Lithography-free micro- and nanostructuring based on conventional plasma etching

In now-a-days semiconductor and MEMS technologies the photolithography is the working horse for fabrication of functional devices. The conventional way (so called Top-Down approach) of microstructuring starts with photolithography, followed by patterning the structures using etching, especially dry etching. The requirements for smaller and hence faster devices lead to decrease of the feature size to the range of several nanometers. However, the production of devices in this scale range needs photolithography equipment, which must overcome the diffraction limit. Therefore, new photolithography techniques have been recently developed, but they are rather expensive and restricted to plane surfaces. Recently a new route has been presented - so-called Bottom-Up approach - where from a single atom or a molecule it is possible to obtain functional devices. This creates new field - Nanotechnology - where one speaks about structures with dimensions 1 - 100 nm, and which has the possibility to replace the conventional photolithography concerning its integral part - the self-assembly. However, this technique requires additional and special equipment and therefore is not yet widely applicable. This work presents a general scheme for the fabrication of silicon and silicon dioxide structures with lateral dimensions of less than 100 nm that avoids high-resolution photolithography processes. For the self-aligned formation of extremely small openings in silicon dioxide layers at in depth sharpened surface structures, the angle dependent etching rate distribution of silicon dioxide against plasma etching with a fluorocarbon gas (CHF3) was exploited. Subsequent anisotropic plasma etching of the silicon substrate material through the perforated silicon dioxide masking layer results in high aspect ratio trenches of approximately the same lateral dimensions. The latter can be reduced and precisely adjusted between 0 and 200 nm by thermal oxidation of the silicon structures owing to the volume expansion of silicon during the oxidation. On the basis of this a technology for the fabrication of SNOM calibration standards is presented. Additionally so-formed trenches were used as a template for CVD deposition of diamond resulting in high aspect ratio diamond knife. A lithography-free method for production of periodic and nonperiodic surface structures using the angular dependence of the etching rate is also presented. It combines the self-assembly of masking particles with the conventional plasma etching techniques known from microelectromechanical system technology. The method is generally applicable to bulk as well as layered materials. In this work, layers of glass spheres of different diameters were assembled on the sample surface forming a mask against plasma etching. Silicon surface structures with periodicity of 500 nm and feature dimensions of 20 nm were produced in this way. Thermal oxidation of the so structured silicon substrate offers the capability to vary the fill factor of the periodic structure owing to the volume expansion during oxidation but also to define silicon dioxide surface structures by selective plasma etching. Similar structures can be simply obtained by structuring silicon dioxide layers on silicon. The method offers a simple route for bridging the Nano- and Microtechnology and moreover, an uncomplicated way for photonic crystal fabrication.

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.

Vorausschau und Planung neuer Technologiepfade in Unternehmen

Unternehmen konkurrieren in einem globalen Wettbewerb um den Transfer neuer Technologien in erfolgreiche Geschäftsmodelle. Aus diesem Grund stehen sie zunehmend der Herausforderung gegenüber, technologische Potenziale frühzeitig zu identifizieren, zu bewerten und Strategien für das Erschließen dieser Potenziale zu entwickeln. Dies ist zentraler Gegenstand der Vorausschau und Planung neuer Technologiepfade. In der vorliegenden Arbeit wird gemeinsam mit vier Unternehmen ein Leitfaden für die Strategiefindung, Entwicklung und Kommerzialisierung neu aufkommender Technologien entwickelt und angewendet. Den Ausgangspunkt der Arbeit bildet eine systematische Aufarbeitung des Forschungsstandes der Vorausschau und Planung neuer Technologien. Anschließend wird ein Beschreibungsmodell der Entstehung neuer Technologiepfade in technologiebasierten Innovationssystemen entwickelt. Auf Basis dieses Modells werden unterschiedliche Kategorien von Einflussfaktoren definiert, die als Analyserahmen für die neu entstehende Technologie dienen. Auf Basis der in der Literatur dokumentierten Abläufe, Teamstrukturen und Methoden (z.B. Roadmaps, Szenarien, Datenbankanalysen) wird ein sechsstufiger Ansatz für die Durchführung der Vorausschau und Planung neuer Technologiepfade konzipiert. Dieser Ansatz wird in vier Firmen für die Vorausschau und Planung neuer Technologien angewendet. Die untersuchten Technologien lassen sich den Feldern Biotechnologie, Nanotechnologie, Umwelttechnologie und Sensorik zuordnen. Zentrales Ergebnis der Arbeit ist ein entsprechend der Erfahrungen in den Unternehmen angepasster Ansatz für die Vorausschau und Planung neuer Technologiepfade. Dieser Ansatz ist in Abhängigkeit von Unternehmens- und Technologiecharakteristika für die weitere Anwendung konkretisiert. Dabei finden die zu beteiligenden Organisationseinheiten, zu betrachtende Einflussfaktoren sowie anwendbare Methoden besondere Berücksichtigung. Die Arbeit richtet sich an Personen in Führungspositionen im Bereich des strategischen Technologiemanagements sowie der Forschung und Entwicklung in Unternehmen, die Strategien für neu aufkommende Technologien entwickeln. Weiterhin sind die Ergebnisse der Arbeit für Wissenschaftler auf dem Gebiet der Methoden zur Vorausschau und Strategieentwicklung für neue Technologien von Interesse.