Ce travail de thèse est focalisé sur la détermination, de manière non-destructive, d'interfaces profondément enterrées dans des empilements multi-couches utilisés dans les conditions de technologie réelles au travers d'une méthode innovante basée sur la photoémission avec utilisation de rayons-x de haute énergie (HAXPES) et l'analyse du fond continu inélastique. Au cours de cette thèse, une procédure numérique a été développée pour quantifier la correspondance entre la mesure du fond continu faite par HAXPES et la simulation du fond continu représentative d'une distribution en profondeur donnée. Cette méthode permet de trouver la distribution en profondeur d'un élément grâce à une procédure semi automatisée. Dans un premier temps cette méthode a été testée en étudiant une couche ultra fine de lanthane enterrée à une profondeur >50 nm dans un dispositif de grille métallique high-k. L'influence des paramètres utilisés lors de l'analyse y est étudiée et révèle l'importance principale d'un paramètre en particulier, la section efficace de diffusion inélastique. La combinaison de mesures HAXPES avec l'analyse du fond continu inélastique utilisant cette nouvelle méthode permet d'augmenter la profondeur de sonde jusqu'à un niveau sans précédent. Ainsi l'échantillon peut être sondé jusqu'à 65 nm sous la surface avec une haute sensibilité à une couche nanométrique. Dans un second temps, la méthode précédemment validée d'analyse de fond continu inélastique est combinée avec une étude haute résolution des niveaux de cœur dans un échantillon servant de source dans un transistor à haute mobilité. Les deux analyses sont complémentaires puisqu'elles permettent d'obtenir la distribution en profondeur des éléments ainsi que leur environnement chimique. Le résultat donne une description complète des diffusions élémentaires dans l'échantillon suivant les différentes conditions de recuit. / This thesis tackles the challenge of probing in a non-destructive way deeply buried interfaces in multilayer stacks used in technologically-relevant devices with an innovative photoemission method based on Hard X-ray PhotoElectron Spectroscopy (HAXPES) and inelastic background analysis. In this thesis, a numerical procedure has been implemented to quantify the matching between a HAXPES measured inelastic background and a simulated inelastic background that is representative of a given depth distribution of the chemical elements. The method allows retrieving depth distributions at large depths via a semi-automated procedure. First, this method has been tested by studying an ultra-thin layer of lanthanum buried at depth >50 nm in a high-k metal gate sample. The influence of the parameters involved in the analysis is studied unraveling the primary importance of the inelastic scattering cross section. The combination of HAXPES with inelastic background analysis using this novel method maximizes the probing depth to an unprecedented level, allowing to probe the sample up to 65 nm below the surface with a high sensitivity to a nm-thick layer. Second, the previously-checked inelastic background analysis is combined with that of high resolution core-level spectra in the case of the source part of a high electron mobility transistor. The two analyses are complementary as they allow retrieving the elemental depth distribution and the chemical state, respectively. The result gives a complete picture of the elemental intermixing within the sample when it is annealed at various temperatures. / Denne afhandling omhandler problemet med at probe dybt begravede grænseflader i multilags stacks, som bruges i teknologisk relevante devices, med en innovativ fotoemissions metode, der er baseret på Hard X-ray PhotoElectron Spectroscopy (HAXPES) og analyse af den uelastiske baggrund. I afhandlingen er en numerisk procedure blevet implementeret til at kvantificere forskellen mellem en HAXPES målt uelastisk baggrund og en modelleret baggrund, som svarer til en given dybdefordeling af atomerne. Metoden muliggør, med en halv-automatisk procedure, at bestemme dybdefordelingen i store dybder. Metoden er først blevet testet ved at studere et ultra-tyndt lag af lanthan, som er begravet i en dybde > 50 nm i en high-k-metal-gate prøve. Indflydelsen af parametrene der ingår i analysen er blevet studeret for at opklare den primære betydning af det anvendte uelastiske spredningstværsnit. Kombinationen af HAXPES med analyse af den uelastiske baggrund og brug af den nye numeriske metode giver en hidtil uset probe-dybde, som giver mulighed for at probe den atomare sammens ætning i op til 65 nm dybde under overfladen og med høj følsomhed af et kun nm tykt lag. Dernæst er den uelastiske baggrundsanalyse blevet kombineret med højopløst core-level spektroskopi for at studere de aktive dele i en høj-elektronmobilitets transistor. De to analyser er komplementære, idet de henholdsvis bestemmer den atomare fordeling og atomernes kemiske bindingstilstand. Resultatet giver et fuldstændigt billede af atomernes omfordeling i prøven når denne opvarmes til forskellige temperaturer.

