Es wird eine Alternative zum Ätzen von Siliciumnitrid (SiNx) auf Silicium-Wafern vorgestellt. Herkömmliche Verfahren zum Ätzen von SiNx auf Silicium-Wafern arbeiten mit Flusssäure oder Phosphorsäure. Zu diesen Chemikalien werden alternative organische Komplexbildner zum Ätzen von SiNx vorgestellt, welche im Gegensatz zu den herkömmlichen Substanzen weniger giftig und umweltschädlich sind. Bei den organischen Komplexbildnern handelt es sich um die Stoffgruppen der Hydroxycarbonsäuren und Aminosäuren. Für diese Substanzen wurden die ersten wichtigen Parameter für einen Einsatz in der Halbleiterindustrie untersucht. Dabei handelt es sich um Einflüsse durch die Herstellungsprozesse des SiNx selbst, des pH-Wertes, der chemischen Struktur des organischen Komplexbildners und die Konzentrations- und Temperaturabhängigkeit. Es werden für die Reaktion auch die ersten Reaktionsmechanismen postuliert.:1 Einleitung...................... 1 1.1 NachhaltigkeitinderHalbleiterindustrie................. 2 1.2 Nasschemische Ätzmethoden für Siliciumnitrid (SiNx).......... 5 1.3 ZieledieserForschungsarbeit........................ 9 2 Material und Methoden 11 2.1 Probenkörper ................................ 11 2.2 Ätzversuche ................................. 12 2.3 Charakterisierung.............................. 15 3 Ätzmittel für SiNx 25 3.1 Chemischer Aufbau von organischen Komplexbildnern für Siliciumnitrid.... 25 3.2 UntersuchungderMorphologie....................... 25 3.3 XPS-AnalysederOberfläche........................ 33 3.4 WirksameGruppen............................. 35 4 Methodenentwicklung zur Bestimmung von Ätzraten, Selektivität und Isotropie.... 37 4.1 Ätzrate.................................... 37 4.2 Selektivität................................. 39 4.3 Methoden zur Bestimmung der Schichtdickendifferenz .......... 43 4.4 Fehlerbetrachtung und Zusammenfassung der Methoden........ 46 4.5 Zusammenfassung der Messmethoden................... 51 5 Parameter mit Einfluss auf den Ätzprozess 53 5.1 Einfluss des Herstellungsprozesses..................... 53 5.2 Einfluss des pH-Wertes auf den SiNx-Abbau ................... 55 5.3 Einfluss von Wasser auf die Reaktion ................... 56 5.4 Einfluss der Struktur ............................ 57 5.5 Konzentrations- und Temperaturabhängigkeit der Ätzrate von Ätzmitteln 60 5.6 Untersuchung des kinetischen Verlaufs der Reaktion . . . . . . . . . . . 69 5.7 Untersuchung der Isotropie......................... 72 6 Postulierte Reaktionsmechanismen 77 6.1 Abbau des Stickstoffs aus der SiNx-Oberfläche . . . . . . . . . . . . . . 77 6.2 Abbau des Si aus der SiNx-Oberfläche................... 78 6.3 Milchsäure als Katalysator zum Abbau von elementarem Si . . . . . . . 80 6.4 NMR-Analyse................................ 82 7 Zusammenfassung und Ausblick 87 7.1 Zusammenfassung.............................. 87 7.2 Ausblick................................... 89 6.5 Ergebniszusammenfassung der postulierten Reaktionsmechanismen . . . 86

[pt] A inundação com água de baixa salinidade é uma estratégia de recuperação avançada de petróleo (EOR) em reservatórios carbonatados, onde a concentração e composição da salmoura são cruciais para a remoção do óleo. Este estudo investigou os aspectos químicos e físicos da inundação com água de baixa salinidade e seu impacto na recuperação de petróleo, focando na interação e modificações na interface óleo-calcita. Medidas de FTIR foram utilizadas para caracterizar a adsorção e quantificar a remoção de óleo mineral Nujol em monocristais de calcita clivados no plano (104), antes e após condicionamentos nas salmouras em diferentes condições. Os resultados mostraram que o Nujol forma um filme contínuo na superfície da calcita, impedindo sua dissolução nas condições de condicionamento nas salmouras de menor teor de sal. A quantidade de óleo removido variou conforme a salinidade da salmoura. Nas condições