Depuis les premiers travaux publiés en 2004, le graphène est obtenu par trois principales techniques, l’exfoliation, le dépôt chimique en phase vapeur et la graphitisation du carbure de silicium. Seules les deux dernières sont adaptées aux technologies standards de la microélectronique. Une autre méthode est étudiée dans ce travail, consistant à faire croitre le graphène par épitaxie par jets moléculaires. Le SiC a été utilisé comme substrat du fait du faible désaccord de maille avec le graphène et de sa compatibilité avec les processus technologiques. La croissance de graphène a été obtenue avec succès sur les deux faces du SiC, à partir d’une source de carbone solide. La gamme de température utilisable est restreinte du fait de l’amorphisation ou de la graphitisation. La structure du graphène dépend fortement de la face du SiC considérée, de façon analogue à ce qui est obtenu par graphitisation (plan d’interface riche en C et empilement graphite sur la face Si, absence de couche d’interface et plans tournés et découplés électroniquement sur la face C). Les bandes de valence ont été mesurées en spectroscopie de photoélectrons résolue angulairement, et présentent la dépendance linéaire caractéristique du graphène aux points de Dirac. Cependant, la présence de défauts dans le matériau induit une forte réduction de la mobilité électronique. Cette dernière a été améliorée en réalisant la croissance épitaxiale sous un flux de Si externe, à plus haute température. / Since the first publications in 2004, three techniques are mainly used to grow graphene, exfoliation, chemical vapor deposition and graphitization on silicon carbide. Only the two latter ones are suitable with microelectronics technological processes. In this thesis, another method of growth is studied, molecular beam epitaxy. SiC has been chosen as substrate, because of the weak lattice mismatch with graphene and for technology compatibility. Thin films of graphene have been successfully grown from a solid carbon source on both faces of SiC. Amorphization and graphitization restrain the growth temperature range. The MBE graphene structure depends on the considered SiC face, as graphene grown by graphitization does (C-rich interface layer and graphite stacking on the Si face, rotated and electronically uncoupled graphene layers on the C face). The valence bands have been measured by angle resolved photoelectron spectroscopy and show the characteristic Dirac cone along the ΓК direction. However, defects are present in the MBE film, resulting in low electron mobility. This last point has been improved by growth under an external silicon flux, allowing higher temperature to be used.

In this thesis 3D diamond detectors were fabricated using an ultrafast femtosecond (120 fs) pulse length laser, with a 800nm wavelength, to induce a phase change of diamond to graphite to form electrodes in the diamond bulk. Graphitic electrodes, with diameters of O(um), were fabricated using a known processing technique and were enhanced further through the use of a Spatial Light Modulator (SLM), which is a new technology in this field. These detectors were subsequently characterised through the use of particle beams, and this work also presents methods for characterising such detectors: A pair of crossed polarisers to determine the stress induced by the electrodes on the diamond bulk; Raman spectroscopy to assess the relative quantity of diamond:graphite formed; Scanning Electron Microscopy (SEM) to image the starting (seed) and finishing (exit) sides of electrode formation; and current-voltage (I-V) measurements to calculate the electrical properties of the electrodes. These characterisation methods (alongside the use of particle beams) serve as a means to compare the two fabrication techniques and to determine the optimum fabrication parameters to produce 3D diamond detectors for use as tracking detectors in high luminosity environments such as those in the Large Hadron Collider (LHC). This work shows that using a higher beam energy and translation speed of the focal spot results in electrodes of lower electrical resistivity, which is an ideal characteristic for a tracking detector. These higher processing parameters also result in more graphitic structure on the seed and exit sides of the diamond, determined separately via Raman spectroscopy and SEM. An increased beam energy also results in larger electrode diameters, reducing the active area of the detector and inducing more stress in the diamond bulk. These measurements therefore indicate an upper limit on the fabrication parameters. A further study into these processing parameters shows the translation speed scales with the pulse repetition rate of the laser and allows for fast fabrication of 3D diamond detectors. Two devices were fabricated with and without the use of an SLM, with a more uniform detector response (through characterisation by particle beams), lower electrical resistivity, and more graphitic material observed for SLM-fabricated electrodes. The benefits of square and hexagonal cell structures were also investigated with both structures showing a similar response to particle beams. A lower charge sharing region is observed in hexagonal cells and indicates potentially different applications for these cell geometries. Transient Current Technique (TCT) measurements were also taken on both detectors, where faster charge collection and higher quality data were seen for the SLM-fabricated device. These measurements indicate a preference in the use of an SLM for the future fabrication of 3D diamond tracking detectors. These TCT measurements were then compared to simulations to extract the charge carrier properties in diamond. Only qualitative agreement was obtained, motivating further work in this area to fully understand the charge carrier dynamics and demonstrate the future viability of 3D diamond detectors.

