abstract: Recent improvements in energy resolution for electron energy-loss spectroscopy in the scanning transmission electron microscope (STEM-EELS) allow novel effects in the low-loss region of the electron energy-loss spectrum to be observed. This dissertation explores what new information can be obtained with the combination of meV EELS energy resolution and atomic spatial resolution in the STEM. To set up this up, I review nanoparticle shape effects in the electrostatic approximation and compare the “classical” and “quantum” approaches to EELS simulation. Past the electrostatic approximation, the imaging of waveguide-type modes is modeled in ribbons and cylinders (in “classical" and “quantum" approaches, respectively), showing how the spatial variations of such modes can now be imaged using EELS. Then, returning to the electrostatic approximation, I present microscopic applications of low-loss STEM-EELS. I develop a “classical” model coupling the surface plasmons of a sharp metallic nanoparticle to the dipolar vibrations of an adsorbate molecule, which allows expected molecular signal enhancements to be quantified and the resultant Fano-type asymmetric spectral line shapes to be explained, and I present “quantum” modelling for the charged nitrogen-vacancy (NV-) and neutral silicon-vacancy (SiV0) color centers in diamond, including cross-sections and spectral maps from density functional theory. These results are summarized before concluding. Many of these results have been previously published in Physical Review B. The main results of Ch. 2 and Ch. 4 were packaged as “Enhanced vibrational electron energy-loss spectroscopy of adsorbate molecules” (99, 104110), and much of Ch. 5 appeared as “Prospects for detecting individual defect centers using spatially resolved electron energy loss spectroscopy” (100, 134103). The results from Ch. 3 are being prepared for a forthcoming article in the Journal of Chemical Physics. / Dissertation/Thesis / Doctoral Dissertation Physics 2020

Les premières photographies couleurs produites par Edmond Becquerel au Muséum d’Histoire naturelle à Paris en 1848 ont suscité un débat scientifique intense tout au long du XIXème siècle. La question de l’origine des couleurs de ces photographies a vu s’affronter les partisans d’une hypothèse pigmentaire et ceux d’une hypothèse interférentielle. Au cours du XXème siècle, cette question n’a pas été définitivement tranchée. Ce travail doctoral se propose d’appréhender la nature de ces images dites « photochromatiques » par une approche expérimentale. Nous nous sommes dans un premier temps intéressés aux étapes de sensibilisation du plaqué argent et d’exposition de la surface sensible aux rayonnements visibles, dans le but de répliquer le procédé Becquerel et de comprendre la photosensibilité de ces images. Les propriétés optiques des couches sensibles et colorées ont été caractérisées en spectroscopie UV-visible et mises en relation avec leurs compositions chimiques (étudiées en XAS) et leurs morphologies, de l’échelle micro- à nanométrique (étudiées en MEB et TEM). La grande sensibilité des échantillons aux faisceaux photoniques (UV-visible et rayons X) et électroniques a imposé un développement méthodologique afin de comprendre et de limiter les effets de sonde. Les résultats de cette recherche permettent de réfuter l’hypothèse de phénomènes interférentiels comme origine des couleurs des images photochromatiques, hypothèse qui prévaut dans la littérature depuis la fin du XIXème siècle. Les couches sensibles et colorées sont constituées de grains de chlorure d’argent micrométriques décorés de nanoparticules d’argent. Ces nanoparticules d’argent, que nous avons étudiées en EELS low loss, sont responsables de l’absorption dans le visible des couches sensibles et colorées par résonance de plasmons de surface. Ceci nous conduit à proposer une origine plasmonique aux couleurs des images photochromatiques, hypothèse discutée dans cette thèse. / The first colour photographs were produced in 1848 by Edmond Becquerel at the Museum of natural History in Paris. The origin of their colours motivated an intense debate between the scientists during the XIXth century. Two main hypotheses were proposed, namely a pigmentary hypothesis and an interferential hypothesis. Nowadays the question of the colours of those photochromatic images is still not settled and this doctoral research aims at addressing it by an experimental approach. We first studied the sensitizing of the silver plate and the exposure of the sensitive surface to light in order to replicate the Becquerel process and to gain information on the photosensitivity of these images. The optical properties of the sensitized and coloured layers were characterized by UV-visible spectroscopy and related to their chemical composition (studied by XAS) and their morphologies, from the micro to the nanoscale (studied by SEM and TEM). A methodological development was necessary to understand and overcome the sensitivity of the samples to photonic beams (UV-visible and X-rays) and electronic beams. The results allow us to reject the interferential hypothesis, which prevailed since the end of the XIXth century. The sensitized and coloured layers consist in micrometric silver chloride grains decorated by silver nanoparticles. Besides, these nanoparticles, which we investigated by low loss EELS, are responsible for the visible absorption of sensitized and coloured layers through surface plasmon resonance. We suggest that the photochromatic images colours have a plasmonic origin and hereby discuss this hypothesis.