experimentais investigadas, a superfície de calcita recém clivada é mais eficientemente convertida de oleofílica para hidrofílica quando condicionada em condição de salinidade intermediaria (LS75). A remoção de óleo foi quantificada por meio de análise FTIR semiquantitativa, variando de aproximadamente 20 por cento de óleo removido para água de formação (FW) até cerca de 81 por cento após condicionamento em LS75. A análise espectroscópica indicou uma competição entre a incorporação de espécies iônicas da salmoura na interface e a dissolução da calcita, afetando diretamente na cristalinidade da superfície. O condicionamento com água deionizada (DW) não resultou na remoção ideal de óleo devido à maior dissolução e readsorção de moléculas de óleo. O estudo também constatou que o magnésio exerceu maior influência na remoção de óleo da superfície em comparação com o cálcio. As superfícies previamente hidratadas com FW e DW apresentaram alterações significativas. A hidratação com FW não necessariamente causa dissolução, mas promove a adsorção de grupos OH, criando pontos de ancoragem para o óleo. Em contraste, a hidratação com DW resultou na perda de cristalinidade, gerando defeitos na superfície. Em ambos os casos, foram observadas mudanças nas bandas de vibração características do nujol, sugerindo diferentes interações do óleo com a superfície. Comparando a quantidade de óleo adsorvida nas três condições estudadas, a calcita hidratada com FW apresentou a maior quantidade de óleo adsorvido, associado à adsorção de íons na superfície. / [en] Low salinity water flooding is an advanced oil recovery (EOR) strategy in carbonate reservoirs, where the concentration and composition of the brine are crucial for oil removal. This study investigated the chemical and physical aspects of low salinity water flooding and its impact on oil recovery, focusing on the interaction and modifications at the oil-calcite interface. FTIR measurements were used to characterize the adsorption and quantify the removal of mineral oil Nujol on calcite single crystals cleaved along the (104) plane, before and after conditioning in brines under different conditions. The results showed that Nujol forms a continuous film on the calcite surface, preventing its dissolution under aging conditions in lower salinity brines. The amount of oil removed varied according to the salinity of the brine. Under the experimental conditions investigated, the freshly cleaved calcite surface is more efficiently converted from oleophilic to hydrophilic when conditioned in intermediate salinity condition (LS75). The oil removal was quantified using semiquantitative FTIR analysis, ranging from approximately 20 percent for formation water (FW) to about 81 percent after conditioning in LS75. Spectroscopic analysis indicated a competition between the incorporation of ionic species from the brine at the interface and the dissolution of calcite, directly affecting the surface crystallinity. Conditioning with deionized water (DW) did not result in optimal oil removal due to increased dissolution and re-adsorption of oil molecules. The study also found that magnesium had a greater influence on oil removal from the surface compared to calcium. The surfaces previously hydrated with FW and DW showed significant alterations. Hydration with FW does not necessarily cause dissolution but promotes the adsorption of OH groups, creating anchoring points for the oil. In contrast, hydration with DW resulted in a loss of crystallinity, generating defects on the surface. In both cases, changes in the characteristic vibration bands of nujol were observed, suggesting different interactions of the oil with the surface. Comparing the amount of oil adsorbed under the three conditions studied, the calcite hydrated with FW showed the highest amount of adsorbed oil, associated with ion adsorption on the surface.

No description available.

