Academic literature on the topic 'Spectroscopie HAXPES'

W/B4C multilayers (MLs) consisting of ten layer pairs with varying boron carbide layer thicknesses have been investigated. The ML structures were characterized using grazing-incidence hard X-ray reflectivity (GIXR), resonant soft X-ray reflectivity (RSXR), hard X-ray photoelectron spectroscopy (HAXPES) and X-ray absorption near-edge spectroscopy (XANES). Depth-resolved spectroscopic information on the boron carbide layer in W/B4C MLs was extracted with sub-nanometre resolution using reflectivity performed in the vicinity of the B K-edge. Interestingly, these results show that the composition of boron carbide films is strongly dependent on layer thicknesses. HAXPES measurements suggest that most of the boron is in the chemical state of B4C in the multilayer structures. XANES measurements suggest an increase in boron content and C—B—C bonding with increase in boron carbide layer thickness.

Hard X-ray photoemission spectroscopy (HAXPES) was employed for the structural evaluation of ultrananocrystalline diamond/amorphous carbon (UNCD/a-C) composite films deposited on cemented carbide substrates, at substrate temperatures up to 550 °C by coaxial arc plasma deposition. The results were compared with those of soft X-ray photoemission spectroscopy (SXPES). Since nanocrystalline diamond grains are easily destroyed by argon ion bombardment, the structural evaluation of UNCD/a-C films, without the argon ion bombardment, is preferable for precise evaluation. For samples that were preserved in a vacuum box after film preparation, the sp3 fraction estimated from HAXPES is in good agreement with that of SXPES. The substrate temperature dependencies also exhibited good correspondence with that of hardness and Young’s modulus of the films. On the other hand, the sp3 fraction estimated from SXPES for samples that were not preserved in the vacuum box had an apparent deviation from those of HAXPES. Since it is possible for HAXPES to precisely estimate the sp3 fraction without the ion bombardment treatment, HAXPES is a feasible method for UNCD/a-C films, comprising nanocrystalline diamond grains.

In this work, we present a comprehensive study on real-time monitoring the growth of epitaxial CoxFe3−xO4 thin films grown on SrTiO3(001) substrates via reactive molecular beam epitaxy. The growth process was monitored during evaporation by means of time resolved operando hard X-ray photoelectron spectroscopy (HAXPES). We prepared ultrathin ferrite films using different oxygen partial pressures, showing pure metallic, light oxidic, and cobalt ferrite-like growth. Additional X-ray diffraction measurements confirm HAXPES results.

The GALAXIES beamline at the SOLEIL synchrotron is dedicated to inelastic X-ray scattering (IXS) and photoelectron spectroscopy (HAXPES) in the 2.3–12 keV hard X-ray range. These two techniques offer powerful complementary methods of characterization of materials with bulk sensitivity, chemical and orbital selectivity, resonant enhancement and high resolving power. After a description of the beamline components and endstations, the beamline capabilities are demonstrated through a selection of recent works both in the solid and gas phases and using either IXS or HAXPES approaches. Prospects for studies on liquids are discussed.

The structural and chemical compositions of Y3+ ion-doped CaF2 were investigated as a possible lanthanide hosting material. A series of CaF2 nanomaterials doped with various concentrations of Y3+ ions under the chelating agent ethylene diamine tetraacetic acid (EDTA) were synthesized using the hydrothermal method. The x-ray diffraction results demonstrated that a mixture of cubic CaF2 and [CaY]F2 phases gradually formed with an increasing Y3+ ion concentration. A single [CaY]F2 cubic phase was formed when EDTA was added as the chelating agent. Scanning electron microscopy results demonstrated that the particle size and the morphology of the material depended on the Y3+ concentration and that EDTA (0.5 g) produced a spherical morphology. The surface and bulk chemical compositions were determined using a combined system of soft x-ray photoemission spectroscopy (XPS) (Al-Kα 1486.7 eV) and hard x-ray photoemission spectroscopy (HAXPES) (Cr-Kα 5414.7 eV). The relative changes in the chemical composition of the surface and subsurface/bulk were investigated. The combined XPS-HAXPES analysis demonstrated that the surface impurities in the accessible peaks (Ca 2p, Y 3d, and F 1s) completely diminished in the subsurface region. However, XPS-HAXPES analysis confirmed that the composition of the [CaY]F2 nanomaterial on the surface differs from that in the subsurface region.

