Dipodal Ferrocene Derivatives for Nanostructured Redox-Functionalised Surfaces

Self-assembled monolayers (SAMs) on solid surfaces are of great current interest in science and nanotechnology. This thesis describes the preparation of several symmetrically 1,1’-substituted ferrocene derivatives that contain anchoring groups suitable for chemisorption on gold and may give rise to SAMs with electrochemically switchable properties. The binding groups are isocyano (-NC), isothiocyanato (-NCS), phosphanyl (-PPh2), thioether (-SR) and thienyl. In the context of SAM fabrication, isothiocyanates and phosphanes are adsorbate systems which, surprisingly, have remained essentially unexplored. SAMs on gold have been fabricated with the adsorbates from solution and investigated primarily by X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy. The results of these analytical investigations are presented and discussed in matters of the film quality and possible binding modes. The quality of self-assembled monolayers fabricated from 1,1’-diisocyanoferrocene and 1,1’-diisothiocyanatoferrocene turned out to be superior to that of films based on the other adsorbate species investigated. Films of those absorbates as well as of dppf afforded well-defined SAMs of good quality. All other films of this study based on sulfur containing anchoring groups exhibit chemical inhomogeneity and low orientational order of the film constituents and therefore failed to give rise to well-defined SAMs. Surface coordination chemistry is naturally related to molecular coordination chemistry. Since all SAMs described in this thesis were prepared on gold (111) surfaces, the ferrocene-based ligands of this study have been investigated in their ability for complexation towards gold(I). The sulfur-based ferrocene ligands [fc(SR)2] failed to give stable gold(I) complexes. In contrast, 1,1’-diisocyanoferrocene (1) proved to be an excellent ligand for the complexation of gold(I). Several complexes were prepared and characterised utilising a series of gold(I) acetylides. These complexes show interesting structural motifs in the solid state, since intramolecular aurophilic interactions lead to a parallel orientation of the isocyano moieties, combined with an antiparallel alignment of neighbouring units. The reaction of 1 with the gold(I) acetylide [Au(C≡C–Fc)]n turned out to be very unusual, since the two chemically equivalent isocyano groups undergo a different reaction. One group shows an ordinary coordination and the other one undergoes an extraordinary 1,1-insertion into the Au-C bond. As a sideline of the research of this thesis several ferrocene derivatives have been tested for their suitability for potential surface reactions. Copper(I) mediated 1,3-dipolar cycloadditions of azidoferrocene derivatives with terminal alkynes appeared very promising in this context, but failed to a certain extent in terms of ‘click’ chemistry, since the formation of the triazoles depended on the strict exclusion of oxygen and moisture and yields were only moderate. Staudinger reactions between dppf and azidoferrocene derivatives were also tested. The nucleophilic additions of secondary amines to 1,1’-diisothiocyanatoferrocene led to the respective thiourea derivatives in quantitative yields.

Model Calculations and Implementation of Filters and Hybrid Green VCSELs based on Optical Thin Film Stacks

This work introduced the novel conception of complex coupled hybrid VCSELs for the first time. Alternating organic and inorganic layers in the lasers provide periodic variation of refractive index and optical gain, which enable single mode operation and low threshold of the VCSELs. Model calculations revealed great reduction of the lasing threshold with factors over 30, in comparison with the existing micro-cavity lasers. Tunable green VCSEL has been also designed, implemented and analyzed taking advantage of the broad photoluminescence spectra of the organics. Free standing optical thin films without compressive stress are technologically implemented. Multiple membrane stacks with air gap in between have been fabricated for the implementation of complex coupled VCSEL structures. Complex coupled hybrid VCSEL is a very promising approach to fill the gaps in the green spectral range of the semiconductor lasers.

Oblique Angle Deposition of Germanium Film on Silicon Substrate

The effect of flux angle, substrate temperature and deposition rate on obliquely deposited germanium (Ge) films has been investigated. By carrying out deposition with the vapor flux inclined at 87° to the substrate normal at substrate temperatures of 250°C or 300°C, it may be possible to obtain isolated Ge nanowires. The Ge nanowires are crystalline as shown by Raman Spectroscopy.

Poly-Si₁₋xGex Film Growth for Ni Germanosilicided Metal Gate

Scaling down of the CMOS technology requires thinner gate dielectric to maintain high performance. However, due to the depletion of poly-Si gate, it is difficult to reduce the gate thickness further especially for sub-65 nm CMOS generation. Fully silicidation metal gate (FUSI) is one of the most promising solutions. Furthermore, FUSI metal gate reduces gate-line sheet resistance, prevents boron penetration to channels, and has good process compatibility with high-k gate dielectric. Poly-SiGe gate technology is another solution because of its enhancement of boron activation and compatibility with the conventional CMOS process. Combination of these two technologies for the formation of fully germanosilicided metal gate makes the approach very attractive. In this paper, the deposition of undoped Poly-Si₁₋xGex (0 < x < 30% ) films onto SiO₂ in a low pressure chemical vapor deposition (LPCVD) system is described. Detailed growth conditions and the characterization of the grown films are presented.