This thesis addresses simulation of electrochemical experiments, with an emphasis on processes of diffusional mass transport to electrode surface. Following system has been studied: • Applying theoretical modeling and experimentation is shown that even significant surface roughness produced by deliberate polishing or scratching is not sufficient to be distinguished in cyclic voltammetry experiments conducted under the usual conditions. In stripping voltammetry experiment the shape of the voltammograms strongly depends on the model of the electron transfer but is not always sensitive to the precise model of the electrode surface; the conditions under which this is the case are identified, and generic roughness effects on stripping voltammetry are quantified. Electrode roughness can have a significant effect on the stripping of the metals from the solid electrode especially in respect of the voltammetric waveshape. • We first consider two different models of electrodes covered with electroinactive layers: the electrode is covered with a uniform layer and the layer contains pinholes. Both models are simulated and then compared to identify conditions under which they can be distinguished. Next we propose generic model to predict the influence of electroactive layer on the cyclic voltammetric. The conditions under which deviation from the behavior of a planar electrode are predicted. • We first consider one electron, one proton and next two electron, two proton reduction of surface bound species. Two mechanisms of reaction are considered: stepwise and concerted. Voltammetry studied under the three regimes of protons mass transport: infinitely fast (fully buffered solution), infinitely slow (infinitely high surface coverage of electrode) and intermediate case of finite rate of diffusional mass transport to electrode surface. Types of voltammograms observed in each case are presented and discussed. • Theory of chronoamperometry on disc and ring-recessed microelectrodes and their arrays is reported. Three and four different regimes of transient current versus time can be observed at microelectrode arrays of disc and ring electrodes, accordingly. A generic, accurate and easy to use method of experimental chronoamperometric data analysis is proposed. It is shown that the method can be applied to the simultaneous measurement of D and nC in solution. • The fabrication, characterization, and use of arrays of ring-recessed disk generator-colector microelectrodes are reported. Experiments and simulations relating to time- of-flight experiments in which material electrogenerated at a disk is diffusionally transported to the ring are reported. We further study voltammetry of electrochemically active species which undergoes first and second order chemical reactions. Current transients are found to be sensitive to the diffusion coefficient of both the reduced and oxidised species as well as to the rate of the chemical reaction and its mechanism.

Metal oxides are of immense technological importance. Their wide variety of structural and electronic characteristics leads to a flexibility unrivalled by other groups of materials. However, there is still much debate about the fundamental properties of some of the most widely used oxides, including TiO₂ and In₂O₃. This work presents high quality, in-depth characterisation of these two oxides in pure and doped form, including soft and hard X-ray photoelectron spectroscopy and X-ray diffraction. Bulk samples as well as thin film samples were prepared analysed. For the preparation of thin films a high quality sol-gel dip-coating method was developed, which resulted in epitaxial films. In more detail the organisation of the thesis is as follows: Chapter 1 provides an introduction to key ideas related to metal oxides and presents the metal oxides investigated in this thesis, In₂O₃, Ga₂O₃, Tl₂O₃, TiO₂, and SnO₂. Chapter 2 presents background information and Chapter 3 gives the practical details of the experimental techniques employed. Chapters 4 presents reciprocal space maps of MBE-grown In₂O₃ thin films and nanorods on YSZ substrates. Chapters 5 and 6 investigate the doping of In₂O₃ bulk samples with gallium and thallium and introduce a range of solid state characterisation techniques. Chapter 7 describes the development of a dip-coating sol-gel method for the growth of thin films of TiO₂ and shows 3D reciprocal space maps of the resulting films. Chapter 8 concerns hard x-ray photoelectron spectroscopy of undoped and Sn-doped TiO₂. Chapter 9 interconnects previous chapters by presenting 2D reciprocal space maps of nano structured epitaxial samples of In₂O₃ grown by the newly developed sol-gel based method. Chapter 10 concludes this thesis with a summary of the results.