Les mémoires à pont conducteur (CBRAM) sont une option actuellement étudiée pour la prochaine génération de mémoires non volatiles. Le stockage des données est basé sur la commutation de la résistivité entre les états de résistance élevée (HRS) et faible (LRS). Sous polarisation électrique, on suppose qu'un trajet conducteur est créé par la diffusion des ions de l'électrode active dans l'électrolyte solide. Récemment, une attention particulière a été portée sur les dispositifs contenant un élément semi-conducteur tel que le tellure, fonctionnant avec des courants réduits et présentant moins de défaillances de rétention. Dans ces « subquantum CBRAMs », le filament est censé contenir du tellure, ce qui donne une conductance de 1 atome (G₁atom) significativement réduite par rapport aux CBRAMs standard et permettant ainsi un fonctionnement à faible puissance. Dans cette thèse, nous utilisons la spectroscopie de photoélectrons par rayons X (XPS) pour étudier les réactions électrochimiques impliquées dans le mécanisme de commutation des CBRAMs à base de Al₂O ₃ avec des alliages ZrTe et TiTe comme électrode active. Deux méthodes sont utilisées: i) spectroscopie de photoélectrons par rayons X de haute énergie non destructive (HAXPES) pour étudier les interfaces critiques entre l'électrolyte (Al₂O ₃ ) et les électrodes supérieure et inférieure et ii) les faisceaux d'ions à agrégats gazeux (GCIB), une technique de pulvérisation qui conduit à une dégradation plus faible de la structure, avec un profilage en profondeur XPS pour évaluer les distributions des éléments en profondeur. Des mesures ToF-SIMS sont également effectuées pour obtenir des informations complémentaires sur la répartition en profondeur des éléments. Le but de cette thèse est de clarifier le mécanisme de changement de résistance et de comprendre les changements chimiques aux deux interfaces impliquées dans le processus de « forming » sous polarisation positive et négative ainsi que le mécanisme de « reset ». Pour cela, nous avons effectué une comparaison entre le dispositif vierge avec un état formé, i.e. l'échantillon après la première transition entre HRS et LRS et un état reset, i.e. l'échantillon après la première transition entre LRS et HRS.L'analyse du « forming » positif pour les dispositifs ZrTe / Al₂O ₃ a montré une libération de Te liée à l’oxydation de Zr due au piégeage de l'oxygène de l'Al₂O ₃ sous l’effet du champ électrique. D'autre part, pour les dispositifs TiTe / Al₂O ₃, la présence d'une couche importante d'oxyde de titane à l'interface avec l'électrolyte a provoqué une dégradation permanente de la cellule en polarisation positive. Pour le « forming » négatif, nos résultats montrent un mécanisme hybride, à savoir une combinaison de formation de lacunes d'oxygène dans l'oxyde provoquée par la migration de O2- entraîné par le champ électrique vers l'électrode inférieure et la libération de tellure pour former des filaments conducteurs. De plus, les résultats obtenus par profilométrie XPS et ToF-SIMS ont indiqué une possible diffusion de Te dans la couche d'Al₂O ₃. Lors du « reset », il y a une recombinaison partielle des ions oxygène avec les lacunes d'oxygène près de l'interface TiTe / AlAl₂O ₃ avec une perte de Te. Un mécanisme hybride a également été observé sur les dispositifs ZrTe / Al₂O ₃ pendant le « forming » négatif. En tenant compte du rôle important de la migration d'oxygène dans la formation / dissolution des filaments, nous discutons également des résultats obtenus par XPS avec polarisation électrique in- situ (sous ultravide) pour mieux comprendre le rôle de l'oxydation de surface et des interfaces dans la commutation résistive
