Le développement de l’industrie microélectronique a été jusqu’à récemment essentiellement basé sur une augmentation régulière des performances des composants liée à une réduction toujours plus poussée de leurs dimensions dans la continuité de la loi de Moore. Cette évolution se heurte cependant aux limitations intrinsèques des propriétés physiques du couple silicium-silice sur lesquelles elle repose. La diversification des matériaux intégrés sur Si devient ainsi un enjeu majeur du développement de cette industrie. Dans ce contexte, les oxydes dits fonctionnels forment une famille de matériaux particulièrement intéressante : leurs propriétés physiques (ferroélectricité, ferromagnétisme, diélectricité, piézoélectricité, effet Pockels fort) ainsi que la possibilité de les combiner sous forme d’hétérostructures par épitaxie ouvrent la voie à la fabrication de composants innovants et ultraperformants pour des applications dans les domaines de la micro et de l’optoélectronique, de la spintronique, des micro-ondes et des MEMS. Ces oxydes, et plus spécifiquement ceux appartenant à la famille des pérovskites, sont classiquement épitaxiés par ablation laser (PLD), pulvérisation cathodique ou dépôt de vapeur chimique (CVD) sur des substrats de SrTiO3 (STO). Cependant, ces substrats sont inadaptés aux applications industrielles du fait de leur taille limitée au cm2 et de leur qualité structurale médiocre. Par ailleurs, définir une stratégie pour intégrer ces matériaux sur Si est indispensable pour le développement d’une filière susceptible d’avoir des débouchés applicatifs. Dans ce contexte, l’utilisation de l’épitaxie par jets moléculaires (l’EJM) pour la croissance de ces oxydes est particulièrement pertinente, puisque cette technique permet de fabriquer des couches minces monocristallines de STO sur Si et sur GaAs, ce qui ouvre la voie à l’intégration d’oxydes fonctionnels sur ces substrats via des templates de STO. Cependant, l’EJM est une technique peu mature pour la croissance des oxydes fonctionnels, et doit donc être développée pour cet objectif. C’est le but de ce travail de thèse, financé par un contrat CIFRE avec la société RIBER, équipementier pour l’épitaxie par jets moléculaires, et entrant dans le cadre d’un laboratoire commun entre RIBER et l’INL pour le développement de l’EJM d’oxydes fonctionnels. Nous présentons tout d’abord les développements techniques que nous avons menés autour d’un réacteur EJM « oxydes » prototype. Nous montrons notamment comment nous avons pu améliorer la fiabilité des sources d’oxygène, Sr, Ba et Ti nécessaires à l’épitaxie de matériaux clés que sont le STO et le BaTiO3 ferroélectrique. Nous montrons ensuite comment ces développements techniques nous ont permis de mieux comprendre et mieux maîtriser la croissance de templates de STO sur Si, et en particulier que la cristallisation du STO, initialement amorphe sur Si, est catalysée par un excès de Sr aux premiers stades de la croissance. Nous montrons comment il est possible de contrôler cet excès de Sr pour qu’il ne détériore pas la qualité des couches minces, et nous proposons d’une manière plus générale une étude de l’influence de la stoechiométrie de l’alliage sur ses propriétés structurales. Nous montrons également comment l’utilisation de notre source d’oxygène à plasma permet d’obtenir une oxydation satisfaisante des couches minces d’oxyde. Nous donnons enfin quelques exemples d’intégration sur Si d’oxydes fonctionnels (PZT piézoélectrique, BaTiO3 ferroélectrique) réalisés sur des templates de STO/Si. Nous avons enfin initié l’étude de la croissance par EJM de STO sur des substrats de GaAs et enfin, réaliser la première démonstration d’intégration de PZT ferroélectrique monocristallin sur GaAs. / The development of microelectronics industry has been, until recently, essentially based on the regular improvement of device performances thanks to the downscaling strategy as a continuity of Moore’s law. This evolution is now confronted to the intrinsic physical properties limitations of the material used in the silicon industry (Si and SiO2). Integrating different materials on silicon thus becomes a major challenge of industry development. In this context, functional oxides form a very interesting family of materials: their physical properties (ferroelectricity, ferromagnetism, piezoelectricity, strong Pockels effect) and the possibility to combine them (heterostructures) by epitaxy opens a way for fabricating innovating and high-performance components for applications in micro and optoelectronic, spintronic, micro-waves and MEMs… These oxides and specifically those belonging to the perovskite