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<p>Alumina-Zirconia thin films were grown on a range of substrates using dual magnetron sputtering. Film growth was achieved at a relatively low temperature of 450 °C and at higher temperatures up to 810 °C. The films were grown on well-defined surfaces such as silicon (100) but also on industrially relevant substrates such as hardmetal (WC-Co). Radio frequency power supplies were used in combination with magnetron sputtering to avoid problems with target arcing. A range of film compositions were possible by varying the power on each target. The influence of sputtering target were investigated, both ceramic oxide targets and metallic targets being used.</p><p>The phase composition of the as-deposited films was investigated by x-ray diffraction. The pure zirconia films contained the monoclinic zirconia phase, while the pure alumina films appeared either amorphous or contained the gamma-alumina phase. The composite films contained a mixture of amorphous alumina, gamma-alumina and the cubic zirconia phase. In-depth high-resolution electron microscopy studies revealed that the microstructures consisted of phase-separated alumina and zirconia nanocrystals in the case of the nanocomposites. In-situ spectroscopy was also performed to characterise the nature of the bonding within the as-deposited films.</p><p>The oxygen stoichiometry in the films was investigated as a possible reason for the stabilisation of the cubic zirconia phase in the nanocomposite. Ion beam techniques such as Rutherford backscattering scattering and electron recoil detection analysis were used in these studies. The growth of films with ceramic targets led to films that may be slightly understoichiometric in oxygen, causing the phase stabilisation. The growth of films from metallic targets necessitates oxygen rich plasmas and it is not expected that such films will be oxygen deficient.</p><p>Initial attempts were also made to characterise the mechanical properties of the new material with nanoindentation. The nanocomposite appeared to have greater resistance to wear than the pure zirconia film. In doing so, some surface interactions and some material interactions have been studied.</p> / Report code: LIU-TEK-LIC-2006:41

<p>Two new methods for calculating the double differential scattering cross-section (DDSCS) in electron energy loss spectroscopy (EELS) have been developed, allowing for simulations of sample geometries which have been unavailable to earlier methods of calculation. The new methods concerns the calculations of the <em>thickness function</em> of the DDSCS. Earlier programs have used an analytic approximation of a sum over the lattice vectors of the sample that is valid for samples with parallel entrance and exit surfaces.The first of the new methods carries out the sum explicitly, first identifying the unit cells illuminated by the electron beam, which are the ones needed to be summed over. The second uses an approach with Fourier transforms, yielding a final expression containing the <em>shape amplitude</em>, the Fourier transform of the <em>shape function</em> defining the shape of the electron beam inside the sample. Approximating the shape with a polyhedron, one can quickly calculate the shape amplitude as sums over it’s faces and edges. The first method gives fast calculations for small samples or beams, when the number of illuminated unit cells is small. The second is more efficient in the case of large beams or samples, as the number of faces and edges of the polyhedron used in the calculation of the shape amplitude does not need to be increased much for large beams. A simulation of the DDSCS for magnetite has been performed, yielding diffraction patterns for the L₃ edge of the three Fe atoms in its basis.</p>