Conducting bridging resistive random accessmemories (CBRAMs) are one option currently investigated for the next generation of non volatile memories. Data storage is based on switching the resistivity between high (HRS) and low (LRS) resistance states. Under electrical bias,a conductive path is assumed to be created by ions diffusion from the active electrode into the solid electrolyte. Recently, special attention has been drawn to devices containing an elemental semiconductor such as tellurium, operating with reduced currents and less retention failures. In these subquantum CBRAM cells, the filament is thought to contain tellurium , yielding a 1-atomconductance (G₁atom) significantly reduced compared to standard CBRAMs and thus allowing low power operation. In this thesis, we use X-rayphotoelectron spectroscopy (XPS) to learn about electrochemical reactions involved in the switching mechanism of Al₂O₃ based CBRAMswith ZrTe and TiTe alloys as active electrode. Two methods are used: i) non-destructive Hard X-ray photoelectron spectroscopy (HAXPES) to investigate the critical interfaces between the electrolyte (Al₂O₃) and the top and bottom electrodes and ii) Gas Cluster Ion Beams (GCIB), a sputtering technique that leads to lower structure degradation, combined with XPS depth profiling to evaluate chemical depth distributions. To FSIMS measurements are also performed to get complementary in-depth chemical information.The aim of this thesis is to clarify the driving mechanism and understand the chemical changes at both interfaces involved in the forming process under positive and negative polarization as well as the mechanism of the reset operation. For that,we performed a comparison between as-grown state, i.e. the pristine device with a formed state,i.e. the sample after the first transition between HRS and LRS, and reset state, i.e. the sample after the first transition between LRS and HRS.Conducting bridging resistive random access memories (CBRAMs) are one option currently investigated for the next generation of non-volatile memories. Data storage is based on switching the resistivity between high (HRS) and low (LRS) resistance states. Under electrical bias,a conductive path is assumed to be created byions diffusion from the active electrode into the solid electrolyte. Recently, special attention has been drawn to devices containing an elemental semiconductor such as tellurium, operating with reduced currents and less retention failures. In these subquantum CBRAM cells, the filament is thought to contain tellurium , yielding a 1-atom conductance (G₁atom) significantly reduced compared to standard CBRAMs and thus allowing low power operation. In this thesis, we use X-ray photoelectron spectroscopy (XPS) to learn about electrochemical reactions involved in the switching mechanism of Al₂O₃ based CBRAMs with ZrTe and TiTe alloys as active electrode. Twomethods are used: i) non-destructive Hard X-rayphotoelectron spectroscopy (HAXPES) toinvestigate the critical interfaces between the electrolyte (Al₂O₃) and the top and bottom electrodes and ii) Gas Cluster Ion Beams (GCIB), a sputtering technique that leads to lower structure degradation, combined with XPS depth profiling to evaluate chemical depth distributions. To FSIMS measurements are also performed to get complementary in-depth chemical information.The aim of this thesis is to clarify the driving mechanism and understand the chemical changes at both interfaces involved in the forming process under positive and negative polarization as well as the mechanism of the reset operation. For that,we performed a comparison between as-grown state, i.e. the pristine device with a formed state,i.e. the sample after the first transition between HRS and LRS, and reset state, i.e. the sample after the first transition between LRS and HRS

