Based on a previously completed design for a soft X-ray (50-1100 eV) emission spectrometer, an endstation was constructed for the Resonant Elastic and Inelastic X-ray Scattering (REIXS) beamline at the CLS. The optical design employed techniques and software tools developed in-house using ray-tracing and diffraction grating efficiency calculations to analyze and compare existing designs and to propose a new design with superior performance. This design employs Rowland circle geometry to achieve a theoretical resolving power in excess of 2,500 in our range of interest. In addition, a novel optical design for a larger extremely high resolution spectrometer has been completed to provide theoretical resolving powers exceeding 10,000 throughout the higher end of the spectrum. To accommodate this optical design a completely new mechanical design was required, involving significant mechanical, electrical, vacuum and software engineering. Countless custom fabricated parts were required along with numerous o -the-shelf secondary instruments and systems. All told, this entirely student-managed project has cost over $1.5M and taken over 5 years. Construction is finally complete and the endstation is currently being commissioned. Necessary design changes made during the mechanical design process resulting in the selection of a more suitable, but lower resolution, detector. This reduced the theoretical maximum resolving power to 1,800 for the first order gratings and roughly 5,000 for the third order gratings. Commissioning is still underway, but first order resolutions in the range of 1,000 - 2,000 have been recorded as have third order resolutions exceeding 4,000. Publication quality data has been collecting by members of this research group and invited external users have successfully grown and measured samples here. Two of the optical elements required rework and upon their delivery the system commissioning will be completed and peer-reviewed access will begin.

In processing and data storage mainly ferromagnetic (FM) materials are being used. Approaching physical limits, new concepts have to be found for faster, smaller switches, for higher data densities and more energy efficiency. Some of the discussed new concepts involve the material classes of correlated oxides and materials with antiferromagnetic coupling. Their applicability depends critically on their switching behavior, i.e., how fast and how energy efficient material properties can be manipulated. This thesis presents investigations of ultrafast non-equilibrium phase transitions on such new materials. In transition metal oxides (TMOs) the coupling of different degrees of freedom and resulting low energy excitation spectrum often result in spectacular changes of macroscopic properties (colossal magneto resistance, superconductivity, metal-to-insulator transitions) often accompanied by nanoscale order of spins, charges, orbital occupation and by lattice distortions, which make these material attractive. Magnetite served as a prototype for functional TMOs showing a metal-to-insulator-transition (MIT) at T = 123 K. By probing the charge and orbital order as well as the structure after an optical excitation we found that the electronic order and the structural distortion, characteristics of the insulating phase in thermal equilibrium, are destroyed within the experimental resolution of 300 fs. The MIT itself occurs on a 1.5 ps timescale. It shows that MITs in functional materials are several thousand times faster than switching processes in semiconductors. Recently ferrimagnetic and antiferromagnetic (AFM) materials have become interesting. It was shown in ferrimagnetic GdFeCo, that the transfer of angular momentum between two opposed FM subsystems with different time constants leads to a switching of the magnetization after laser pulse excitation. In addition it was theoretically predicted that demagnetization dynamics in AFM should occur faster than in FM materials as no net angular momentum has to be transferred out of the spin system. We investigated two different AFM materials in order to learn more about their ultrafast dynamics. In Ho, a