Electron cloud is an unwanted effect limiting the performance of particle accelerators with positively charged particle beams of high-intensity and short bunch spacing. However, electron cloud caused by beam induced multipacting can be sufficiently suppressed if the secondary electron yield (SEY) of accelerator chamber surface is lower than unity. Usually, the SEY is reduced by two ways: modification of surface chemistry and engineering the surface roughness. The objective of this PhD project is a systematic study of SEY as a function of various surface related parameters such as surface chemistry and surface morphology, as well as an effect of such common treatments for particle accelerators as beam pipe bakeout and surface conditioning with a beam, ultimately aiming to engineer the surfaces with low SEY for the electron cloud mitigation. In this work, transition metals and their coatings and laser treated surface were studied as a function of annealing treatment and electron bombardment. The transition metal thin films have been prepared by DC magnetron sputtering for further test. In the first two Chapter of this thesis, the literature review on electron emission effect is introduced, which includes the process of the electron emission, the influence factor and examples of low SEY materials. In the third Chapter, the experimental methods for SEY measurements and surface investigation used in this work are described. In Chapter 4, the SEY measurement setup which is built by myself are introduced in detail. In Chapter 5 transition metals and their coatings and non-evaporable getter (NEG) coatings have been studied. All the samples have been characterized by SEY measurements, their surface morphology was analysed with Scanning Electron Microscopy (SEM) and their chemistry was studied with X-ray Photoelectron Spectroscopy (XPS). Different surface treatments such as conditioning by electron beam, thermal treatment under vacuum on the sample surfaces have been investigated. For example, the maximum SEY (δmax) of as-received Ti, Zr, V and Hf were 2.30, 2.31, 1.72 and 2.45, respectively. After a dose of 7.9x10-3 C mm-2, δmax of Ti drops to 1.19. δmax for Zr, V and Hf drop to 1.27, 1.48 and 1.40 after doses of 6.4x10-3 C mm-2, 1.3x10-3 and 5.2x10-3 C mm-2, respectively. After heating to 350 °C for 2.5 hours, the SEY of bulk Ti has dropped to 1.21 and 1.40, respectively. As the all bulk samples have a flat surface, there are no difference of morphology. So this reduction of SEY is believed to be a consequence of the growth of a thin graphitic film on the surface after electron bombardment and the removal of the contaminations on the surface after annealing. Chapter 6 of this thesis is about the laser treated surface. Laser irradiation can transform highly reflective metals to black or dark coloured metal. From SEM results, metal surfaces modified by a nanosecond pulsed laser irradiation form a highly organised pyramid surface microstructures, which increase the surface roughness. Due to this reason, δmax of as-received laser treated surface could be lower than 1, which can avoid the electron cloud phenomenon. In this Chapter, the influence of different laser treatment parameters, such as power, hatch distance, different atmospheres on SEY has been investigated. Meanwhile, different surface treatments such as electron conditioning and thermal treatments are studied on the laser treated surface with the investigation of XPS. For example, the δmax of as-received type I with hatch distance 50, 60 and 80 μm in Air are 0.75, 0.75 and 0.80, respectively. After heating to 250 °C for 2 hours, in all case the δmax drop to 0.59, 0.60, 0.62, respectively. The SEYs of all as-received samples are lower than 1 due to the increasing the roughness on the surface by the special pyramid structure. After thermal treatment, the SEY reduces even further. This is caused by removing the contaminations on the surfaces. In conclusion, the present study has largely improved the knowledge of the electron cloud mitigation techniques by surface engineering of vacuum chambers. On the one hand, the surface treatments can modify the surface chemistry, such as the produce the graphic carbon layer on the surface by electron condition and the removal the contamination layer on the top of the surface by thermal treatment. On the other hand, the SEY could be critically low by engineering the surface roughness. Both methods allow reaching δmax less than unity. The efficiency of laser treated surface for e-cloud was demonstrated for a first time leading to a great interest to this new technology application for existing and future particle accelerators.