Monolayers of the cationic surfactant hexadecyltrimethylammonium halide (CTAX, where X = F¯, Cl¯, Br¯, and I¯) have been studied at the air-water and oilwater interfaces. At the air-water interface, the effects of the halide counterion and the addition of counterion were investigated. Sum-frequency spectroscopy (SFS), ellipsometry, and surface tensiometry indicated that the counterion changed the efficiency and effectiveness of the surfactant, both decreasing in the order of Br¯> Cl¯>F¯. The addition of salt in the form of 0.1 M KX was found to reduce the cmc but had little effect on the limiting area per molecule attained at the cmc, which increased from 44 Ų for CTAB to 65 Ų for CTAC and ca. 94 Ų for CTAF. Neither SFS nor ellipsometry provided any firm evidence for specific effects of the halide ions on the structure of the surfactant monolayers. For CTAB monolayers in the absence of excess electrolyte, the effect of area per molecule on the sum-frequency (SF) spectra was studied. Mixed monolayers of CTAB and tetradecane at the air-water interface exhibit a first-order phase transition from a conformationally disordered to a conformationally ordered state as the temperature is lowered. The phase transition occurs ca. 11 °C above the bulk melting point of tetradecane. A new experimental arrangement is described for acquiring SF spectra from surfactants at the oil-water interface. The key features of this approach are the stabilisation of a thin oil film between a sapphire prism and an aqueous phase, and the use of total internal reflection to enhance the total signal and discriminate against signals from other interfaces in the system. With this new methodology, the first SF vibrational spectra of surfactant monolayers at an alkane-water interface were obtained. Surface tensiometry was used to characterise the monolayers further. The structure of CTAB monolayers at the hexadecane-water interface was determined by SFS and compared with monolayers of CTAB at the air-water interface. At low concentrations, CTAB/hexadecane showed the expected features in the C-H stretching region, characteristic of a conformationally disordered monolayer. As the bulk concentration approached the critical micelle concentration, the spectra changed to one characteristic of a more ordered, upright conformation. Ellipsometric measurements supported this conclusion. This qualitative structural change is not observed in analogous monolayers at the air-water interface or CCl₄-water interface, or in surfactant solutions in contact with a hydrophobic solid surface.

F₁-ATPase, the sector of ATP synthase where the synthesis of cellular ATP occurs, is a rotary molecular motor in its own right. Driven by ATP hydrolysis, direct observation of the rotation of the central axis within single molecules of F₁ is possible. Operating at close to 100% efficiency, F₁ from thermophilic Bacillus has been shown to produce ~40pN˙nm of torque during rotation. This thesis details the groundwork required for the direct measurement of the torque produced by F₁ using a rotary angle clamp, an optical trapping system specifically designed for application to rotary molecular motors. Proof-of-concept experiments will be presented thereby demonstrating the ability to directly manipulate single F₁ molecules from Escherichia coli and yeast mitochondria (Saccharomyces cerevisiae), along with activation of F₁ out of its inhibited state by the application of external torque. Despite in-depth knowledge of the rotary mechanism of F₁ from thermophilic Bacillus, the rotation of F₁ from Escherichia coli is relatively poorly understood. A detailed mechanical characterization of E.coli F₁ will be presented here, with particular attention to the ground states within the catalytic cycle, notably the ATP-binding state, the catalytic state and the inhibited state. The fundamental mechanism of E.coli F₁ appears to depart little from that of F₁ from thermophilic Bacillus, although, at room temperature, chemical processes occur faster within the E.coli enzyme, in line with considerations regarding the physiological conditions of the different species. Also presented here is the verification of the rotary nature of yeast mitochondrial F₁. The torque produced by F₁ from thermophilic Bacillus, E.coli and yeast mitochondria is the same, within experimental error, despite their diverse evolutionary and environmental origins.