metallic AFM below T ≈ 130 K, we found that the AFM Ho can not only be faster but also ten times more energy efficiently destroyed as order in FM comparable metals. In EuTe, an AFM semiconductor below T ≈ 10 K, we compared the loss of magnetization and laser-induced structural distortion in one and the same experiment. Our experiment shows that they are effectively disentangled. An exception is an ultrafast release of lattice dynamics, which we assign to the release of magnetostriction. The results presented here were obtained with time-resolved resonant soft x-ray diffraction at the Femtoslicing source of the Helmholtz-Zentrum Berlin and at the free-electron laser in Stanford (LCLS). In addition the development and setup of a new UHV-diffractometer for these experiments will be reported. / In der Datenspeichertechnologie werden bisher hauptsächlich ferromagnetische Materialien eingesetzt. Da mit diesen aber physikalische Grenzen erreicht werden, werden neue Konzepte gesucht, um schnellere und kleinere Schalter, größere Datendichten und eine höherere Energieeffizienz zu erzeugen. Unter den diskutierten Materialklassen finden sich komplexen Übergangsmetalloxide und Materialien mit antiferromagnetischer Kopplung. Die Anwendbarkeit solcher Materialien hängt stark davon ab, wie schnell sich deren Eigenschaften verändern lassen und wieviel Energie dafür eingesetzt werden muss. Die vorliegende Arbeit beschäftigt sich mit ultraschnellen, Nicht-Gleichgewicht-Phasenübergängen genau in solchen Materialien. In Übergangsmetalloxiden führt die enge Kopplung zwischen den unterschiedlichen Freiheitsgraden zu einem effektiven niederenergetischen Anregungsspektrum. Diese Anregungen sind oft verknüpft mit spektakulären makroskopischen Eigenschaften, wie z.B. dem kolossalen Magnetowiderstand, Hochtemperatur-Supraleitung, Metall- Isolator-Übergang, die oft von nanoskaliger Ordnung von Spins, Ladungen, orbitaler Besetzung sowie Gitterverzerrungen begleitet sind. Dadurch werden diese Materialien interessant für Anwendbarkeit. Magnetit, ein Prototyp eines solchen funktionalen Materials zeigt einen Metall-Isolator-Übergang bei T = 123 K. Untersucht man die Ladungs- und orbitale Ordnung sowie die Struktur nach einer optischen Anregung, so findet man, dass die elektronische Struktur und Gitterverzerrung, die kennzeichnend für die Tieftemperaturphase sind, innerhalb der Zeitauflösung des Experiments von 300 fs zerstört wird. Der eigentliche Metall-Isolator-Übergang zeigt sich erst nach 1.5 ps. Die Ergebnisse zeigen, dass MITs in funktionalen Materialien bis zu tausend Mal schneller geschaltet werden können als in vorhandenen Halbleiter-Schaltern. Seit kurzem rücken auch ferrimagnetische und antiferromagnetische Materialen in den Fokus des Interesses. Es wurde im Ferrimagnet GdFeCo gezeigt, dass der Transfer von Drehimpuls zwischen zwei entgegengesetzten Subsystemen mit unterschiedlichen Zeitkonstanten zu einem Umschalten der Magnetisierung führt. Zudem wurde vorhergesagt, dass Demagnetisierungsdynamiken in antiferromagnetischen Materialien schneller ablaufen soll als in ferromagnetischen, da kein Drehimpuls aus dem Spinsystem abgeführt werden muss. Damit wir mehr über antiferromagnetische Dynamik erfahren haben wir zwei unterschiedliche Antiferromagneten untersucht, um sie mit den bekannten FM zu vergleichen. Im metallischen AFM Holmium fanden wir, dass die magnetische Ordnung schneller und zehnmal energieeffizienter zerstört werden kann als in vergleichbaren FM Metallen. In Europium-Tellurid, einem antiferromagnetischem Halbleiter, haben wir den Zerfall der magnetischen Ordnung im Hinblick auf Wechselwirkungen mit der Struktur untersucht. Wir fanden auf kurzen Zeitskalen eine eher entkoppelte Dynamik. Eine Ausnahme ist ein schneller Beitrag zur Gitterdynamik, den wir mit dem Wegfall von Magnetostriktion erklären. Die hier gezeigten Ergebnisse wurden mit Hilfe zeitaufgelöster resonanter weicher Röntgenbeugung an der Femtoslicing Strahlungsquelle des Helmholtz-Zentrums Berlin und am freien Elektronenlaser LCLS gemessen. Zusätzlich wird über die Entwicklung und den Bau eines UHV-Diffraktometers für diese Experimente berichtet.