Ce travail vise à utiliser la spectroscopie de photoélectrons à rayons X durs (HAXPES) à l'échelle du laboratoire dans la perspective de l'analyse du fond continue inélastique (IBA) pour des applications dans le domaine de la métrologie afin de fournir des mesures d'épaisseur de matériaux technologiquement pertinents pour les mémoires et transitors de puissance. Nous cherchons à répondre au besoin d'une méthode adaptée pour les processus de contrôle en salle blanche et l'analyse de routine. Les échantillons présentés dans ce travail ont été fabriqués par des procédés préindustriels et sont représentatifs de la technologie des dispositifs réels avec des préoccupations telles que des phénomènes de diffusion et des couches et interfaces actives profondément enfouies. Dans ce travail, nous évaluons la technique HAXPES-IBA par le biais des logiciels QUASES en étudiant les paramètres libres, les contributions des opérateurs et l'incertitude du résultat de distribution en profondeur. Nous présentons une analyse autonome en accédant aux spectres de photoémission haute-énergie des éléments de chaque couche de l'échantillon, enregistrés avec un nouvel instrument HAXPES (PHI Quantes) équipé d'une source de laboratoire délivrant la radiation Cr Kα (hv = 5414,72 eV). Tout d'abord, des échantillons de référence d'épaisseur rigoureusement contrôlés (films minces Al2O3 et HfO2) ont été étudiés pour confirmer la précision de la méthode IBA par rapport à des techniques de référence hautement quantitatives. Les déterminations d'épaisseur HAXPES-IBA d'échantillons bicouches comportant une couche de surface aussi épaisse que 25 nm et une couche enterrée d'environ 2,5 nm se sont avérées être en excellent accord avec les résultats obtenus par réflectivité des rayons X (XRR) avec une incertitude de la solution IBA sub-namométrique. La nécessité de sélectionner l'énergie d'excitation en HAXPES appropriée en fonction de l'épaisseur totale des films a été démontrée grâce à l'analyse de spectres HAXPES enregistrés avec une radiation Ga Kα (hv = 9251,74 eV). Enfin, nous appliquons la méthode à des échantillons technologiques réalistes. Dans la première étude, nous présentons les résultats d'épaisseur d'une série d'échantillons de film ALD d'Al2O3 déposés sur GaN, représentatifs d'un transistor à haute mobilité électronique (HEMT) MOS à grille encastrée. Les mesures quantitatives de spectrométrie de masse d'ions secondaires (SIMS) complètent la technique IBA en confirmant le besoin d'un spectre de référence. Dans la deuxième étude, la méthode HAXPES-IBA est combinée avec la pulvérisation ionique pour confirmer l'épaisseur de recouvrement Ti/TiN dans une structure Ti/HfO2 utilisée pour la technologie de mémoire d'accès aléatoire résistive à l'oxyde (OxRRAM). Enfin, nous fournissons un résumé critique des progrès à réaliser pour une méthode HAXPES-IBA fiable et précise, entièrement intégrée dans un environnement de contrôle en ligne
This work uses lab-scale hard X-ray photoelectron spectroscopy (HAXPES) in the perspective of inelastic background analysis (IBA) for applications in the metrology field in order to provide thickness measurements of technologically relevant materials in memory and power devices. We seek to meet the need for a method adapted for inline processes and routine analysis. The samples presented in this work were fabricated by pre-industrial processes and are representative of real device technology with concerns like complex interdiffusion properties and deeply buried active layers and interfaces. In this work, we evaluate the HAXPES-IBA technique executed with QUASES software by studying the free parameters, the operator contributions, and uncertainty in the depth distribution. We present a self-contained analysis by accessing high energy photoelectron spectra of elements from each sample layer recorded with a novel lab-scale HAXPES instrument (PHI Quantes) fitted with a Cr Kα photon source (hv = 5414.72 eV). First, highly controlled reference samples of known thicknesses (Al2O3 and HfO2 thin films) were studied to confirm the accuracy of the IBA method through validation against highly quantitative reference techniques. HAXPES-IBA thickness determinations of bilayer samples with a thick overlayer up to 25 nm and a buried layer of approximately 2.5 nm were found to be in excellent agreement with results from X-ray reflectivity (XRR) with fitting uncertainty of the IBA solution in the sub-nanometer range. The need to select the appropriate HAXPES excitation energy depending on total film thickness was demonstrated thanks to complimentary HAXPES measurements recorded with Ga Kα radiation (hv = 9251.74 eV). Finally, we apply the method to realistic technological samples. In the first study, we present thickness results from a sample class of Al2O3 films deposited over GaN by atomic layer deposition (ALD), representative of a recessed gate MOS channel High Electron Mobility Transistor (HEMT). Quantitative secondary ion mass spectrometry (SIMS) measurements compliment the IBA technique by confirming need for reference spectrum. In the second study, the HAXPES-IBA method is combined with ion sputtering to confirm the Ti/TiN overlayer thickness in a Ti/HfO2-based structure used for oxide resistive random access memory (OxRRAM) technology. We provide a critical summary of advances to reach for an accurate and reliable HAXPES-IBA method fully-integrated into inline process control

