Die Oberflächeneigenschaften eines Festkörpers können mit Hilfe dünner, durch Selbstorganisation gebildeter Molekülschichten aus Alkoxysilan-Molekülen gezielt verändert werden. Mikrostrukturierte selbstangeordnete Monolagen (SAM) können für die Anwendung in Bauelementen aus organischen Halbleitern von großem Interesse sein. Mikrokontaktdruck und Photolithographie sind zwei etablierte Verfahren, die jedoch Vorlagen und Masken zur Strukturierung benötigen. Dadurch entstehen bei häufig wechselnden Strukturen nicht zu vernachlässigende Rüstzeiten und Kosten. In der vorliegenden Arbeit wird die Erzeugung lateral strukturierter Schichten von Octadecyltrichlorsilan (OTS) auf Siliziumoxidoberflächen am konkreten Beispiel zweier alternativer, sowohl maskenloser als auch kontaktloser Methoden demonstriert: (i) Tintenstrahlverfahren als rein additive Strukturierung, und (ii) laserinduzierte, photothermische Desorption als subtraktive Strukturierung einer OTS-SAM . Für das Tintenstrahldruckverfahren wird an einem Kontaktwinkelmessgerät eine Methode zur Beobachtung und Auswertung der Tropfenverdampfung implementiert und ein Modell für kleine Tropfen entwickelt. Für die subtraktive Strukturierung werden an einem selbst entwickelten Versuchsaufbau die leistungs- und geschwindigkeitsabhängige Strukturbreite untersucht. Die Ergebnisse der beiden Technologieansätze werden verglichen. / With help of thin layers of alkoxysilane molecules formed by self-assembly, the surface properties of solids can be controlled. Microstructured self-assembled monolayers (SAMs) are interesting for applications in components based on organic semiconductors. Two established technologies for the structuring of molecular monolayers are microcontact printing and photolithography, for which templates and masks need to be structured. In this way, setting times and costs are high if variable patterns have to be structured. In this work, the fabrication of laterally structured monolayers from octadecyltrichlorosilane (OTS) is demonstrated for two examples of alternative, both template-free and maskless technologies: (i) inkjet as a purely additive method, and (ii) photothermal laser desorption as a subtractive structuring of an OTS-SAM. For the inkjet technology, a method for the observation and analysis of the evaporation of a droplet is implemented at a goniometer and a mathematical model for small inkjet droplets is extrapolated, For the subtractive laser structuring, the achievable patterning resolution is investigated as a function of laser intensity and scanning speed. The results of both technological approaches are compared.

We developed new methods for controlling and studying microtubules (MTs) outside the complex workings of the living cell. Several surface treatments for preventing MT fouling on surfaces were analyzed and, for the first time, a self-assembled monolayer (SAM) was developed which prevented MT adsorption in the absence of passivating proteins. The morphology and thickness of the SAM was measured to determine the mechanism of formation and origin of the MT-resistant behavior. The SAM was integrated into electron beam lithography for patterning and manipulating MTs using electrophoresis. Reversible MT adsorption and patterning and alignment of single MTs were achieved. We characterized the mechanism for the MT migration under electric field with a focus on the electrodynamics of the flow cell and the forces acting on the MT, along with the time dependence of the process.

An alkyl-containing self-assembled monolayer is grafted on the silicon surface by a nature process in solutions. The alkyl thin film was used as the lubricant for the silica interface, usually applied to the MEMS or NENS domains. The ability of reducing friction for silica device at room temperature was improved, but little was known as the thin films existed at higher temperature during device was working or operating. In this study, we used Hexyltrichlorosilane (C6), Dodecyltrichlorosilane (C12), and Octadecyltrichlorosilane (C18) molecules to form self-assembled monolayers (SAMs) on silicon, and these monolayers exhibited different molecular packing properties due to different interactions between the molecules. Fourier transform infrared spectroscopy (FTIR) revealed that the short chain-length (C6) molecules exhibited poor packing on the surface at room temperature, and that the molecular packing of C6 was thermally stable up to 500 K. But the C12 and C18 monolayers exhibited abrupt blue shifts in FTIR at temperatures between 300 and 575 K, with stable packing observed over several temperature ranges. Furthermore, water contact angle measurements showed the C6, C12, and C18 molecular films changed from hydrophobic to hydrophilic as the sample temperature was increased. Atomic force microscopy (AFM) images revealed that pits had formed in the C18 monolayer after the temperature was increased to 460 K, which were caused by the molecular reorganization of C18 on the surface. This resulted in an abrupt change in the friction coefficient for the C18 monolayer at 460K as compared to the short C6 and C12 monolayers. However, the friction coefficients for all the SAM films still increased with temperature. Understanding the temperature-dependent behavior of SAM film molecules will assist in the design of better anti-wear monolayers to improve performance and increase lifetimes in modern MEMS and NEMS devices.