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Au point de convergence entre les sciences fondamentales et les sciences appliquées, les nanosystèmes connaissent depuis une dizaine d'années un développement industriel à l'échelle planétaire. Parmi ces nanosystèmes, les agrégats, petites particules constituées de quelques atomes (ou molécules) à plusieurs milliers d'unités, constituent véritablement "le chaînon manquant" entre l'atome isolé et le solide massif. L'étude des interactions dans les agrégats permettrait de comprendre comment l'atome est influencé par son environnement lorsqu'il est inclus dans un système dense au sein d'autres atomes. La nanoparticule (NP) est constituée de plusieurs milliers à millions d'atomes, ses dimensions étant exprimées en nanomètres (nm, 1 nm = 10^{-9} m).L'engouement que suscitent les agrégats et les NPs est lié à leurs propriétés physiques particulières mais également à leur grande surface spécifique (rapport surface/volume). Il en résulte une grande réactivité liée à des sites réactionnels plus nombreux. Cette caractéristique est exploitée dans de très nombreux domaines d'applications (catalyse hétérogène, dépollution, photovoltaïque, nanomédecine).Cette expansion des activités "nanotechnologiques" implique le développement de méthodes de caractérisation de ces nouveaux types de matériaux, qui sont bel et bien présents dans notre vie.Parmi les méthodes de caractérisation de la matière, la spectroscopie de photoélectrons (XPS) générés par rayonnement synchrotron a, depuis longtemps, prouvé son efficacité pour l'étude des atomes, molécules et des matériaux, et s'est imposée en tant que technique de choix en science des surfaces. L'idée de ces travaux de thèse est de combiner la sélectivité atomique de la spectroscopie appliquée à la matière diluée, avec la sensibilité de surface de la spectroscopie X-mous sur les matériaux pour étudier des nanosystèmes (agrégats et NPs) en phase gazeuse par XPS dans le domaine d'énergie allant de 100 eV à 1000 eV.Nous présentons dans cette thèse les premiers résultats obtenus par cette approche sur la ligne de lumière PLEIADES du synchrotron SOLEIL, ligne à ultra-haute résolution dédiée à l'étude de la matière diluée. Les expériences ont porté sur des matériaux très utilisés dans les secteurs industriel et biomédical, en l'occurrence les NPs de TiO2, de Silicium et les NPs de polystyrène fonctionnalisées par des dérivés glucidiques}. Nous montrons comment l'XPS de NPs isolées nous permet de répondre à des questionnements concrets, comme la réactivité de surface des NPs, les processus et les dynamiques d'oxydation, l'inclusion d'hétéroatomes ainsi que l'interface ligand/NP. Les résultats présentés ici montrent non seulement la faisabilité de la méthode, mais plus encore, prouvent qu'il est possible d'adresser des problématiques appliquées ayant trait à des phénomènes réactionnels surfaciques, sur des NPs isolées, aléatoirement orientées. / During the past decade, a world-wide industrial expansion of nanosystems has been taking place at the junction between fundamental and applied sciences. Among these nanosystems, clusters, defined as small particles whose constitution ranges from few atoms (or molecules) to several thousand units, constitute "the missing link" between the isolated atom and the bulk solid. Studying the interactions in the aggregates would allow to understand how the atom is influenced by its neighborhood when it is included in a dense system within other atoms. "Nanoparticle" (NP) is usually defined as a system extanding from several thousands to millions of atoms, and its size is expressed in nanometer (nm, 1 nm = 10^{-9} m).This interest for nanosystems mainly results from their particular physical properties at the nanometer scale, but also from their large "surface to bulk" ratio. Hence, more active sites are available at the surface, enhancing their reactivity. This characteristic is used in numerous fields of applications (heterogeneous catalysis, cleanup, photovoltaics, nanomedicine).% and is also relevant in natural processes (atmospheric sprays, volcanic eruptions).This expansion of the "nanotechnological" activities involves the development of new methods for the characterization of these new kinds of materials, which take a considerable part in our daily life. Among the methods of matter characterization, synchrotron radiation based soft X-ray spectroscopy has shown to be a powerful technique for the study of atoms and molecules as well as materials, and appears today as an efficient technique of characterization in surface science.The idea of this thesis is to combine the atomic selectivity of the spectroscopy applied to dilute matter, with the surface sensitivity of soft X-ray spectroscopy, to study isolated nanosystems (clusters and NPs) in the gas phase, by XPS in the energy range of soft X-ray (typically 100 eV to 1000 eV). We present in this thesis the first results obtained by this approach at the PLEIADES beamline of SOLEIL synchrotron radiation facility. PLEIADES is a ultra-high resolution beamline dedicated to the study of dilute matter. The experiments carried out in this work relate to materials often used in the industrial and biomedical fields: TiO2 NPs, Silicon and glycosylated polystyrene NPs. We show how XPS on isolated NPs allows us to answer concrete questions, as the surface reactivity of the NPs, processes and oxidation dynamics, the doping efficiency or the interface ligand/NP. The results presented here not only show the feasibility of the method, but much more than that, prove that it is possible to give insight about surface chemical processes occuring on isolated, randomly oriented NPs.