This thesis presents work based on the interactions of water soluble caboxylated zinc phthalocyanines (Pcs) and coreshell quantum dots (QDs). The Pcs are ZnPc(COOH)₈ and ZnPc(COOH)₄ and coreshell QDs are CdTe@ZnS-GSH. GSH = L-glutathione. Characterization and photophysical studies of conjugates were carried out. The approach of coordinating Pcs to QDs was achieved using an organic cross linker, N-N’-dicyclohexylcarbodiimide (DCC) at pH 10 at room temperature. Employing atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman, infrared and X-ray photoelectron spectroscopies, the formation of the conjugates was confirmed. Upon conjugation with Pc derivatives, the fluorescence quantum yield of CdTe@ZnS-GSH decreased due to energy transfer from the QDs to the Pc. The average fluorescence lifetime of the CdTe@ZnS-GSH QD also decreased upon conjugation. The föster resonance energy transfer (FRET) behaviour of CdTe@ZnS-GSH-ZnPc(COOH)₄ conjugates was compared to that of CdTe@ZnS-GSH-ZnPc(COOH)₈. Higher FRET efficiencies were observed for CdTe@ZnS-GSH-ZnPc(COOH)₄-mixed or CdTe@ZnS-GSH-ZnPc(COOH)₄-linked compared to the corresponding CdTe@ZnS-GSH-ZnPc(COOH)₈-mixed or CdTe@ZnS-GSH-ZnPc(COOH)₈-linked. Triplet quantum yield (ΦT) and lifetime (ΤT) of ZnPc(COOH)₈ were found to increase in the presence of coreshell QDs. Though the singlet quantum yield (ΦΔ) value of ZnPc(COOH)8 was lower than ΦT , there was a slight upsurge in the ΦT in the presence of QDs. / Microsoft� Word 2010 / Adobe Acrobat 9.53 Paper Capture Plug-in

En raison de leur faible consommation d'énergie, les mémoires non volatiles (MNV) sont En raison de leur faible consommation d'énergie, les mémoires non-volatiles sont particulièrement intéressantes pour l'électronique portative (clé USB, téléphone, ordinateur portable …). Les mémoires Flash, qui dominent le marché, atteignent leurs limites physiques et doivent être remplacées. L'introduction de nouveaux matériaux et architectures mémoire est proposée. Les mémoires OxRRAM (Oxide Resistive Random Access Memory) sont des candidats potentiels. Il s'agit de structures M-O-M (Métal-Oxyde-Métal). Le stockage de l'information est basé sur la modulation de la résistance de l'oxyde à l'application d'un champ électrique ou d'un courant. Une meilleure compréhension du mécanisme de changement de résistance de ces dispositifs est nécessaire pour contrôler leurs performances. Nous nous intéressons au claquage diélectrique de l'oxyde, qui initie le mécanisme de changement de résistance. Les mesures physico-chimiques à l'échelle nanométrique sont indispensables à sa compréhension et font défaut dans la littérature. Dans cette thèse, nous proposons des mesures physico-chimiques, des mesures électriques et des méthodes de préparation d'échantillon adaptées. Les oxydes de nickel et d'hafnium sont investigués. En plus de la dégradation électrique (chute de résistance), les modifications de ces deux oxydes sont investiguées à trois niveaux : la composition chimique, la morphologie et la structure électronique. Mots-clés : mémoire résistive, mécanisme de changement de résistance, claquage diélectrique, NiO, HfO2, spectroscopie de photoélectrons, microscopie électronique en transmission, microscopie à forme atomique, lacunes d'oxygène. / With low energy consumption, non-volatile memories are interesting for portative applications (USB, mobile phone, laptop …). The Flash memory technology is reaching its physical boundaries and needs to be replaced. New materials and architectures are currently investigated. Oxide Resistive Random Access Memory (OxRRAM) is considered as a good candidate. It is based on a M-O-M (Metal-Oxide-Metal) stack. The information is stored using an electric field or a current that modulates the resistance of the oxide. A better understanding of the resistance switching mechanism is required in order to control the performances of the devices. We investigate the dielectric breakdown that activates the resistance switching properties. Physico-chemical characterization at the nanoscale is required. In this work, we propose proper physico-chemical and electrical measurements. Sample preparation is also considered. Nickel and hafnium oxide are investigated. Besides the evolution of the electrical properties, we analyze the oxide modification at three levels : the chemical composition, the morphology and the electronic structure. Keywords : resistive memory, resistance switching mechanism, dielectric breakdown, NiO, HfO2, photoelectron spectroscopy, electronic transmission microscopy, atomic force microscopy, oxygen vacancies.