family are classicaly grown by Laser Ablation (PLD), sputtering or by chemical vapour deposition (CVD) on STO substrates. These substrates are inappropriate for industry applications due to their limited size (1cm²) and their relatively bad structural quality. On the other hand, defining a strategy for integrating these materials on silicon is essential for future applications. In this context, using molecular beam epitaxy (MBE) for the growth of oxides is particularly relevant since this technique allows fabricating monocristalline thin films of STO on Silicon and on GaAs, which open the way of integrating other functional oxides on this substrates via templates of STO. However, MBE is not a mature technique for functional oxides growth. The purpose of this PhD work, financed by a CIFRE contract with the RIBER Company, equipment manifacturer for molecular beam epitaxy, is to develop the growth of functional oxides by MBE. It enters into the framework of a joint laboratory signed between RIBER and INL In this work, we first present technical development performed on a prototype MBE reactor dedicated to oxide growth. We show by then how these technical developments allow a better understanding and control of the growth of STO on Si templates, in particular the crystallisation of initially amorphous STO on Silicon, which is catalysed by an excess of Sr at the first stage of the growth. We demonstrate how it is possible to control this Sr excess so that it does not affect the film quality. We propose a study of the effect of STO cationic stoechiometry on the structural properties. We also show how the use of a conveniently designed oxygen plasma source allows for obtaining good oxidation of the oxide thin films. Finally, we detail a few examples of integration of functional oxides (piezoelectric PZT, ferroelectric BTO) on templates STO/Si. We have also studied the growth of STO on GaAs substrates by MBE and we demonstrate the first integration of monocristalline ferroelectric PZT on GaAs.

La diversification des fonctionnalités intégrées dans les systèmes micro-optoélectroniques est l'un point clé du développement de ces filières. Combiner sur une même puce des matériaux ayant des propriétés différentes doit permettre de faire émerger de nouveaux concepts de composants basés sur de nouveaux effets physiques ou sur la combinaison des propriétés physiques des matériaux intégrés. Parmi les matériaux d'intérêt, les semi-conducteurs III-V présentent des propriétés optiques exceptionnelles et sont couramment utilisés pour réaliser des composants photoniques. Les oxydes fonctionnels, quant à eux, offrent une grande variété de propriétés physiques qui en font des matériaux très prometteurs pour de nombreuses applications. Dans ce contexte, l'objectif global de cette thèse est de démontrer la possibilité d'intégrer des oxydes fonctionnels cristallins sur des hétérostructures à base de GaAs par épitaxie, et de montrer que de telles structures peuvent présenter des propriétés nouvelles pour la photonique. Plus précisément, nous avons focalisé nos efforts sur l'intégration de couches minces de PZT sur des structures à puits quantiques InGaAs/GaAs via des couches tampons de SrTiO3 (STO). Nous avons étudié et développé la croissance par épitaxie par jets moléculaires (MBE) des templates de STO sur GaAs. La forte hétérogénéité entre ces deux types de matériaux nécessite d'avoir recours à des stratégies d'ingénierie d'interface spécifiques et à un excellent contrôle des paramètres de croissance. Nous avons mis en évidence les effets bénéfiques sur la qualité structurale du STO d'une préparation de la surface de GaAs au Ti. Pour ces études, nous avons utilisé la spectroscopie de photoélectrons (XPS, in-situ ou en collaboration avec la ligne TEMPO du synchrotron SOLEIL) et microscopie électronique en transmission (TEM, en collaboration avec le LPN). Ces expériences nous ont permis de sonder structure et chimie de l'interface semi-conducteur/oxyde. Nous avons également étudié les mécanismes de croissance et de cristallisation du STO sur GaAs, en mettant notamment en œuvre des expériences d'XPS in-situ au synchrotron SOLEIL. La compréhension de ces mécanismes spécifiques nous a permis d'adapter les conditions de croissance du STO et d'obtenir des couches tampons d'excellente qualité. Nous avons étudié la croissance de couches minces de PZT sur des structures à puits quantique d'In- GaAs/GaAs via des templates de STO. Nous avons tout d'abord montré que les procédés standards de croissance de PZT (sol-gel ou ablation laser (collaboration avec l'IEF)) conduisaient à de fortes dégradations des puits