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

Le succès des oxydes de métaux de transition lamellaires (LiMO2, M : Ni, Co, Mn) en tant que matériaux d’électrode positive est dû à leurs capacités à intercaler de manière réversible les ions lithium en préservant l’intégrité cristalline de l’électrode. Bien que les LiMO2, soit largement étudiés et utilisés, les mécanismes en jeu à l’échelle électronique lors de la désinsertion/insertion du lithium ne sont toujours pas clarifiés. Cette thèse a pour objectif d’appréhender les mécanismes de compensation de charge dans les matériaux d'électrode positive LiMO2 pendant leur cyclage. En particulier, le rôle des métaux de transition et des ions d'oxygène dans le processus d'oxydoréduction reste à élucider en différenciant les processus de surface de ceux du bulk du matériau.Pour ce faire, grâce à une approche qualitative et quantitative basée sur la spectroscopie de photoémission de rayons X de laboratoire et synchrotron, mous et durs (XPS, HAXPES), nous avons résolu la structure électronique et chimique des électrodes LixMO2 depuis l'extrême surface jusqu'à ~20-30 nm. Nous avons mis en évidence des points communs et des différences sur la nature chimique et l’épaisseur de la couche de passivation de surface « solide electrolyte interphase- SEI », la structure électronique à proximité de la SEI et dans le volume des électrodes en fonction de la nature du métal de transition. Le couplage entre HAXPES et simulation à base de model de cluster (CMT) et de théorie de la fonctionnelle de densité (DFT) a permis de réinterpréter le rôle de l’oxygène dans les processus de transfert de charge. Ainsi, nous avons identifié, à chaque étape de la déinsertion du lithium dans LixMO2, la contribution de la répulsion Coulombique « 3d-3d » et le transfert de charge « 2p-3d » entre l'oxygène et le métal (Δ). L'analyse expérimentale et théorique des spectres des niveaux de cœur des composés LiCoO2 et LiNiO2 à différents stades de la delithiation a mis évidence la présence d’un régime de transfert de charge négatif indiquant le rôle prépondérant des ions oxygène dans le mécanisme de compensation de charge
This thesis has the objective to understand the redox compensation mechanism of positive electrode materials sustaining lithium-ion battery (dis-)charge processes. The study is conducted for LiNiO2, Li2MnO3, and LiCoO2, archetype materials for the state-of-art high-energy positive electrode materials Li[NixMnyCoz]O2. Despite these materials having been studied for decades, the link between electronic correlations and redox mechanism during (de-)lithiation is not well understood. In particular, the role of transition metals and oxygen ions in the redox process is yet to be clarified and resolved in-depth from the surface towards the bulk.To this goal, we establish a novel methodology based on laboratory- and synchrotron-based soft and hard X-ray photoemission spectroscopy (XPS, HAXPES) to probe qualitatively and quantitatively the electronic structure from the extreme surface down to ~20-30 nm. This allows us to follow the evolution of positive solid electrode-electrolyte interphase, surface electrode material degradation, and bulk electronic structure upon cycling. Notably, the thickness and chemical structure of the surface degradation layer depends on the increase of oxygen valence, related to its interaction with the transition metal. Subsequently, we investigate the evolution of the bulk electronic structure upon cycling by analyzing the transition metal 2p core-level HAXPES spectra with electronic structure simulations based on density functional (DFT) and cluster model (CMT) theories. We evaluate the role of transition metals and oxygen in the redox process by quantifying the 3d-3d Coulomb repulsion and oxygen ligand-metal 2p-3d charge transfer (Δ). The spectra analysis for LiCoO2 and LiNiO2 highlights a decrease of Δ towards the negative charge transfer regime indicating a leading role of the oxygen ions in the charge compensation mechanism. The delithiation process is therefore controlled by the local electron transfer from oxygen 2p orbitals to limit charge accumulation in the metal 3d orbitals