Examination of the paper insulation and copper stress braiding during stripdown of a number of Current Transformers (FMK type 400kV) has revealed the presence of dark deposits. Copper foils are often interspersed within layers of paper insulation and mineral oil found in transformer windings. The dark deposits were often found in association with these foils, affecting several layers of paper in addition to the layer in contact with the copper foil. This thesis describes the research undertaken to identify these deposits and establish a mechanism for the transportation through the paper layers. Preliminary investigation using scanning electron microscopy (SEM) in conjunction with energy dispersive X-ray analysis (EDX) has shown these dark deposits to be copper based. X-ray photoelectron spectroscopy was used to show that the transport of the copper deposit through the paper insulation was working under the influence of a diffusion controlled process, related to Fick's law. Laboratory studies in support of work designed to eliminate the problem have shown that corrosion of copper occurs in mineral oils containing a trace of oxygen. This corrosion is non protective in character and leads to migration of copper into adjacent layers of paper. It has been shown that the transport of copper through several layers of paper can be measured by XPS and that the concentration from one paper winding to the next declines in accord with Fick's law for non-steady state diffusion. Measurements of surface concentrations by XPS correlate well with measurements made with atomic absorption spectroscopy on solutions of extracts of the contaminated paper. The laboratory measurements have allowed determination of the diffusion coefficients and activation energy for the transport process and thus give a basis for interpretation of the diffusion profiles found in the transformer in terms of time and temperature of operation. The diffusion process is temperature dependant. The results have been used to produce long term prediction curves.

Doctor of Philosophy / Department of Chemistry / Peter M.A. Sherwood / This dissertation will examine the fabrication of different phosphorus containing films and their use as corrosion preventative films and adhesion materials between polymers and metal and metal alloys. Orthophosphate films are used in several metals and metal alloys to prevent corrosion and promote adhesion between paints or polymers and metal substrates. One key component is to examine the use of different phosphorus containing acids that might lead to phosphorus containing films which would compliment the mainly orthophosphate films currently in use. The objectives of this study are to see if it is possible to fabricate different phosphorus containing films, use them to adhere polymers to metal and metal alloys, and test the phosphorus containing films’ and polymer films’ corrosion protection properties. The thermoplastic resin, Poly(ether ketone ketone), or PEKK was found to adhere well to different phosphorus containing films and protect the underlying layers from oxidation in 4-D water. The phosphorus containing films were created by electrochemical deposition in different 5 M phosphorus containing acids. The metal or metal alloy was abraded to remove the native oxide and treated in the electrochemical cell. The second, separate polymer films were created by dip coating the metal or metal alloy in a polymer solution. The film thickness in both cases was controlled to be less than 100Å to ensure that the underlying metal or metal alloy could be detected. The surface chemical analysis was collected using X-ray photoelectron spectroscopy, or XPS. Core level and valence band XPS were used to distinguish the differences in the chemistry at the surfaces. The valence band XPS spectra were interpreted using spectra generated by multiple scattered wave calculations and band structure calculations. In the cases were more than one film was present subtraction and addition spectrum were used to interpret the chemistry in the interface region of the films.