quantiques du fait des réactions chimiques entre l'oxyde et le matériau III-V. Nous avons étudié les mécanismes de ces dégradations et mis en évidence une forte affinité chimique entre l'As, le Pb et le Sr. Pour pallier cette difficulté, nous avons modifié le procédé de croissance du PZT ainsi que l'hétérostructure III-V (enfouissement du puits, ajout d'AlAs ...). Ces actions combinées nous ont permis de réaliser des couches minces de PZT ferroélectriques sur des structures à puits quantiques d'InGaAs/GaAs. Nous avons ensuite défini un design d'émetteur accordable basé sur une hétérostructure PZT/GaAs/InGaAs. De tels émetteurs ont été réalisés en collaboration avec l'IEF) et mesurés leurs propriétés mécaniques et optiques en effectuant des expériences sous champ. Enfin, nous avons effectué un certain nombre d'études préliminaires visant à démontrer la possibilité d'intégrer des hétérostructures à base de GaAs sur des substrats de Si recouverts de couches tampons de STO. Nous avons pour cela envisagé et étudié la possibilité d'utiliser des composés Zintl-Klemm d'interface susceptibles de minimiser l'énergie d'interface entre le GaAs et le STO. / Diversification of the materials and functionalities integrated on silicon is an important issue for further progression in the field of micro-optoelectronics. The monolithic heterogeneous integration of new materials on silicon, and more generally the combination on the same wafer of materials having different physical properties is a key challenge. Amongst the materials of interest, III-V semiconductors are the object of specific attention because their optoelectronic and transport properties are superior to those of silicon. Similarly, the so-called functional oxides have interesting physical properties (ferroelectricity, ferromagnetism, piezoelectricity, etc.) making them suitable for various applications (NVM, energy harvesters, MEMS . . . ). In this context, the goal of this thesis is to demonstrate the possible integration of crystalline functional oxides on GaAs-based heterostructures using epitaxy and that such structures show new properties for photonic. More precisely, we focused on integration PZT thin film on InGaAs/GaAs quantum wells structures thanks to SrTiO3 (STO) buffer layer. We first studied and developed the growth of STO on GaAs templates using molecular beam epitaxy (MBE). Because of the strong heterogeneity between the two materials, specific interface engineering strategies are required. We highlight the benefit of a Ti-based GaAs surface treatment on the structural quality of STO. For these studies we used photoelectrons spectroscopy (XPS, in-situ and collaboration with TEMPO beam line of SOLEIL synchrotron) and transmission electron spectroscopy (TEM, collaboration with LPN/C2N). Those experiments allowed us to probe both structural and chemical aspects of the semiconductor/ oxide interface. We also studied the growth mechanism of STO on GaAs through in-situ XPS experiments at SOLEIL. Thanks to the understanding of those specifics mechanisms, we could accommodate the growth conditions to obtain good quality STO buffer layers. Then we studied the growth of thin film PZT on InGaAs/GaAs quantum well structures by means of STO templates. We first showed that standard growth process (sol-gel and pulsed laser deposition at IEF/C2N) lead to strong deterioration of quantum well due to chemical reactions between the oxide and the III-V material. We studied the mechanisms involved in this deterioration and highlight the strong chemical affinity between As, Pb and Sr. To palliate this difficulty, the growth process of PZT has been modify and an AlAs “sacrificial” layers has been added in order to limit the oxygen difiusion into the substrate. Thanks to these two solutions, it has been possible to realize a PZT ferroelectric thin film on an InGaAs/GaAs quantum well heterostructure. A tunable source based on such heterostructure has been designed. In this device, the strain induced in the ferroelectric PZT by an electric field is transmitted to the substrate and the quantum well modifying its emitted wavelength. We simulated this device in order to optimize its dimensions. Then we realized this device (collaboration with IEF/C2N) and measured its mechanical and optical properties under an electric field. We also performed preliminary studies in order to demonstrate the possible integration of GaAs-based heterostructures on Si substrates in by the means of STO buffer layer. We considered the use of Zintl- Klemm compounds to minimize the interface energy between GaAs and STO allowing 2D growth of the semiconductor on the oxide.