Synthetic graphite is an important industrial material, used in nuclear reactors, electrodes and many other applications. Graphitisation of coke is the solid-state transformation of the disordered carbon atoms into a well-ordered hexagonal graphite structure, requiring temperatures as high as 2 600 ºC. Catalytic graphitisation using metals or metal compounds allows the rearrangement of atoms to occur at lower temperatures. The extent of catalytic graphitisation is markedly dependent on the structural ordering of the parent coke, the catalyst concentration and the reaction conditions. Solvent extraction of coal using dimethylformamide (DMF) as a solvent yields a refined coal solution referred to as Refcoal solution. Cokes of solvent-refined Tshikondeni coal derivatives have been found to be graphitisable. The activity of acetylacetonate and hydroxyquinolinate complexes of Al, Ca, Cu, Fe and Zr for catalysing the graphitisation of Refcoal cokes at 1 600 and 2 000 ºC was investigated. The effect of residence time on the catalytic graphitisation of Refcoal cokes was investigated by heat-treating cokes for two and six hours at 1 600 °C. For iron(III)acetylacetonate, the effect of metal concentrations was studied. Samples were analysed using thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy and optical microscope techniques. The results show that calcium(II)acetylacetonate catalyses the graphitisation of Refcoal cokes. The degree of graphitisation increases with an increase in the iron concentration. However, iron promotes localised graphitisation, probably in the vicinity of the catalyst particles. / Dissertation (MSc (Chemistry))--University of Pretoria, 2008. / Chemistry / unrestricted

Les fontes à graphite sphéroïdal sont aujourd’hui très largement utilisées en raison de leurs bonnes propriétés mécaniques. La forme sphéroïdale du graphite est obtenue le plus souvent par l’ajout de magnésium ou de cérium lors de l’élaboration des fontes. Le graphite sphéroïdal peut être obtenu par graphitisation à l'état solide des fontes totalement ou partiellement solidifiées dans le système métastable. L’objectif de ce travail est d’étudier l’effet du traitement de graphitisation à l’état solide sur la croissance du graphite nodulaire d’une fonte à paroi mince qui présente une structure truitée à l'état brut de coulée. Cette fonte a été étudiée par microscopie optique, microscopies électronique à balayage et en transmission, spectroscopie Raman et spectroscopie de perte d'énergie des électrons. Des traitements thermiques assurant une graphitisation totale et partielle pour décomposer la cémentite formée à la solidification en graphite et en austénite ont été réalisés. Les nodules deviennent plus nombreux et leur taille augmente en fonction du temps de graphitisation. La microstructure après traitement thermique est composée de nodules de graphite et de ferrite. La spectroscopie Raman a été utilisée pour caractériser les nodules de graphite d’échantillons ayant été entièrement graphitisés à différentes températures dans le domaine austénitique. L’analyse par spectroscopie Raman ne montre aucune différence significative entre les spectres Raman enregistrés sur le graphite formé lors de la solidification et à l’état solide. Les caractérisations microstructurales par microscopie électronique en transmission montrent que le graphite à l’état brut de coulée présente une structure caractérisée par une zone interne où le graphite est désorienté. Une déformation mécanique due à la contraction lors de la solidification métastable induit la formation de cette zone. Cette zone disparaît par recristallisation après traitement de graphitisation totale pour former à la fin des secteurs coniques rayonnant à partir du germe et se développant vers la périphérie. Les résultats de ces travaux ont permis une meilleure compréhension de la structure de graphite nodulaire à l’état solide et montre aussi que le mécanisme de croissance du graphite nodulaire est le même lors de la solidification et de la transformation à l'état solide. / Spheroidal graphite iron castings are today widely used because of their good mechanical properties. The spheroidal shape of graphite is most often obtained by the addition of magnesium or cerium during the casting process. Spheroidal graphite can be formed at the solid-state by graphitization of cast irons which solidified partly or totally in the metastable system. The purpose of this work is to study the effect of solid-state graphitization treatment on the growth of nodular graphite of a thin wall casting which has a mottled structure at the as-cast state. This cast iron was studied using optical microscopy, scanning and transmission electron microscopy, Raman spectroscopy and electron energy loss spectroscopy. Heat treatments ensuring a total and partial graphitization to decompose the cementite formed at the solidification in graphite and austenite were realized. The nodules become more numerous and their size increases according to the time of graphitization. The microstructure after heat treatment is composed of graphite nodules and ferrite. Raman spectroscopy has been used to characterize graphite nodules in as-cast state and in samples having been fully graphitized at various temperatures in the austenite field. The results show no significant difference between Raman spectra recorded on these various samples, suggesting graphite grows with the same mechanism during either solidification or hightemperature (so-called first stage) graphitization. Transmission electron microscopy characterizations show that nodules in the as-cast material presents a multi-fold structure characterized by an inner zone where graphite is misoriented and an outer zone where it is well crystallized. In heat-treated samples, graphite nodules consist of well crystallized sectors radiating from the nucleus. These observations suggest that the misoriented zone appears because of mechanical deformation when the liquid contracts during its solidification. During heat-treatment, this zone disappears by recrystallization. The results of the present work lead to a better understanding of the nodular graphite structure in the solid state and also show that nodular graphite growth mechanism is the same during solidification and solid-state transformation.