Cette thèse vise à améliorer la méthode d'analyse du fond continu inélastique afin de l'appliquer à des cas qui présentent un intérêt technologique. En effet, ces améliorations sont cruciales car elles portent sur des critères de précision et de gain de temps, plus particulièrement pour l’étude de dispositifs présentant plusieurs couches profondément enterrées de matériaux bien distincts. Ainsi, l'analyse du fond continu inélastique associée à la spectroscopie de photoélectrons à rayons X durs (HAXPES) présente un grand intérêt car l’HAXPES permet de sonder plus profondément dans un échantillon qu'avec la spectroscopie de photoélectrons à rayons X classique (XPS). Ce présent travail porte sur des échantillons technologiquement pertinents, principalement des transistors à haute mobilité d'électrons (HEMTs), à certaines étapes cruciales de leur processus de fabrication, tels que des recuits. Il est donc très important que ces analyses soient effectuées de manière non destructive afin de préserver les interfaces enterrées. Ce sont souvent l'emplacement de phénomènes complexes qui sont critiques pour les performances du dispositif et une meilleure compréhension est une condition préalable à l’amélioration des dispositifs. Dans ce travail, les phénomènes de diffusion en profondeur sont étudiés grâce à l’analyse du fond continu inélastique associée à l’HAXPES (en utilisant le logiciel QUASES) pour des profondeurs allant jusqu'à 60 nm. Les résultats de distribution en profondeur présentent des écarts par rapport aux mesures TEM inférieures à 5%. Le choix des paramètres d'entrée de la méthode est discuté pour une large gamme d'échantillons et des règles simples en sont issues qui rendent l'analyse réelle plus facile et plus rapide à effectuer. Enfin, il a été montré que la spectromicroscopie faite avec la technique HAXPEEM peut fournir des spectres à chaque pixel utilisables pour l’analyse du fond continu inélastique. Cela peut fournir une cartographie 3D de la distribution en profondeur des éléments de manière non-destructive
This thesis aims at improving the inelastic background analysis method in order to apply it to technologically relevant samples. Actually, these improvements are utterly needed as they concern criteria of accuracy and time saving particularly for analysis of devices presenting deeply buried layers with different materials. For this purpose, the interest of the inelastic background analysis method is at its best when combined with hard X-ray photoelectron spectroscopy (HAXPES) because HAXPES allows to probe deeper in the sample than with conventional X-ray photoelectron spectroscopy (XPS). The present work deals with technologically relevant samples, mainly the high-electron mobility transistor (HEMT), at some crucial steps of their fabrication process as annealing. Actually, it is very important that these analyses shall be performed non-destructively in order to preserve the buried interfaces. These are often the location of complex phenomena that are critical for device performances and a better understanding is often a prerequisite for any improvement. In this thesis, the in-depth diffusion phenomena are studied with the inelastic background analysis technique (using the QUASES software) combined with HAXPES for depth up to 60 nm. The depth distribution results are determined with deviations from TEM measurements smaller than a typical value of 5%. The choice of the input parameters of the method is discussed over a large range of samples and simple rules are derived which make the actual analysis easier and faster to perform. Finally, it was shown that spectromicroscopy obtained with the HAXPEEM technique can provide spectra at each pixel usable for inelastic background analysis. This is a proof of principle that it can provide a 3D mapping of the elemental depth distribution with a nondestructive method
Denne afhandling har til formål at forbedre den uelastiske baggrundsanalysemetode til anvendelser i den til teknologiske industri. Faktisk er disse forbedringer absolut nødvendige, for at opnå nøjagtighed og tidsbesparelse, især for analyse af prøver med dybt begravede lag af forskellige materialer. Til det formål er interessen for den uelastiske baggrundsanalysemetode bedst i kombination med hård røntgenfotoelektron-spektroskopi (HAXPES), fordi HAXPES gør det muligt at probe dybere i prøven end med konventionel røntgenfotoelektron-spektroskopi (XPS). Dette arbejde beskæftiger sig med teknologisk relevante prøver, hovedsagelig høj-elektron mobilitetstransistor (HEMT), på nogle afgørende trin i deres fremstillingsproces som fx annealing. Faktisk er det meget vigtigt, at disse analyser udføres på en ikke-destruktiv måde for at bevare de begravede grænseflader. Det er ofte her de komplekse fysiske fænomener opstår, som er kritiske for fuktionaliteten, og en bedre forståelse af grænsefladerne er ofte en forudsætning for at kunne forbedre denne. I denne afhandling studeres de dybdegående diffusionsfænomener med den uelastiske baggrundsanalyse teknik (ved hjælp af QUASES software) kombineret med HAXPES for dybder op til 60 nm. Dybdestributionsresultaterne har afvigelser fra TEM-målinger mindre end en typisk værdi på 5%. Valget af input parametre for metoden er diskuteret på bagground af et stort udvalg af prøver samt omfattende simuleringer og enkle regler er udledt, hvilket gør den praktiske analyse nemmere og hurtigere at udføre. Endelig blev det vist, at spektromikroskopi opnået med HAXPEEM-teknikken kan tilvejebringe spektre ved hver enkelt pixel som kan anvendes til uelastisk baggrundsanalyse. Dette viser at i princippet kan en 3D-billeddannelse af den elementære dybdefordeling bestemmes ikke destruktivt