De två kemiskt nära besläktade metallerna niob (Nb) och tantal (Ta) räknas av Europakommissionen som kritiska råmaterial. Detta på grund av en kraftigt ökad efterfrågan och en geografiskt koncentrerad global produktion av dem. Det här arbetet utgör en del av ett större projekt som bedrivs av EuroGeoSurveys (EGS); GeoERA FRAME, som har till syfte att kartlägga förekomsten av kritiska råmaterial inom EU. Två granitpegmatitiska prov från Kolsva fältspatgruva har undersökts med avseende på deras kemi och mineralogi; dels sådana som tentativt identifierats som kolumbitmineral och dels sådana som innehåller ett samarskitliknande mineral. I arbetet har tre huvudsakliga analysmetoder använts: 1) optisk mikroskopi, 2) svepelektronmikroskopi (SEM) med energidispersiv mikrokemisk analys (EDS), samt 3) pulverröntgendiffraktionsanalys (XRD). De kemiska analyserna som genomfördes på ”kolumbit-proven” visade att de bestod av kolumbit-(Fe), med generell formel AB2O6 och med en järndominans i A-katjonposition och niobdominans i B-katjonposition. Analyserna visad även på förekomst av mineral tillhörande pyroklorsupergruppen. De samarskitartade mineralen uppvisade en partiell likhet med samarskitgruppmineral (generell formel ABO4), men med hög grad av metamiktisering, dåliga stökiometrier, låga REE-halter, samt med varierande järn- och kalciumdominans i tentativ A-katjonposition och niobdominans i B-katjonpositionen. Även aluminiumsilikater, mineral från spinellgruppen samt hematit påvisades. Uppsprickning av de metamikta och spröda samarskitartade mineralen har möjliggjort en fluidmedierad omvandling, vilket bl.a. lett till bildning av sekundär radiogen blyglans. Resultaten av undersökningarna bekräftar att Kolsvapegmatiten representerar ett lokalt niob-tantalmineraliserat system. / The two chemically related metals niobium (Nb) and tantalum (Ta) are classified by the European Commission as critical raw materials. This is due to a highly increased demand and a limited global supply situation for these metals. This work is a part of a larger project run by EuroGeoSurveys (EGS); the GeoERA FRAME, which aims to map the distribution of critical raw materials in the EU. Two granitic pegmatite samples from the Kolsva feldspar mine were studied with regards to their chemistry and mineralogy. They had been tentatively identified as consisting of a columbite mineral and a samarskite-like mineral, respectively. In the project, three main analytical methods have been used: 1) optical microscopy, 2) scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS), and 3) powder X-ray diffraction analysis (XRD). The analyses performed on the “columbite samples” indicated that most of them were columbite-(Fe), general formula AB2O6, with an iron dominance in the A-cation position and niobium dominance in the B-cation position. The analyses also indicated the presence of minerals belonging to the pyrochlore supergroup. The analyses of the samarskite-like minerals yielded results showing a partial resemblance to the samarskite group minerals (general formula ABO4), but with a high degree of metamictisation, poor stoichiometries, low to very low REE contents, variable iron and calcium-dominance in a tentative A-cation position and niobium-dominance in the B-cation position. Aluminium silicates, minerals from the spinel group and hematite were also observed in this assemblage. Fracturing of the brittle, metamict samarskite-like minerals have enabled a fluid-mediated alteration, which a.o. led to the formation of secondary radiogenic galena. The study confirms that the Kolsva pegmatite represents a locally Nb-Ta mineralised system.

This thesis refers to Fe-based biodegradable materials and their potencial aplications in medicine, especially as temporary bone implants. This work generaly summaries aplications of biomaterial in medicine with more interest kept on biodegradable materials and their in-vivo corrosion. The experimental part refers to conduction of porous Fe-based materials with silica addition. The structure of prepared specimens is identified by EDX and XRD analysis. The imersion test and electrochemical studies were conducted to observe corrosion behaviour with respect to different concentration of silica. Potenciodynamic curves were obtained to determine corrosion potencial and corrosion current density of prepared samples.