Different approaches to surface modification were investigated in this work on gold, glassy carbon, multi-walled carbon nanotube paper and on single-walled carbon nanotubes adsorbed on glassy carbon. These approaches include electrochemical grafting, electropolymerisation, click chemistry, axial ligation, adsorption and self-assembled monolayers. The modified surfaces were characterised using a variety of techniques; predominantly electrochemistry, scanning electrochemical microscopy and X-ray photoelectron spectroscopy. For the formation of self-assembled monolayers on gold, four new manganese(III) phthalocyanines (1a-d), octa-substituted at the peripheral position with pentylthio, decylthio, benzylthio, and phenylthio groups were synthesized and characterised. X-ray photoelectron spectroscopy was used to show the formation of a sulphur-gold bond. A number of approaches using 4-azidoaniline (2a) combined with azide-alkyne click chemistry and electrochemistry were also used to anchor ferrocene and pyridine moieties on to the carbon surfaces, including direct in situ diazotation and grafting, electropolymerisation, and the synthesis of the diazonium salt followed by grafting. Iron phthalocyanine was linked to the pyridine-clicked surfaces through axial ligation, where the strong axial bond formed by the interaction between the central metal and the lone pair of the nitrogen in the pyridine group resulted in stable modified electrodes. The potential of these surfaces for the detection of analytes such as thiocyanate, hydrazine and sulphite are briefly shown as well. This work also describes for the first time the possibility of performing local micro-electrochemical grafting of a gold substrate by 4-azidobenzenediazonium (2b) using scanning electrochemical microscopy in a single and simple one step approach, without complications from adsorption.

Abstract In this work, evolution of structural properties of anhydrous and hydrated alkali halide clusters are studied using synchrotron radiation based photoelectron spectroscopy. Alkali metal core level spectra of small anhydrous RbCl, RbBr, CsCl and CsBr clusters indicate a NaCl structure. For larger CsBr clusters a structural phase transition to CsCl structure is likely the case. Alkali halide core level spectra of mixed RbBr-water clusters indicate that at dilute concentration the salt is dissolved by the water cluster but ion pairing increases with concentration. Modeling of gas phase cluster formation and electronic structure calculations of core level chemical shifts are used to interpret the experimental spectra.

This thesis is concerned with the chemistry and physics of C(100) surfaces of diamond. The polished and cleaned C(100) surface is examined by surface microscopy (Atomic-force Microscopy), electron diffraction (Low-energy Electron Diffraction) and photoemission (X-ray Photoelectron Spectroscopy and Ultra-violet Photoelectron Spectroscopy). Results are presented on the presence of oxygen, nitrogen and hydrogen/deuterium on the C(100) surface. Finally, the valence band structure of diamond is probed by angle-resolved photoemission. We have confirmed by AFM that the grooves from the soft polishing process are present on a polished C(100) surface and found sporadic traces of hard polish on a surface polished in the soft polishing direction. XPS studies have verified heating cycles by electron beam bombardment as a suitable cleaning procedure for pure reconstructed C(100) surfaces. By allowing the crystal to cool slowly, the first experimental evidence of quarter-order LEED spots have been found, which suggest that buckled dimerisation might have occurred similar to those on Si(100) and Ge(100). We present the first experimental electron spectroscopy results for a nitrogen impurity in diamond by showing the N KLL Auger spectrum. An attempt to smooth a C(100) surface of diamond by an atomic hydrogen plasma did not succeed. AFM studies showed no evidence for the surface smoothing reported in other studies, but the results enable us to explain the different plasma published in the literature. The valence band of diamond is investigated by off-normal ARUPS. The features observed are consistent with possible transitions, which are determined using bulk band structure calculations and comparison with the experimental binding energies.

Title: Model systems with the use of CeO2 for bioapplication Author: Sofiia Bercha Department: Department of Surface and Plasma Science Supervisor: Ing. Nataliya Tsud Ph.D., Department of Surface and Plasma Science Abstract: This thesis is focused on the investigation of model systems for bioapplications. Interfaces between biomolecules and inorganic materials were studied by means of advanced surface science techniques with emphasis on the molecular electronic structure and bonding geometry as a function of material morphology and/or molecular deposition method. For the histidine/cerium oxide system it is demonstrated that the morphology of the oxide determines the mechanism of the molecular adsorption. The presence of an aqueous medium does not alter the histidine interaction with the nanostructured cerium oxide. For the adenine/cerium oxide system we have shown that the adenine molecule chemisorbs on CeO2 intact via nitrogen atoms, independent of the oxide morphology and deposition technique. The adenine molecule was found to decompose on a reduced surface of the cerium oxide. Combining experimental and theoretical methods two distinct phases of adenine on CeO2 were found. For adenine/Cu(111) system it was shown that the strong interaction with the surface keeps the molecule intact on the surface till...