Low energy (tens of eV) polyatomic cations were used as probes for characterization of monolayers of spontaneously chemisorbed thiols on gold. Characteristics including chemical composition, surface order and orientation of the self-assembled monolayers (SAMs) can be derived by monitoring the products of projectile ion neutralization, surface-induced dissociation (SID), and ion-surface reactions.To study the influence of the terminal group chemical structures and orientations of the SAMs on ion-surface interactions, a series of semi-fluorinated alkane thiols with difluoromethylenes buried underneath hydrocarbon terminal groups were examined (CH3CF2CH2− and CH3CH2CF2−). Compared to terminally fluorinated SAMs, they showed more projectile ion neutralization and less internal to vibrational energy deposition into precursor ions. Projectile ion-hydrocarbon reactions decreased significantly when difluoromethylenes are one or two bonds away from the terminal group. Furthermore, ion-surface reaction results on surfaces with odd and even chain lengths suggested that they have similar terminal methyl orientations to their hydrocarbon counterparts.Mixed monolayers of CF3CF2(CH2)14SH (F-SAMs) and CH3(CH2)15SH (H-SAMs) with systematically changing electron transfer, energy deposition and ion-surface reaction were prepared using mixed thiols solution and micro-contact printing (μ-CP). The solution mixture system showed linear variations in electron transfer and energy deposition with different F-SAM surface concentrations, while non-linear changes occur for ion-surface reaction suggesting strong lateral interactions between the two components. These interactions are minimized in the μ-CP system containing domains of each thiol. Energy deposition on the patterned surfaces varies non-linearly with changing F-SAM concentration which differs from the homogenously mixed system.To explore SID with a 90 collision angle, eV SID of a series of protonated peptide ions were performed in an in-line sector Time-Of-Flight (TOF) mass spectrometer. The results were compared to keV collision-induced dissociation (CID) data collected with the same instrument. Fragmentation efficiency for SID was higher than CID for those peptides. In addition to the excellent control over laboratory collision energies with SID, different amount of energy deposition can be achieved when varying surface composition, e.g. using mixed F-SAM/H-SAM.Reactive ion scattering spectrometry (RISS) results provided more in-depth knowledge of low energy ion-surface interactions that will promote usage of RISS as a novel surface characterization technique.