The demanding structural applications (e.g. aerospace, biomedical, etc.) require new materials with improved mechanical performance. The novel Ti-based dendrite + nano-/ultrafine-structured (Ti-based DNUS) composites exhibit an advantageous combination of high compressive strength (2000 – 2500 MPa) and large compressive ductility (10 – 30 %) already in the as-cast state [1,2] and, therefore, can be referred as high-performance materials. However, these Ti-based composites frequently exhibit very low or even lack of tensile ductility [3]. Therefore, the aim of this research work is to develop high strength Ti-based DNUS composites with pronounced tensile plasticity and to correlate the mechanical properties with their microstructure. In order to reach the goal, the high-strength Ti66Nb13Cu8Ni6.8Al6.2 (at.%) alloy exhibiting large compressive ductility [4] was selected for the modification. The microstructure of Ti66Nb13Cu8Ni6.8Al6.2 is composed of two metallographic constituents including β-Ti dendrites and an interdendritic component. The β-Ti dendrites are enriched in Nb and, therefore, Nb is referred as “dendritic element” whereas the interdendritic component is enriched in Ni and Cu and, therefore, these are referred as “interdendritic elements”. To perform a systematic study of the “interdendritic elements” (Ni, Cu and Co) effect on microstructure, a number of alloys with different concentration and types of alloying elements (Ti-Nb-Cu-Ni-Al, Ti-Nb-Co-Ni-Al, Ti-Nb-Cu-Co-Al and Ti-Nb-Ni(Co)-Al) were developed. It was shown that a higher concentration of the “interdendritic elements” in a composition within one alloy system corresponds to a higher volume fraction of the interdendritic component. Additionally, the crystal structure of the interdendritic phases is affected by type of the “interdendritic elements”. Since the most advanced applications (e.g. aerospace) require materials with high specific strengths, the new ductile Ti-Nb-Cu-Ni-Al alloys were modified to reduce their density, i.e. the Nb was substituted by lighter V. As a result, a new family of Ti-V-Cu-Ni-Al alloys with improved specific strength compared to the Ti-Nb-Cu-Ni-Al alloys was developed. Additionally, moduli of resilience of the Ti-V-Ni-Cu-Al alloys are superior when compared with those of the commercial Ti-based spring materials. The effect of microstructure on deformation of the newly developed alloys was studied through the in-situ microstructural analysis of samples at different strained states by means of scanning electron microscopy. To reveal the effect of the metallographic constituents on strength, the microhardness mapping of the new alloys was performed. Using the obtained empirical principles of microstructure adjustment, a new Ti68.8Nb13.6Co6Cu5.1Al6.5 (at.%) alloy with a large static toughness (superior to those of the recently developed Ti-based metallic glass composites) was developed. This large static toughness is due to both high strength and significant tensile plasticity. To study the effect of microstructure on tensile plasticity of Ti68.8Nb13.6Co6Cu5.1Al6.5 the in-situ microstructural analysis of samples at different strained states in the scanning electron microscope as well as the transmission electron microscopy studies were performed. / Der erhöhte Anspruch an strukturelle Anwendungen (z.B. Luftfahrt, Biomedizin, etc.) verlangt neue Werkstoffe mit verbesserten mechanischen Leistungsfähigkeiten. Neuartige Ti-basierte dendritische nano-/ultrafeine Komposite (Ti-basierte DNUS Komposite) besitzen eine vorteilhafte Kombination von hoher Druckfestigkeit mit großer plastischer Verformbarkeit unter Druckbelastung bereits im Gusszustand [1,2] wodurch sie als hochleistungsfähige Werkstoffe angesehen werden. Jedoch besitzen diese Ti-basierte DNUS Komposite heufig eine stark verringerte oder gar keine Duktilität unter Zugbelastung [3]. Deswegen ist es das Ziel dieser Forschungsarbeit neue hochfeste Ti-basierte DNUS Komposite mit ausgeprägter Duktilität unter Zugbelastung zu entwickeln und die mechanischen Eingeschaften mit ihrer Mikrostruktur zu korrelieren. Um dieses Ziel zu erreichen wurde die hochfeste Legierung Ti66Nb13Cu8Ni6.8Al6.2 (at.