Carbon-based materials are poised to be an important class of 21st century materials, for bio-medical, bio-electronic, and bio-sensing applications. Diamond and polymers are two examples of carbon-based materials of high interest to the bio-materials community. Diamond, in its conductive form, can be used as an electrochemical bio-sensor, whilst its nanoparticle form is considered a non-inflammatory platform to deliver drugs or to grow neuronal cells. Polymers, especially when chemically modified, have been used extensively in biological environments, from anti-microbial use to drug delivery. The large-scale use of either material for biological use is limited by two factors: ease of chemical modification and the paucity of knowledge of their surface chemistry in aqueous media. This thesis addresses aspects of both these issues. The first study reported is an in situ study of the adsorption dynamics of an exemplar globular protein (bovine serum albumin, BSA) on nanodiamond using the relatively novel quartz crystal microbalance with dissipation (QCM-D) technique. For the first time, QCM-D enabled the detailed study of protein dynamics (i.e. kinetics, viscoelastic properties, overlayer structure, etc.) onto nanodiamond thin films having various surface chemistry and roughness. The dynamics of protein adsorption is found to be sensitive to surface chemistry at all stages of adsorption, but it is only sensitive to surface roughness during initial adsorption phases. Our understanding of the nanodiamond-biology interface is enhanced by this study, and it suggests that QCM-D is useful for the study of the surface chemistry of nanoparticle forms of inorganic materials. A second study concerns a novel surface functionalization scheme, based on carbene and azo-coupling chemistry, which has been recently introduced as a practical, facile method for modifying the surfaces of polymers. Using modern surface characterization techniques, it is demonstrated that a chemical linker can be attached to polystyrene surfaces using carbene-based chemistry, and that further chemical functionality can be added to this chemical linker via an azo-coupling reaction. In situ studies of protein dynamics at these interfaces were conducted using QCM-D, thus enabling a link between specific protein behaviour and the polymer surface chemical termination chemistry to be made. A third area of study of investigates the use of diamond electrodes as a bio-sensor for dopamine under physiological conditions. For these conditions, ascorbic acid interferes with the dopamine oxidation signal, in ways that render the two signals irresolvable. Various modifications are used in attempts to reduce this interference, including: small and large cathodic treatments, grafting of electro-active polymers, addition of carbon nanotubes, and hydrogen plasma treatment. Those modifications leading to the hydrogen-termination of diamond are shown to work the best. Notably, hydrogen plasma treatment effects the complete electrochemical separation of dopamine and ascorbic acid at a diamond electrode. This is the first time this has been accomplished without adding non-diamond materials to the diamond electrode surface.

Atomic layer deposition (ALD) of copper films is getting enormous interest. Ultrathin Cu films are applied as the seed layer for electrochemical deposition (ECD) of copper in interconnect circuits and as the non-magnetic material for the realization of giant magnetoresistance (GMR) sensors. Particularly, Co/Cu multi-layered structures require sub 4.0 nm copper film thickness for obtaining strong GMR effects. The physical vapor deposition process for the deposition of the copper seed layers are prone to non-conformal coating and poor step coverage on side-walls and bottoms of trenches and vias, and presence of overhanging structures. This may cause failure of interconnections due to formation of voids after copper ECD. ALD is the most suitable technology for the deposition of conformal seed layers for the subsequent ECD in very high aspect ratio structures, also for the technology nodes below 20 nm. Surface chemistry during the ALD of oxides is quite well studied. However, surface chemistry during the ALD of pure metal is rather immature. This knowledge is necessary to optimize the process parameters, synthesize better precursors systems, and enhance the knowledge of existing metal ALD processes. The major goal of this work is to understand the surface chemistry of the used precursor and study the growth of ultrathin copper films using in-situ X-ray photoelectron spectroscopy (XPS). Copper films are deposited by ALD using the precursor mixture consisting of 99 mol% [(nBu3P)2Cu(acac)], as copper precursor and 1 mol% of Ru(η5 C7H11)(η5 C5H4SiMe3), as ruthenium precursor. The purpose in having catalytic amount of ruthenium precursor is to obtain the Ru doped Cu2O layers for subsequent reduction with formic acid at temperatures below 150 °C on arbitrary substrates. Two different approaches for the growth of ultrathin copper films have been studied in this dissertation. In the first approach, direct thermal ALD of copper has been studied by using H2 as co-reactant on Co as catalytic substrate. In the second approach, Ru-doped Cu2O is deposited by ALD using wet-O2 as co-reactant on SiO2 as