<p>Lithium ion insertion into electrode materials is commonly used in rechargeable battery technology. The insertion implies changes in both the crystal structure and the electronic structure of the electrode material. Side-reactions may occur on the surface of the electrode, which is exposed to the electrolyte and form a solid electrolyte interface (SEI). The understanding of these processes is of great importance for improving battery performance. The chemical and physical properties of water and alcohols are complicated by the presence of strong hydrogen bonding. Various experimental techniques have been used to study geometrical structures and different models have been proposed to view the details of how these liquids are geometrically organized by hydrogen bonding. However, very little is known about the electronic structure of these liquids, mainly due to the lack of suitable experimental tools.</p><p>This thesis addresses the electronic structure of liquids and lithium battery materials using resonant inelastic X-ray scattering (RIXS) at high brightness synchrotron radiation sources. The electronic structure of battery electrodes has been probed, before and after lithiation, studying the doping of electrons into the host material. The chemical composition of the SEI on cycled graphite electrodes was determined. The local electronic structure of water, methanol and mixtures of the two have been examined using a special liquid cell. Results from the study of liquid water showed a strong influence on the 3a₁ molecular orbital and orbital mixing between molecules upon hydrogen bonding. The study of methanol showed the existence of ring and chain formations in the liquid phase and the dominating structures are formed of 6 and 8 molecules. Upon mixing of the two liquids, a segregation at the molecular level was found and the formation of new structures, which could explain the unexpected low increase of the entropy.</p>

Lithium ion insertion into electrode materials is commonly used in rechargeable battery technology. The insertion implies changes in both the crystal structure and the electronic structure of the electrode material. Side-reactions may occur on the surface of the electrode, which is exposed to the electrolyte and form a solid electrolyte interface (SEI). The understanding of these processes is of great importance for improving battery performance. The chemical and physical properties of water and alcohols are complicated by the presence of strong hydrogen bonding. Various experimental techniques have been used to study geometrical structures and different models have been proposed to view the details of how these liquids are geometrically organized by hydrogen bonding. However, very little is known about the electronic structure of these liquids, mainly due to the lack of suitable experimental tools. This thesis addresses the electronic structure of liquids and lithium battery materials using resonant inelastic X-ray scattering (RIXS) at high brightness synchrotron radiation sources. The electronic structure of battery electrodes has been probed, before and after lithiation, studying the doping of electrons into the host material. The chemical composition of the SEI on cycled graphite electrodes was determined. The local electronic structure of water, methanol and mixtures of the two have been examined using a special liquid cell. Results from the study of liquid water showed a strong influence on the 3a1 molecular orbital and orbital mixing between molecules upon hydrogen bonding. The study of methanol showed the existence of ring and chain formations in the liquid phase and the dominating structures are formed of 6 and 8 molecules. Upon mixing of the two liquids, a segregation at the molecular level was found and the formation of new structures, which could explain the unexpected low increase of the entropy.

This thesis is devoted to first-principles simulations of bio- and nano-materials,focusing on various soft x-ray spectra, ground-state energies and structures of isolated largemolecules, bulk materials, and small molecules in ambient solutions. K-edge near-edge x-ray absorption fine structure (NEXAFS) spectra, x-ray emission spectra, andresonant inelastic x-ray scattering spectra of DNA duplexes have been studied by means oftheoretical calculations at the density functional theory level. By comparing a sequence of DNAduplexes with increasing length, we have found that the stacking effect of base pairs has verysmall influence on all kinds of spectra, and suggested that the spectra of a general DNA can bewell reproduced by linear combinations of composed base pairs weighted by their ratio. The NEXAFS spectra study has been extended to other realistic systems. We have used cluster modelswith increasing sizes to represent the infinite crystals of nucleobases and nucleosides, infinitegraphene sheet, as well as a short peptide in water solution. And the equivalent core holeapproximation has been extensively adopted, which provides an efficient access to these largesystems. We have investigated the influence of external perturbations on the nitrogen NEXAFSspectra of guanine, cytosine, and guanosine crystals, and clarified early discrepancies betweenexperimental and calculated spectra. The effects of size, stacking, edge, and defects to theabsorption spectra of graphene have been systematically analyzed, and the debate on theinterpretation of the new feature has been resolved. We have illustrated the influence of watersolvent to a blocked alanine molecule by using the snapshots generated from molecular dynamics. Multi-scale computational study on four short peptides in a self-assembled cage is presented. It isshown that the conformation of a peptide within the cage does not corresponds to its lowest-energyconformation in vacuum, due to the Zn-O bond formed between the peptide and the cage, and theconfinement effect of the cage. Special emphasis has been paid on a linear-scaling method, the generalized energy basedfragmentation energy (GEBF) approach. We have derived the GEBF energy equation at the Hartree-Focklevel with the Born approximation of the electrostatic potential. Numerical calculations for amodel system have explained the accuracy of the GEBF equation and provides a starting point forfurther refinements. We have also presented an automatic and efficient implementation of the GEBFapproach which is applicable for general large molecules. / QC 20110404