Plasma polymerization of C[subscript 4]F[subscript 8] thin film on high aspect ratio silicon molds

High aspect ratio polymeric micro-patterns are ubiquitous in many fields ranging from sensors, actuators, optics, fluidics and medical. Second generation PDMS molds are replicated against first generation silicon molds created by deep reactive ion etching. In order to ensure successful demolding, the silicon molds are coated with a thin layer of C[subscript 4]F[subscript 8] plasma polymer to reduce the adhesion force. Peel force and demolding status are used to determine if delamination is successful. Response surface method is employed to provide insights on how changes in coil power, passivating time and gas flow conditions affect plasma polymerization of C[subscript 4]F[subscript 8].

Data Protection Act links to film, slides, quesions; overview notes

Published on Jun 7, 2012 by icocomms This ICO training video helps answer questions about the Data Protection Act, its impact on the working environment and how to handle and protect people's information. (Produced by Central Office of Information, Crown Copyright 2006)

The Phenomenology of the Political: Cavell on Film

A lengthy defense of Cavell on film and politics in response to an article by Joshua Dienstag

Film, TV and music : multi-level photocopiable activities for teenagers.

Este recurso para el profesor contiene actividades que abarcan temas de interés para los jóvenes como el cine, la música y la televisión. Proporciona material didáctico adicional, que puede fotocopiarse, para los niveles elemental, intermedio y avanzado.

Proyecto curricular del área de Inglés : film workshop.

Material publicado por el Departamento de Educación, Universidades e Investigación del Gobierno Vasco. Se trata de materiales curriculares que pretenden servir para la formación del profesorado y que ejemplifican y marcan pautas para el trabajo según los nuevos planteamientos curriculares de la LOGSE. Los que aquí se presentan pretenden aumentar el interés de los alumnos por la lengua y mostrar cómo el mundo del espectáculo puede servir de base para el estudio de la cultura y civilización de otros países. Ofrecen un conjunto de actividades que permiten la realización de un trabajo interdisciplinar, pudiendo implicar a varios seminarios (Historia, Lengua, Filosofía, etc.), y adoptan un enfoque comunicativo, primando la utilización de recursos auténticos: audiovisuales (películas), textos escritos (fuentes de información, literarios, etc.) y musicales (canciones). En resumen, los contenidos del documento pueden enmarcarse: - dentro del área; - dentro de una línea transversal (Educación en Medios de Comunicación Social); y - bajo un planteamiento interdisciplinar.

Cómo limpiarse las gafas : fragmento de una carta : sobre el análisis del film.

Visión de cómo se ha de analizar una película, utilizando distintos instrumentos para comentar cada film. En primer lugar, se describen los distintos tipos de análisis existentes, y después, se exponen varios ejemplos de análisis, con distintos instrumentos cada uno, de manera que respondan a las necesidades que plantee cada film. Además, ha de tenerse en cuenta el ámbito de aplicación de cada procedimiento de análisis.

El apagón analógico : el British Film Institute y la educación en los tres últimos decenios.

Resumen basado en el de la revista. - El artículo pertenece a una sección monográfica de la revista dedicada a Lenguajes fílmicos en la memoria colectiva de Europa

Film scoring.

Resumen tomado de la publicación. - El artículo pertenece a una sección de la revista dedicada a: El aula de música y las competencias básicas

Some of my favourite film stars : una experiencia de aula utilizando Internet.

Se describe la experiencia llevada a cabo con alumnos de primero de ESO en la asignatura de Inglés y que consistía en la búsqueda de un personaje de su interés en la página web: www.biography.com y en analizar su biografía a través de diversas actividades utilizando el idioma inglés. Los objetivos del trabajo son: desarrollar la capacidad lectora de los alumnos en inglés aún cuado no entiendan todo, leer para obtener la información específica, aprender a intuir el significado de palabras desconocidas por el contexto, practicar el vocabulario y las estructuras estudiadas, conseguir que los alumnos adquieran confianza a la hora de enfrentarse a páginas web en inglés y capacitar a los alumnos para que realicen búsquedas en Internet de material en inglés.

Reliable entertainment: Spanish consumers' preferences regarding a film's country of origin

This article contributes to the study of cinema audiences in Europe by analyzing the actual behavior of Spanish moviegoers and their level of satisfaction. We modeled moviegoers’ choice of film by country of origin (U.S.A., Spain, and other countries) according to a set of determinants: (1) consumers’ interpretation of several sources of information, (2) motivations and (3) choice rules. We found three clear consumer stereotypes related to each type of film: (1) U.S.A. films were preferred by almost everyone (especially families and younger audiences); (2) Spanish films had audiences composed of middle-age and middle-class moviegoers; and (3) European productions were preferred by a social or intellectual elite. U.S.A. films dominate the Spanish market for the reason that they provide most of what moviegoers prefer, namely, familiar, reliable entertainment in Spanish; three characteristics that are not satisfied by Spanish and European films. Additionally, we discuss the implications for the European cultural policy