Diese Arbeit beinhaltet unsere Studien an selbstorganisierenden Monoschichten (engl. SAM = self- assembled monolayer) einiger aromatischer Thiole auf Gold- und Kupferoberflächen. Die Bildung von Monoschichten von Thiophenol, 4-Mercaptophenol, 4-Nitrothiophenol, 4-Aminothiophenol, 1,4-Dithiobenzol, 4-Mercaptopyridin und 2-Mercaptopyridin auf Au und Cu wurde untersucht und charakterisiert. Das abschirmende Verhalten und die strukturelle Anordnung dieser Monoschichten wurden mit Hilfe elektrochemischer und spektroskopischer Methoden geprüft und bestimmt. Zyklische Voltammetrie und oberflächenverstärkte Raman Spektroskopie wurden intensiv zur Aufklärung von Elektronentransferreaktionen an diesen mit SAMs modifizierten Oberflächen genutzt. Elektrochemische Studien von Monoschichten aus Thiophenol, 4-Mercaptophenol, 4-Nitrothiophenol, 4-Aminothiophenol, 1,4-Dithiobenzol, 4-Mercaptopyridin und 2-Mercaptopyridin in 0,1 M wässriger KClO4-Lösung lassen schlussfolgern, dass diese Moleküle schwefelseitig an die Substratoberfläche gebunden sind. In 0,1 M wässriger KClO4-Lösung aufgenommene zyklische Voltammogramme an Gold- und Kupferoberflächen, welche mit oben genannten, aromatischen Thiolen beschichtet wurden, legen nahe, dass Adsorptionsschichten von Thiophenol und 1,4-Dithiobenzol eine stärkere Tendenz zum Abschirmen besitzen als andere. Durch das Einbringen von Kupferproben, welche mit genannten aromatischen Thiolen behandelt wurden, in 0,1 M Silbernitrat-Lösung können sehr leicht Silber-Nanodendritstrukturen erhalten werden. Abscheidezeit und Konzentration der Silbernitrat-Lösung haben einen großen Einfluss auf das Wachstum der Silber-Nanodendritstrukturen auf den modifizierten Kupferproben. Diese Silber-Nanodendritstrukturen besitzen eine hohe katalytische Aktivität hinsichtlich der Oxidation von Hydroquinon. Untersuchungen zur Korrosion an polykristallinem Kupfer, welches mit obigen aromatischen Thiolen modifiziert wurde, in 0,1 M Silbernitrate-Lösung ließen vermuten, dass dieses Kupfersubstrat mehr anodisches Verhalten zeigte als reines Kupfer bei ähnlichen Bedingungen. Zyklische Voltammetrie an wie oben behandeltem Kupfer in 0,1M wässriger KClO4-Lösung zeigte, dass die Geschwindigkeit der Kupferauflösung bei diesen Messungen erhöht war gegenüber anderen, in welchen reines Kupfer bei identischen Bedingungen eingesetzt wurde. / It deals with our studies on self-assembled monolayers of aromatic thiols on gold and copper surfaces. Monolayer formation of thiophenol, 4-mercaptophenol, 4-nitrothiophenol, 4-aminothiophenol, 1,4-dithiobenzene, 4-mer¬cap¬to¬pyridine and 2-mercaptopyridine on Au and Cu surfaces was studied and characterized. The blocking behaviour and structural arrange¬ments of these monolayers were evaluated and characterized using electrochemical and spec¬troscopic techniques. Cyclic voltammetry and surface enhanced Raman spectroscopy were extensively used for the study of electron transfer reactions on these SAM modified surfaces. Electrochemical and spectroelectrochemical studies of thiophenol, 4-mercaptophenol, 4-nitrothiophenol, 4-aminothiophenol, 1,4-dithiobenzene, 4-mercaptopyridine and 2-mercaptopyridine monolayers in aqueous solution of 0.1 M KClO4 suggest that these molecules adsorbed to substrate. Cyclic voltammetry of gold and copper covered with these aromatic thiolates recorded in aqueous solution of 0.1 M KClO4 suggests that adlayers of thio¬phenol and 1,4-dithiobenzene exhibit more blocking behavior than the other ones. Silver nanodendritic structures are easily produced by placing copper samples modified with these aromatic thiolates into 0.1 M silver nitrate solution. Deposition time and concentration of silver nitrate solution have great influence on growing up silver nanodendritic structures on the surface of modified copper samples. These silver nanodendritic structures exhibit electrocatalytic activity towards the oxidation of hydroquinone. Corrosion investigation of polycrystalline copper modified with these aromatic thiolates in 0.1 M silver nitrate solution suggest that copper substrate might be more anodic compared to bare copper under identical condition. Cyclic voltammetry of copper modified with these aromatic thiolates suggests that the rate of dissolution copper in aqueous solution of 0.1 M KClO4 is higher than bare copper in the same condition.

This thesis is an investigation of surface morphology and electronic structure of self-assembled monolayers (SAMs) and solid water films deposited on these SAMs using metastable impact electron spectroscopy (MIES) and infrared reflection-absorption spectroscopy (IRRAS). MIES uses electronically excited slow helium atoms which interact exclusively with the outermost surface layer. The results suggested that in the SAMs containing an odd number of carbon atoms the molecular orbitals localized on the terminal methyl groups are more exposed at the surface compared to those with an even number of carbon atoms. It was also established that solid water films are more uniform on a SAM substrate containing an odd number of carbon atoms. Thermal transformation of amorphous solid water to polycrystalline ice was also observed. MIES suggested that the molecular orbital of water attributed to the lone pair on the oxygen atom became less accessible at the surface upon the transformation.

<p>This study firstly reports the development, characterisation, and application of thick-film acetylcholinesterase (AChE) biosensors based on a gold electrode modified with a mercaptobenzothiazole (MBT) self-assembled monolayer and either poly(omethoxyaniline) (POMA) or poly(2,5-dimethoxyaniline) (PDMA) in the presence of polystyrene(4-sulphonic acid) (PSSA). The Au/MBT/POMA-PSSA/AChE and Au/MBT/PDMA-PSSA/AChE biosensors were then applied to successfully detect standard organophosphorous and carbamate pesticides in a 0.1 M phosphate buffer, 0.1 M KCl (pH 7.2) solution. Secondly, it reports the construction of the Au/MBT/PANI/AChE/PVAc thick-film biosensor for the determination of certain organophosphate and carbamate pesticide solutions in selected aqueous organic solvent solutions.</p>