The physical properties of the protective passive films formed on the surface of stainless steels under electrochemical polarization in different electrolytes were studied. The structure of these films was analyzed as a function of depth using photoelectron spectroscopy (PES). Depth profiling (using PES) of the surface layer was achieved by either changing the angle of incidence to achieve different analysis depths (ARXPS), by argon ion etching, or by varying the energy of the incoming x-rays by the use of synchrotron radiation. The use of hard x-rays with high resolution (HAXPES) provided novel quantified information about the nickel content underneath the passive films. A complex environment was found in these surface layers composed of an outermost monolayer of iron on top of a layer of chromium hydroxides covering an underlayer of chromium oxides. Molybdenum was enriched in the interface between the metal and oxide. Nickel is enriched underneath the passive film and therefore nickeloxides are only present in the surface layer in low concentrations. A comparison was performed on austenitic and duplex stainless prepared by hot isostatically pressed (HIP) or cast and forged processes. HIP stainless steel was produced using the burgeoning technique of pressing gas atomized powders together. The structure of these steels is far more homogenous with a lower porosity than that of the conventionally prepared equivalents. It was shown that hot HIP austenitic steel had better pitting corrosion resistance than its conventional counterpart. Finally, the duplex steel was cycled in a Li-ion battery to explore its potential application as a current collector. It was shown that the passive film formed in the organic solvents is similar in composition and thickness to the films formed in aqueous solutions. However, it is doubtful if steel could be used as current collector in batteries due to its high reactivity with lithium.

With an increasing demand for renewable energy sources, research efforts on different solar cell technologies are increasing rapidly. The dye-sensitized solar cell (DSC) is one such technology, taking advantage of light absorption in dye molecules. The liquid based DSC contains several interesting and important interfaces, crucial for the understanding and development of the solar cell performance. Examples of such interfaces include dye-semiconductor, electrode-electrolyte and solute-solvent interfaces. Ultimately, complete interfaces with all these components included are of particular interest. One major challenge is to understand the key functions of these systems at an atomic level and one way to achieve this is to use an element specific and surface sensitive tool, such as photoelectron spectroscopy (PES). This thesis describes the use and development of PES for studying interfaces in the DSC. The materials part of the thesis focuses on interfaces in DSCs studied with PES and the methodology development parts focus on methods to use PES for investigations of solvated heterogeneous interfaces of interest for photoelectrochemical systems such as the DSC. More specifically, beginning with standard vacuum techniques, dye molecules bound to a semiconductor surface have been studied in terms of energy level alignment, surface coverage and binding configuration. To increase the understanding of solvation phenomena present in the liquid DSC, liquid jet experiments have been performed in close combination with theoretical quantum calculations. As a step towards an in-situ method to measure a complete, functioning (in operando) solar cell, methodology development and measurements performed with higher sample pressures are described using new high pressure X-ray photoelectron spectroscopy techniques (HPXPS).

Photoelectron spectroscopy is an experimental method to study the electronic structure in matter. In this thesis, a combination of soft and hard X-ray based photoelectron spectroscopy has been used to obtain atomic level understanding of electronic structures and energy level alignments in mesoscopic solar cells. The thesis describes how the method can be varied between being surface and bulk sensitive and how to follow the structure linked to particular elements. The results were discussed with respect to the material function in mesoscopic solar cell configurations. The heart of a solar cell is the charge separation of photoexcited electrons and holes, and in a mesoscopic solar cell, this occurs at interfaces between different materials. Understanding the energy level alignment between the materials is important for developing the function of the device. In this work, it is shown that photoelectron spectroscopy can be used to experimentally follow the energy level alignment at interfaces such as TiO2/metal sulfide/polymer, as well as TiO2/perovskite. The electronic structures of two perovskite materials, CH3NH3PbI3 and CH3NH3PbBr3 were characterized by photoelectron spectroscopy and the results were discussed with support from quantum chemical calculations. The outermost levels consisted mainly of lead and halide orbitals and due to a relatively higher cross section for heavier elements, hard X-ray excitation was shown useful to study the position as well as the orbital character of the valence band edge. Modifications of the energy level positions can be followed by core level shifts. Such studies showed that a commonly used additive in mesoscopic solar cells, Li-TFSI, affected molecular hole conductors in the same way as a p-dopant. A more controlled doping can also be achieved by redox active dopants such as Co(+III) complexes and can be studied quantitatively with photoelectron spectroscopy methods. Hard X-rays allow studies of hidden interfaces, which were used to follow the oxidation of Ti in stacks of thin films for conducting glass. By the use of soft X-rays, the interface structure and bonding of dye molecules to mesoporous TiO2 or ZnO could be studied in detail. A combination of the two methods can be used to obtain a depth profiling of the sample.