%) [4], die eine große plastische Verformbarkeit unter Druckbelastung aufweist, ausgewählt. Die Mikrostruktur von Ti66Nb13Cu8Ni6.8Al6.2 setzt sich aus zwei metallographischen Konstituenten, einschließlich β-Ti Dendriten und einer interdendritischen Komponente, zusammen. Die β-Ti Dendriten sind mit Nb angereichert, weswegen Nb als “dendritisches Element” bezeichnet wird, wohingegen die interdendritische Komponente mit Ni und Cu angereichert ist und deswegen diese als “interdendritische Elemente” bezeichnet werden. Um den Einfluss der “interdendritischen Elemente” (Ni, Cu and Co) auf die Mikrostruktur zu untersuchen wurden Legierungen mit verschiedenen Konzentrationen unterschiedlicher Legierungselemente (Ti-Nb-Cu-Ni-Al, Ti-Nb-Co-Ni-Al, Ti-Nb-Cu-Co-Al and Ti-Nb-Ni(Co)-Al) entwickelt. Es wurde gezeigt, dass eine höhere Konzentration “interdendritischer Elemente” in einer bestimmten Zusammensetzung einem höheren Volumanteil der interdendritischen Komponente entspricht. Zusätzlich wird die Kristallstruktur der interdendritischen Phase sehr stark durch die “interdendritischen Elemente” beeinflusst. Da die meisten hoch entwickelten Anwendungen (z.B. Luftfahrt) gesteigerte spezifische Festigkeiten erforden, wurden die neuen duktilen Ti-Nb-Cu-Ni-Al Legierungen modifiziert um ihre Dichte zu reduzieren, indem Nb durch das leichtere V ersetzt wurde. Als Ergebniss wurde eine neue Familie von Ti-V-Cu-Ni-Al Legierungen, mit im Vergleich zu Ti-Nb-Cu-Ni-Al Legierungen verbesserten spezifischen Festigkeiten, entwickelt. Zusäzlich ist die elastische Formänderungsenergiedichte der neu entwickelten Legierungen höher verglichen mit kommerziellen Ti-basierten Federmaterialien. Der Effekt der Mikrostruktur auf das Verformungsverhalten der Legierungen wurde mittels in-situ mikrostruktureller Analysen verschiedener Verformungszustände im Rasterelektronenmikroskop untersucht. Um ein Einfluss der metallographischen Konstituenten auf die Festigkeit zu bestimmen wurden Mikrohärtekarten erstellt. Unter Verwendung der erhalten empirischen Prinzipen zur Einstellung der Mikrostruktur wurde eine neue Legierung Ti68.8Nb13.6Co6Cu5.1Al6.5 (at.%) mit hoher statischer Zähigkeit (besser als die der kürzlich entwickelten Ti-basierten gläsernen metallischen Kompositlegierungen) entwickelt. Diese hohe statische Zähigkeit wird sowohl durch die hohe Festigkeit als auch durch die ausgeprägte Plastizität unter Zugbelastung verursacht. Um den Einfluss der Mikrostruktur auf die Plastizität unter Zug zu untersuchen wurde Transmissionelektronmikroskopie sowie in-situ mikrostrukturelle Analysen verschiedener Verformungszustände im Rasterelektronmikroskop durchgefühlt.

Gegenstand der Arbeit ist die Analyse der bei hohen Verformungsgraden in Werkstoffen durch kollektive Bewegung der Versetzungen entstandenen neuen Defektkonfigurationen, die auf der mesoskopischen Skala agieren. Diese so genannte Disklinationen rufen neben starken Gitterdehnungen auch erhebliche lokale Gitterrotationen hervor. Es wurde der Nachweis der Existenz der Disklinationen in plastisch verformten Kristallen geliefert sowie die qualitative und quantitative Analyse der Disklinationskonfigurationen und der Disklinationsstärke durchgeführt. Die Untersuchungen an stark verformten Ein- und Vielkristallen wurden mittels sowohl lokalen Methoden der Transmissions- (TEM, CBED) und Rasterelektronenmikroskopie (REM, EBSD) als auch der integralen Methoden der Röntgenstrukturanalyse (XRD) durchgeführt. Die Ergebnisse haben gezeigt, dass die Entwicklung der Zellblockstruktur mit erheblichem Anstieg der Desorientierungen und Versetzungsdichten in Versetzungswänden verbunden ist und durch die Bildung der Netzwerke von Disklinationen gefördert wird.