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La présente thèse s’inscrit dans le cadre du développement des lasers X-UV générés en régime collisionnel transitoire et a pour objet principal d’étudier l’influence de la mise en forme temporelle des impulsions laser de haute puissance sur l’efficacité de génération de ces sources. Mon travail essentiellement expérimental a consisté à étudier de nouveaux schémas de pompage mettant en oeuvre différents dispositifs permettant de produire des préimpulsions et/ou un piédestal d’ASE au sein de la chaîne laser pilote. Dans ce manuscrit, je présente ces dispositifs et montre l’influence des différents paramètres laser sur l’efficacité de production du laser X-UV. L’étude expérimentale met tout d’abord en évidence une augmentation significative de l’énergie et de la durée de vie dela source laser X-UV en présence d’une préimpulsion.Dans ce contexte, un dispositif a été expérimenté permettant de générer au sein d’un unique faisceau laser, les deux principales impulsions précédées de la pré-impulsion, tout en gardant un contrôle sur leurs caractéristiques spectro-temporelles.Une approche alternative a été expérimentée dans laquelle un laser annexe « Q-switch » à bas coût est utilisé pour générer un plasma peu dense avecde faibles gradients de densité. Ce dernier dispositif a montré d’excellentes performances sur une large plage de longueur d’onde, et a été utilisé pour réaliser une expérience d’injection d’harmoniques d’ordre élevé, générées sur la voies econdaire à partir d’une cellule de gaz d’Argon.Une amélioration notable des caractéristiques spatiales et de la cohérence temporelle du laserX-UV a pu être observée. / The thesis fits within the framework ofsoft x-ray lasers (SXRL) development and has formain objective to study the influence of the temporal shaping of ultra-intense laser pulses, on the efficiency of SXRL generation. My thesiswork consisted in studying, designing and calibrating new pumping schemes through various devices based on the prepulse generation and/or an amount of ASE within the laser driver.In this manuscript, I study their influence on the SXRL generation efficiency by highlighting the optimization parameters such as the delay and the energy ratio between pulses, or the duration of each of them. The experimental study highlights first of all the influence of a prepulse on the SXRL generation efficiency. In the same framework, a device was experimented, allowing to generate within a single laser beam two mainpulses preceded by a prepulse, while maintaining a control over their spectro-temporalcharacteristics.An alternative approach was experimented in which an additional low cost « Q-Switch » lase rwas used to produce a under dense plasma presenting smooth electronic density gradients.This last device has showed excellent performances on a wide wavelength range andhas been used to perfom an experiment of highorder harmonic seeding generated from an Argongas cell on the secondary LASERIX beamline. A noteworthy improvement of the spatial characteristics and the temporal coherence of theSXRL have been observed.

La consommation mondiale d'énergie a fortement augmenté durant le siècle dernier et va continuer de croître au cours des prochaines décennies. Le développement d'énergies durables et alternatives aux énergies fossiles constitue un enjeu crucial pour les générations futures. Dans ce contexte, la fusion thermonucléaire contrôlée serait un candidat de premier choix pour assurer la transition énergétique. Le tokamak, basé sur la fusion par confinement magnétique, est actuellement la solution la plus en vue pour contrôler la réaction de fusion et utiliser cette énergie à des fins civiles.Dans les plasmas de tokamak, les impuretés lourdes comme le tungstène présent dans les éléments de la paroi face au plasma, peuvent migrer vers le plasma de cœur et fortement dégrader les performances fusion par rayonnement. L’objectif de cette thèse est d’utiliser ce rayonnement dans la gamme des X-mous afin d’en déduire des informations sur le transport du tungstène dans le plasma de cœur. Le but est de contrôler à terme cette concentration en impuretés et d’identifier les actuateurs pouvant agir sur cette distribution. / Global energy consumption has increased significantly during the last century and will continue to grow in the coming decades. The development of sustainable energies alternative to fossil fuels is a crucial issue for the future generations. In this context, controlled thermonuclear fusion is a good candidate for the energy transition. Magnetic confinement fusion and tokamaks are currently the most promising solution to control the fusion reaction and use it for civil purposes.In tokamak plasmas, heavy impurities such as tungsten sputtered from plasma-facing components can migrate to the core plasma and strongly degrade fusion performance by radiation. The goal of this PhD thesis is to use this radiation in the soft X-ray range in order to obtain valuable information on tungsten transport in the core plasma. The final perspective is to control the impurity concentration and identify actuators that can act on this distribution.