For sustainable development, it is highly important to limit the loss of energy and materials in machines used for transportation, manufacturing, and other purposes. Large improvements can be achieved by reducing friction and wear in machine elements, for example by the application of coatings. This work is focused on triboactive coatings, for which the outermost layer changes in tribological contacts to form so-called tribofilms. The coatings are deposited by magnetron sputtering (a physical vapor deposition method) and thoroughly chemically and structurally characterized, often theoretically modelled, and tribologically evaluated, to study the connection between the composition, structure and tribological performance of the coatings. Tungsten disulfide, WS2, is a layered material with the possibility of ultra-low friction. This work presents a number of nanocomposite or amorphous coatings based on WS2, which combine the low friction with improved mechanical properties. Addition of N can give amorphous coatings consisting of a network of W, S and N with N2 molecules in nanometer-sized pockets, or lead to the formation of a metastable cubic tungsten nitride. Co-deposition with C can also give amorphous coatings, or nanocomposites with WSx grains in an amorphous C-based matrix. Further increase in coating hardness is achieved by adding both C and Ti, forming titanium carbide. All the WS2-based materials can provide very low friction (down to µ<0.02) by the formation of WS2 tribofilms, but the performance is dependent on the atmosphere as O2 and H2O can be detrimental to the tribofilm functionality. Another possibility is to form low-friction tribofilms by tribochemical reactions between the two surfaces in contact. Addition of S to TiC/a-C nanocomposite coatings leads to the formation of a metastable S-doped carbide phase, TiCxSy, from which S can be released. This enables the formation of low-friction WS2 tribofilms when a Ti-C-S coating is run against a W counter-surface. Reduced friction, at a moderate level, also occurs for steel counter-surfaces, likely due to formation of beneficial iron sulfide tribofilms. The studied coatings, whether based on WS2 or TiC, are thus triboactive, with the ability to form low-friction tribofilms in a sliding contact.

This thesis completes my work as doctoral student of the Scuola di Dottorato in Fisica, Astrofisica e Fisica Applicata at the Università degli Studi di Milano that has been carried out, starting in November 2014, mostly at the Laboratorio TASC of IOM-CNR in the premises of the Elettra - Sincrotrone Trieste and FERMI@Elettra infrastructures, in the framework of the NFFA and APE-beamline facilites, as well as by accessing international large scale infrastructures and laboratories. The activity has addressed the development of experimental methodologies and novel instrumentation oriented to the study of the dynamical properties of highly correlated materials after high energy excitation. The science programme has been carried out by exploiting ultrafast femtosecond probes from the optical regime (Ti-Sa lasers, fibre laser oscillators) to the extreme UV-soft X rays at FERMI, to the picosecond hard X-rays from the SPring-8 and Diamond synchrotron radiation source. The sample synthesis of correlated oxides and its characterization has been performed within the NFFA facility and APE-group collaboration in Trieste as well as the design and construction of the all new laser High Harmonic Generation beam line NFFA-SPRINT and its end station for time resolved vectorial electron spin polarimetry. This report concentrates on the main scientific concern of my work that has been the relaxation of external perturbations in a correlated electron material both in the time and space domain. I have employed Photoelectron Spectroscopy (PES) mostly in the Hard X-ray regime (HAXPES), pushing the boundaries of its application to achieve a coherent perspective. The material I have mainly focused on is La0.67Sr0.33MnO3 (LSMO), of high interest for spintronics. This system is prototypical, yielding the highest simplicity in the class of transition metal oxides. In the spatial investigation, I have controlled with high precision the PES probing depth and I have observed the evolution of one spectral feature. I have identified it as probe of electronic hybridization and long-range ordering. I have studied LSMO films of 40 nm in three substrate-induced strain states (1% tensile in-plane, relaxed, 1% compressive in-plane) and a 18 nm film of (Ga,Mn)As (GMA), a well-studied diluted magnetic semiconductor. I have found that the electronic properties to be modified at significant distances from the surface, 4 nm for LSMO and 1.2 nm for GMA, while strain had no detectable effects. In the temporal study, I have employed HAXPES in pump-probe mode (TR-HAXPES) to observe the evolution of the electronic structure after intense optical excitation. A detailed dynamical characterization with optical techniques has allowed me to identify the characteristic time of the collapse of long-range magnetic order to be significantly longer than the one of elemental transition metals. I have ascribed this effect to the half-metallic character of LSMO. With TR-HAXPES I have observed that the whole electronic band-structure evolution is bottlenecked by the slow response of the magnetization, proceeding on hundreds of picoseconds timescales. Finally, I have described the techniques and the instrumentation that can be used to push these investigations to shorter spatial and temporal scales. This has been realized in the form of the NFFA-SPRINT laboratory, a facility open to users, which I participated in designing and developing.