To meet the global hydrocarbon energy demand, it is imperative either to enhance the production from existing fields by applying innovative engineering solutions or discovering new field /resource areas. Both of these options are investigated by petroleum engineers intensively to tackle the challenges of meeting the ever-increasing demand. Meeting the energy demand as, like any other developing country, Jordan is facing a formidable challenge and requires exploration for conventional and unconventional hydrocarbon resources. As Jordan has a long exploration history for conventional reservoirs, Unconventional resource exploration and production seems to be the way to find new energy sources. Different exploration wells were drilled to evaluate the hydrocarbon potential. This research work is focusing on an experimental investigation to evaluate Jordanian hydrocarbon potential as well as to provide recommendations for future exploration activities in shale resources. The Evaluations were performed through comprehensive laboratory experiments that include measurements of Total Organic Content, Grain density, Pore Size Distribution, Specific Surface Area (BET), Mineralogy, Thermogravimetry Analysis, and Rock-Eval pyrolysis. The petrophysical properties (TOC, grain density, pore size distribution) of Jordanian shale (nine different wells) are investigated. The TOC and grain density are in an inversely proportional relationship. The TOC results show a gradual increment with the depth. All the samples have higher porosity dominated by macro pores. Fourteen (14) samples were selected primarily based on TOC (above 1.5%) for further analysis. The specific surface area results show a proportional relationship with the TOC content. Considering the petrophysical properties and mineralogy, these Jordanian shales broadly can be considered as high porosity clay and mudstone type of shale. Thermogravimetry analysis (TG/DTG) results indicate quantitative information related to organic and inorganic matter. Detection of thermos-reactive minerals, especially clay, carbonate, muscovite, pyrite is possible due to the combination of TG/DTG/DSC. The samples are examined under three different procedures which includes different heating programs. The oxidizing and inert atmospheric conditions (procedure i & ii) have the same heating program whereas procedure iii (inert atmospheric condition) has a heating program similar to the Rock-Eval pyrolysis program. The results of these samples show the complex nature of shale as well as organic matter by reacting in different stages (two or, three stages). Depending of the maturity of organic matter, the reaction occurring temperature range varies. Maximum oxidization reaction peaks happen between 479°C to 502°C. The maximum pyrolysis reaction peaks between 498°C to 521°C. Compared with complex heating (procedure iii) and rock Eval pyrolysis, S2 results indicate a high amount of inorganic compounds. Considering TGA reaction peaks and rock Eval pyrolysis results, these Jordanian shales indicate immature with low hydrocarbon generation potential. The Jordanian shale samples are analyzed by using Rock-Eval pyrolysis. Analysis results are used to interpret petroleum potential in rocks. The most important information includes organic matter types (also connected with the depositional settings), organic matter thermal maturity, and the remaining hydrocarbon generation potential in the current form. The organic geochemical analysis results indicate mostly poor to no source rock potential except JF2-760 samples. The hydrogen index (HI) and oxygen index (OI) result suggests that type iii kerogen and type iii/ iv kerogen are most likely from terrestrial and varied settings origin. The low hydrogen, as well as, low S2 value indicate very little hydrocarbon generation potential. Similarly, The Tmax and PI data indicate immature to early mature source rock status and low conversion scenario. Furthermore, the supercritical CO2 is injected into the samples, which is similar to gas flooding experiments to understand the recovery process. Hydrocarbon recovery or, CO2-shale interaction is determined by comparing three different properties (TOC, SSA, and TGA) pre-and-post supercritical CO2 injection. Supercritical CO2 injection in immature shale shows very limited property changes (TOC, SSA, and TGA) to the samples. However, in presence of hydrocarbon the pre-and post-injection property changes TOC, TGA, and SSA (BET) are noticeable enough to conclude HC recovery. Although in the case of immature shale with no hydrocarbon potential the kerogen or bitumen extraction has not been detected, which can be significant in the case of greenhouse gas storage, especially CCUS. This could reduce the risk of Organic Matter (OM) migration possibility in case immature shale formation is present in a suitable geological location.