Alumina-Zirconia thin films were grown on a range of substrates using dual magnetron sputtering. Film growth was achieved at a relatively low temperature of 450 °C and at higher temperatures up to 810 °C. The films were grown on well-defined surfaces such as silicon (100) but also on industrially relevant substrates such as hardmetal (WC-Co). Radio frequency power supplies were used in combination with magnetron sputtering to avoid problems with target arcing. A range of film compositions were possible by varying the power on each target. The influence of sputtering target were investigated, both ceramic oxide targets and metallic targets being used. The phase composition of the as-deposited films was investigated by x-ray diffraction. The pure zirconia films contained the monoclinic zirconia phase, while the pure alumina films appeared either amorphous or contained the gamma-alumina phase. The composite films contained a mixture of amorphous alumina, gamma-alumina and the cubic zirconia phase. In-depth high-resolution electron microscopy studies revealed that the microstructures consisted of phase-separated alumina and zirconia nanocrystals in the case of the nanocomposites. In-situ spectroscopy was also performed to characterise the nature of the bonding within the as-deposited films. The oxygen stoichiometry in the films was investigated as a possible reason for the stabilisation of the cubic zirconia phase in the nanocomposite. Ion beam techniques such as Rutherford backscattering scattering and electron recoil detection analysis were used in these studies. The growth of films with ceramic targets led to films that may be slightly understoichiometric in oxygen, causing the phase stabilisation. The growth of films from metallic targets necessitates oxygen rich plasmas and it is not expected that such films will be oxygen deficient. Initial attempts were also made to characterise the mechanical properties of the new material with nanoindentation. The nanocomposite appeared to have greater resistance to wear than the pure zirconia film. In doing so, some surface interactions and some material interactions have been studied. / Report code: LIU-TEK-LIC-2006:41

Two new methods for calculating the double differential scattering cross-section (DDSCS) in electron energy loss spectroscopy (EELS) have been developed, allowing for simulations of sample geometries which have been unavailable to earlier methods of calculation. The new methods concerns the calculations of the thickness function of the DDSCS. Earlier programs have used an analytic approximation of a sum over the lattice vectors of the sample that is valid for samples with parallel entrance and exit surfaces.The first of the new methods carries out the sum explicitly, first identifying the unit cells illuminated by the electron beam, which are the ones needed to be summed over. The second uses an approach with Fourier transforms, yielding a final expression containing the shape amplitude, the Fourier transform of the shape function defining the shape of the electron beam inside the sample. Approximating the shape with a polyhedron, one can quickly calculate the shape amplitude as sums over it’s faces and edges. The first method gives fast calculations for small samples or beams, when the number of illuminated unit cells is small. The second is more efficient in the case of large beams or samples, as the number of faces and edges of the polyhedron used in the calculation of the shape amplitude does not need to be increased much for large beams. A simulation of the DDSCS for magnetite has been performed, yielding diffraction patterns for the L3 edge of the three Fe atoms in its basis.

With growing demand for cardiovascular implants, improving the performance of artificial blood-contacting devices is a task that deserves close attention. Current prostheses made of fluorocarbon polymers such as expanded polytetrafluoroethylene (ePTFE) suffer from early thrombosis and require periodic replacement. A great number of attempts have already been made to improve blood compatibility of artificial surfaces, but only few of them found commercial implementation. One of the surfaces under intensive research for cardiovascular use is amorphous carbon-based coatings produced by means of the plasma-assisted deposition. However, this class of coatings can be produced using various techniques leading to a number of coatings with different properties. Carbon coatings produced in different plasmas may be of hard diamond-like type or soft graphite-like type, doping with different elements also changes the surface structure and properties. Taking this into account, the search for blood-compatible coating requires the understanding of surface composition and structure and its influence on blood-compatibility. This work attempts to advance our knowledge of this field. Here, commercial PTFE thin film was used as a working material, which composition corresponds to the composition of modern ePTFE vascular grafts and which compatibility with blood we tried to improve by deposition of nitrogenated amorphous carbon (a-CN) coatings in the plasma. Biocompatibility was assessed by a number of tests including the interaction with whole blood and various cells such as platelets, endothelial cells, neutrophils, and fibroblasts. Most of tests showed the blood compatibility of coated surface is better than that of untreated PTFE. Physico-chemical and morphological properties of coated surfaces were studied in parallel using x-ray photoemission spectroscopy (XPS), electron energy loss spectroscopy (EELS), x-ray absorption spectroscopy (XAS), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM). Some correlation between the structure of coatings and blood compatibility was inferred. It was found that at first nitrogen incorporation into amorphous carbon film stimulates blood compatibility. However, when nitrogen fraction increases over 23-25 %, no further improvement but reduction of blood compatibility was observed. Conclusion is made that for best biomedical performance, nitrogen percentage in a-CN coatings must be adjusted to the optimum value.