non-catalytic substrate. The Ru-doped Cu2O is successfully reduced by using either formic acid or carbon-monoxide on SiO2. / Atomlagenabscheidung (ALD) von Kupfer steht im Fokus der ALD Gemeinschaft. Ultradünne Kupferschichten können als Keimschicht für die elektrochemische Abscheidung (ECD) von Kupfer in der Verbindungstechnologie eingesetzt werden. Sie können ebenfalls für Sensoren, welche auf den Effekt des Riesenmagnetowiderstandes (GMR) basieren, als nicht-ferromagnetische Zwischenschicht verwendet werden. Insbesondere Multischichtstrukturen aus ferromagnetische Kobalt und Kupfer erfordern Schichtdicken von weniger als 4,0 nm, um einen starken GMR-Effekt zu gewährleisten. Das derzeit verwendete physikalische Dampfabscheidungsverfahren für ultradünne Kupferschichten, ist besonders anfällig für eine nicht-konforme Abscheidung an den Seitenwänden und Böden von Strukturen mit hohem Aspektverhältnis. Des Weiteren kann es zur Bildung von Löchern und überhängenden Strukturen kommen, welche bei der anschließenden Kupfer ECD zu Kontaktlücken (Voids) führen können. Für die Abscheidung einer Kupfer-Keimschicht ist die ALD besonders gut geeignet, da sie es ermöglicht, ultradünne konforme Schichten auf strukturierten Oberflächen mit hohem Aspektverhältnis abzuscheiden. Dies macht sie zu einer der Schlüsseltechnologien für Struckturgrößen unter 20 nm. Im Gegensatz zur Oberflächenchemie rein metallischer ALD sind die Oberflächenreaktionen für oxidische ALD Schichten sehr gut untersucht. Die Kenntnis der Oberflächenchemie während eines ALD Prozesses ist essenziel für die Bestimmung von wichtigen Prozessparametern als auch für die Verbesserung der Präkursorsynthese ansich. Diese Arbeit beschäftigt sich mit der Untersuchung der Oberflächenchemie und Charakterisierung des Wachstums von ultradünnen Metall-Cu-Schichten mittels In-situ XPS, welche eines indirekten (Oxid) bzw. direkten Metall-ALD Prozesses abgeschieden werden, wobei die Kupfer-Oxidschichten im Anschluss einem Reduktionsprozess unterworfen werden. Hierfür wird eine Präkursormischung bestehend aus 99 mol% [(nBu3P)2Cu(acac)] und 1 mol% [Ru(η5 C7H11)(η5-C5H4SiMe3)] verwendet. Die katalytische Menge an Ru, welche in der entstehenden Cu2O Schicht verbleibt, erhöht den Effekt der Reduktion der Cu2O Schicht auf beliebigen Substraten mit Ameinsäure bei Wafertemperaturen unter 150 °C. In einem ersten Schritt wird ein direkter thermisches Kupfer ALD-Prozess, unter Verwendung von molekularem Wasserstoff als Coreaktant, auf einem Kobalt-Substrat untersucht. In einem zweiten Schritt wird ein indirekter thermischer Cu2O-ALD-Prozess, unter gleichzeitiger Verwendung von Sauerstoff und Wasserdampf als Coreaktant, mit anschließender Reduktion durch Ameinsäure oder Kohlenstoffmonoxid zu Kupfer auf den gleichen Substraten betrachtet. Die vorliegende Arbeit beschreibt das Wachstum von ultradünnen und kontinuierlichen Kupfer-Schichten mittels thermischer ALD auf inerten- SiO2 und reaktiven Kobalt-Substraten.

This thesis presents the development and redesign of a commercial electrochemical quartz crystal microbalance with dissipation (E–QCM–D). This was used to study factors affecting the efficiency of the four electron reduction catalysed by the fuel cell enzyme bilirubin oxidase from Myrothecium verrucaria immobilised on thiol modified gold surfaces. Within this thesis, the E–QCM–D was used to show that application of a constant potential to bilirubin oxidase adsorbed to thiol-modified gold surfaces causes activity loss that can be attributed to a change in structural arrangement. Varying the load by potential cycling distorts the enzyme by inducing rapid mass loss and denaturation. Attaching the enzyme covalently reduces the mass loss caused by potential cycling but does not mitigate activity loss. Covalent attachment also changes the orientation of the surface bound enzyme as verified by the position of the catalytic wave (related to the overpotential for catalysis) and reactive labelling followed by mass spectrometry analysis. The E–QCM–D was used to show how electrostatic interactions affect enzyme conformation where high pH causes a reduction in both mass loading at the electrode and a reduction in activity. At pH lower than the enzyme isoelectric point, there is a build up of multilayers in a clustered adsorption. When enzyme adsorbs to hydrophobic surfaces there is a rapid denaturation which completely inactivates the enzyme. Changing the surface chemistry from carboxyl groups to hydroxyl and acetamido groups shows that catalysis is shifted to more negative potentials as a result of an enzyme misorientation. Further to this, increasing the chain length of the thiol modifier indicates that an increased distance between surface and enzyme reduces activity, enzyme loading and results in a conformational rearrangement that permits electron transfer over longer distances.