This doctorate thesis focuses on investigating the parameter space involved in numerically modeling the bandgap engineering of a GaInP/InGaAs/Ge lattice matched multi-junction solar cell (MJSC) using InAs/InGaAs quantum dots (QDs) in the middle sub-cell. The simulation environment – TCAD Sentaurus – solves the semiconductor equations using finite element and finite difference methods throughout well-defined meshes in the device to simulate the optoelectronic behavior first for single junction solar cells and subsequently for MJSCs with and without quantum dots under concentrated illumination of up to 1000 suns’ equivalent intensity. The MJSC device models include appropriate quantum tunneling effects arising in the tunnel junctions which serve as transparent sub-cell interconnects. These tunneling models are calibrated to measurements of AlGaAs/GaAs and AlGaAs/AlGaAs tunnel junctions reaching tunneling peak current densities above 1000 A/cm^2. Self-assembled InAs/GaAs quantum dots (QDs) are treated as an effective medium through a description of appropriate generation and recombination processes. The former includes analytical expressions for the absorption coefficient that amalgamates the contributions from the quantum dot, the InAs wetting layer (WL) and the bulk states. The latter includes radiative and non-radiative lifetimes with carrier capture and escape considerations from the confinement potentials of the QDs. The simulated external quantum efficiency was calibrated to a commercial device from Cyrium Technologies Inc., and required 130 layers of the QD effective medium to match the contribution from the QD ground state. The current – voltage simulations under standard testing conditions (1 kW/cm^2, T=298 K) demonstrated an efficiency of 29.1%, an absolute drop of 1.5% over a control structure. Although a 5% relative increase in photocurrent was observed, a 5% relative drop in open circuit voltage and an absolute drop of 3.4% in fill factor resulted from integrating lower bandgap nanostructures with shorter minority carrier lifetimes. However, these results are considered a worst case scenario since maximum capture and minimum escape rates are assumed for the effective medium model. Decreasing the band offsets demonstrated an absolute boost in efficiency of 0.5% over a control structure, thus outlining the potential benefits of using nanostructures in bandgap engineering MJSCs.

Philosophiae Doctor - PhD / This study firstly reports the development, characterisation, and application of thick-film acetylcholinesterase (AChE) biosensors based on a gold electrode modified with a mercaptobenzothiazole (MBT) self-assembled monolayer and either poly(omethoxyaniline) (POMA) or poly(2,5-dimethoxyaniline) (PDMA) in the presence of polystyrene(4-sulphonic acid) (PSSA). The Au/MBT/POMA-PSSA/AChE and Au/MBT/PDMA-PSSA/AChE biosensors were then applied to successfully detect standard organophosphorous and carbamate pesticides in a 0.1 M phosphate buffer, 0.1 M KCl (pH 7.2) solution. Secondly, it reports the construction of the Au/MBT/PANI/AChE/PVAc thick-film biosensor for the determination of certain organophosphate and carbamate pesticide solutions in selected aqueous organic solvent solutions. / South Africa

xvii, 209 p. : ill. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / Altering and controlling the properties of solid surfaces in aqueous or other liquid phase environments has been a sought after objective for decades. With the discovery of chemisorbed self-assembled monolayers, this dream has become a reality. Oxide and metal surfaces can now be readily coated with an array of commercially available products to produce a desired fnctionality. The presence of these coatings on solid surfaces affects properties of the interfacial region by altering interfacial electrostatic fields, changing the structure of interfacial water molecules and altering the interactions of adsorbed species. This dissertation reports on in situ studies of adsorption at several solid/aqueous interfaces using vibrational sum-frequency spectroscopy, a surface specific technique. These studies are augmented by the use of atomic force microscopy and contact angle goniometry to characterize the prepared surfaces and their interactions with adsorbates. The studies investigate how changes in the surface structure and chemistry, as well as the bulk aqueous phase, affect interfacial structure. The studies within are primarily focused on the interactions of water with bare and functionalized fused silica and the relationship between the aqueous phase composition and the structure of fluorocarbon and hydrocarbon self-assembled monolayers. The variations in aqueous structure are then examined in detail using ionic strength controlled experiments to understand the direct interactions of water hydrophobically coated silica. This analysis is followed by an investigation of the competitive adsorption of methanol and water at fluorocarbon and hydrocarbon monolayers which show spectroscopic signatures of the interaction strength between fluorocarbons and hydrocarbons. Further studies are performed using butylammonium chloride to verify these spectroscopic signatures and reveal different molecular structures of adsorbed species at chemically different hydrophobic surfaces. Lastly, specific ion effects on the CaF 2 /water interface are shown using equilibrium and time-resolved sum-frequency spectroscopy. The results of all these studies have implications for an array of surface chemical applications from mineral flotation to biocompatibility. This dissertation includes previously published co-authored material. / Committee in charge: Thomas Dyke, Chairperson, Chemistry; Geraldine Richmond, Advisor, Chemistry; James Hutchison, Member, Chemistry; Mark Lonergan, Member, Chemistry; Qusheng Jin, Outside Member, Geological Sciences