create a more practical sensor by synthesizing hydroxyl functionalized polyaniline thin films. In this study, we designed a process to functionalize polyaniline and deposit it as a thin film on quartz or silicon substrate via a dip coating process. To demonstrate the use of derivatized PANI in biosensing applications, derivatized and underivatized PANI thin films were treated with solutions of L-aspartic (Asp) acid at concentrations ranging from 10-8 mM to 103 mM and monitored utilizing UV-Vis spectroscopy. We found that the derivatized thin films change from deep blue to green color upon addition of Asp solution and showed a decrease in the characteristic quinoid ring peak at 600nm and the appearance of a new polaron peak at 425nm. The underivatized PANI films showed no colorimetric response indicating the hydroxyl functionalized PANI films are a more ideal material for a biosensing and naked eye detection. The polyaniline derivative was characterized using FT-IR spectroscopy, 1H NMR spectroscopy, UV-VIS spectroscopy, and Scanning Electron Microscopy. Additionally, conductivity studies were utilized to explore the material’s effectiveness as an electronic sensor using a 4-point probe to measure resistance.

Xenoliths are pieces from the surrounding bedrock, brought to the surface of the earth by host magma. On Gran Canaria, the largest island in the Canary Islands archipelago, strange xenoliths have been found. They are light in color, porous and very different from the basaltic magma carrying them. By studying petrological features and oxygen isotope content of the xenoliths, the focus of this report will be to investigate their origin. The minerals and texture of 14 samples were studied in thin section, and the δ18O–value was determined for 17 samples. The mineralogical composition of xenolith glass was examined by EPMa. The results show that the xenoliths are rich in silica rich glass, quartz and feldspars, but also have high calcium content. 9 of 14 xenoliths have textures and δ18O–values from 8.1 ‰ to 16.77 ‰, similar to sedimentary rocks. The remaining xenoliths are metamorphosed and exhibit altered phenocrysts, indicating they have been melted and recrystallized. The latter group also has extremely low δ18O–value, which could be explained by the effects of hydrothermal processes. Most likely all the xenoliths originate from the prevolcanic sedimentary deposits beneath Gran Canaria.