The aim of the presented work was to deposit cubic boron nitride thin films by magnetron sputtering under simultaneous stress relaxation by ion implantation. An in situ instrument based on laser deflectometry on cantilever structures and in situ ellipsometry, was used for in situ stress measurements. The characteristic evolution of the instantaneous stress during the layered growth of cBN films observed in IBAD experiments, could be reproduced for magnetron sputter deposition. To achieve simultaneous stress relaxation by ion implantation, a complex bipolar pulsed substrate bias source was constructed. This power supply enables the growth of cBN thin films under low energy ion irradiation (up to 200 eV) and, for the first time, the simultaneous implantation of ions with an energy of up to 8 keV during high voltage pulses. It was demonstrated that the instantaneous stress in cBN thin films can be released down to -1.1 GPa by simultaneous ion bombardment during the high voltage pulses. A simultaneous stress relaxation during growth is possible in the total investigated ion energy range between 2.5 and 8 keV. These are the lowest ion energies reported for the stress relaxation in cBN. Since such a substrate bias power supply is easy to integrate in existing process lines, this result is important for industrial deposition of thin films, not only for cubic boron nitride films. It was found that the amount of stress relaxation depends on the number of atomic displacements (displacements per atom: dpa) that are induced by the high energy ion bombardment and is therefore dependent on the ion energy and the high energy ion flux. In practise, this means that the stress relaxation is controlled by the product of the pulse voltage and the pulse duty cycle or frequency. The cantilever bending measurements were complemented on microscopic scale by x-ray diffraction (XRD). The analysis of the cBN (111) lattice distances revealed a pronounced biaxial compressive state of stress in a non-relaxed cBN film with d(111) being larger in out-of-plane than in in-plane direction. Post deposition annealing at 900 ° C of a sample with an ion induced damage of 1.2 dpa, resulted in a complete relaxation of the lattice with equal in-plane and out-of-plane lattice parameters. In the case of medium-energy ion bombardment, the in-plane and out-of-plane lattice parameters approach the value of the annealed sample with increasing ion damage. This is a clear evidence for stress relaxation within the cBN lattice. The stability of cBN under ion bombardment was investigated by IR spectroscopy and XRD. The crystalline cBN was found to be very stable against ion irradiation. However a short-range ordered, sp3/sp2 - mixed phase may exist in the films, which could be preferably converted to a sp2 -phase at high damage values. From the analysis of the near surface region by XANES, it can be concluded the stress relaxation by the energetic ion bombardment is less at the surface than in the bulk film. This is explained with the dynamic profile of the ion induced damage, that reaches the stationary bulk value in 15-20 nm depth, whereas it is decreasing towards the surface. This fits with the results that the stress relaxation is dependent on the amount of ion induced damage. Comparing the results from substrate curvature measurement, XRD, XANES, and IR spectroscopy possible mechanisms of stress relaxation are discussed. Concluding the results, it can be stated that using simultaneous ion implantation for stress relaxation during the deposition it is possible to produce BN films with a high amount of the cubic phase and with very low residual stress.

Twelve halloysites from different sources in Slovakia, Turkey, China, New Zealand and U.S.A. have been characterized by combination of analytical methods together with the commercial sample of halloysite supplied by Sigma-Aldrich. The aim of this work was to select suitable candidates for to be used as carriers of porphyrine photoactive molecules. In nature, the formation of halloysite is related to the weathering of magmatic rocks or to the hydrothermal alteration of volcanic rocks, frequently in the contact with limestones. Halloysite belong to the kaolinite group, but, contrarily to kaolinite, it contains molecules of water in the interlayer space. It occurs in two forms: hydrated halloysite (10 ?) and dehydrated halloysite (7 ?).Dehydrated halloysites contain more admixtures than hydrated ones ? typically kaolinite, quartz, cristobalite, alunite, gibbsite and in one case also potassium mica. In samples containing both dehydrated halloysite and kaolinite their 001 diffractions overlap. Interaction with formamide was used in these cases to increase the interlayer space of halloysite and thus shift its basal diffraction to lower angles. The basal 001 diffraction of kaolinite after this treatment remains on 7 ?. Silver thiourea method (AgTU) was used to measure the cationic exchange capacity (CEC). Silver...

Title: Preparation and characterization of bi-phasic magnetic nanoparticles Author: Bc. Adam Alemayehu Department: Department of Innorganic Chemistry Supervisors: doc. RNDr. Daniel Nižňanský, Ph.D. RNDr. Václav Tyrpekl, Ph.D. Consultant: M.Sc. Dominika Zákutná Abstract The work is focusing on the magnetic properties of ferrimagnetic spinel ferrites before and after the introduction of a shell on a core particle with different magnetic properties. The core nanoparticles were prepared by hydrothermal decomposition of oleate precursors. The introduction of shell was carried out by hydrothermal treatment of the already prepared core particles. The phase composition, spinel structure and the sizes of the prepared samples were investigated by powder X-ray diffraction and by transmission electron microscopy. Formation of the shell on top of the core particle was determined indirectly, using Mössbauer spectroscopy at room temperature. The interparticle interactions and the particle shape was studied by small angle X-ray scattering. The magnetic properties of the prepared samples were measured on a SQUID magnetometer. Key words: magnetic nanoparticles, core, shell, spinel structure, powder X-ray diffraction, Mössbauer spectroscopy, magnetic measurements, TEM