With growing demand for cardiovascular implants, improving the performance of artificial blood-contacting devices is a task that deserves close attention. Current prostheses made of fluorocarbon polymers such as expanded polytetrafluoroethylene (ePTFE) suffer from early thrombosis and require periodic replacement. A great number of attempts have already been made to improve blood compatibility of artificial surfaces, but only few of them found commercial implementation. One of the surfaces under intensive research for cardiovascular use is amorphous carbon-based coatings produced by means of the plasma-assisted deposition. However, this class of coatings can be produced using various techniques leading to a number of coatings with different properties. Carbon coatings produced in different plasmas may be of hard diamond-like type or soft graphite-like type, doping with different elements also changes the surface structure and properties. Taking this into account, the search for blood-compatible coating requires the understanding of surface composition and structure and its influence on blood-compatibility. This work attempts to advance our knowledge of this field. Here, commercial PTFE thin film was used as a working material, which composition corresponds to the composition of modern ePTFE vascular grafts and which compatibility with blood we tried to improve by deposition of nitrogenated amorphous carbon (a-CN) coatings in the plasma. Biocompatibility was assessed by a number of tests including the interaction with whole blood and various cells such as platelets, endothelial cells, neutrophils, and fibroblasts. Most of tests showed the blood compatibility of coated surface is better than that of untreated PTFE. Physico-chemical and morphological properties of coated surfaces were studied in parallel using x-ray photoemission spectroscopy (XPS), electron energy loss spectroscopy (EELS), x-ray absorption spectroscopy (XAS), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM). Some correlation between the structure of coatings and blood compatibility was inferred. It was found that at first nitrogen incorporation into amorphous carbon film stimulates blood compatibility. However, when nitrogen fraction increases over 23-25 %, no further improvement but reduction of blood compatibility was observed. Conclusion is made that for best biomedical performance, nitrogen percentage in a-CN coatings must be adjusted to the optimum value.

Il existe actuellement deux structures nanotubulaires largement étudiées : les nanotubes de carbone (CNTs) possédant un gap de l'ordre de 1 eV et ceux de nitrure de bore (BN-NTs) dont le gap est compris entre 5 et 6 eV. Parvenir à doper ces nanotubes par substitution d'éléments chimiques pouvant introduire des états donneurs ou accepteurs est supposé être une approche prometteuse pour moduler les propriétés électroniques et optiques de ces nanostructures. Les objectifs de cette thèse ont été doubles. D'une part, il s'est agi de développer des procédés de synthèse modulables pour pouvoir produire différents types de tubes hétéroatomiques. La technique CVD assistée par aérosol et la technique de vaporisation laser ont été utilisées à cette fin. D'autre part, une analyse fine à l'échelle macroscopique et sub-nanométrique des échantillons a été réalisée principalement par microscopie électronique en transmission (HRTEM) et spectroscopie de pertes d'énergies des électrons résolue spatialement (SR-EELS).<br />Il a ainsi été mis en évidence dans ce manuscrit la possibilité de réaliser des nanotubes de type CNx et CBxNy mono- et multi-feuillets. Par ailleurs, une forte tendance à la ségrégation en domaines de type C et BN a été observée avec un localisation préférentielle et une taille des domaine spécifique, fonction de la technique de synthèse utilisée.