Cette thèse est focalisée sur la contribution de l'étude couplée de l’organisation multi-échelle et de la composition isotopique de C et N des carbones de météorites différenciées (acapulcoites – lodranites (A-L)), pour mieux comprendre l’histoire de leur corps-parent. Nous avons systématiquement combiné observations des carbones de ces météorites avec des analogues expérimentaux. Nous avons développé une méthodologie originale couplant l'étude de l'organisation des échelles micrométriques à nanométriques (par Microscopie Electronique par Transmission et Microspectrométrie Raman) et l'analyse isotopique des carbones (par SIMS) sur rigoureusement les mêmes plages de dimensions micrométriques. La comparaison avec les mélanges expérimentaux indique que le graphite d’Acapulco s’est formé par un mode de graphitisation "catalysée par le fer". L’absence de graphitisation des carbones de Lodran dans un environnement riche en fer et chaud est apparemment paradoxale. Toutes nos observations peuvent être réconciliées si nous considérons une collision tardive du corps-parent des A-L avec un corps chondritique apportant matière organique insoluble et chaleur d'impact. Ce scénario est conforté par les analyses isotopiques qui indiquent une formation des carbones des A-L par carbonisation d’un précurseur chondritique et une migration d’effluents carbonés au sein du corps-parent / This thesis is focused on the contribution of the coupling of multi-scale organization and C, N isotopic composition of carbons in differentiated meteorites (acapulcoites – lodranites (A-L)), in order to better understand the history of their parent body. We systematically combined observations of carbons from these meteorites with experimental analogues. We developed an original methodology associating the study of the organization at the micrometre to nanometre scales (by Transmission Electron Microscopy and by Raman Microspectrometry), and the analysis of the isotopic composition of carbons (by SIMS) on strictly the same areas of micrometre dimensions. The comparison with experimental analogues indicates that the Acapulco graphite was formed by a "catalytic" graphitization mode. The absence of graphite in Lodran, in an iron-rich and hot environment, is apparently paradoxical. All our observations can be reconciled if we consider a late collision of the A-L parent body with a chondritic body bringing insoluble organic matter and impact heat. This scenario is strengthened by isotopic analyses, which indicate formation of A-L carbons by carbonization of a chondritic precursor and migration of carbonaceous effluents within the parent-body

The main objective of this industrially important work was to gain an increasing understanding of the properties of some industrially important materials such as CMSX-4 nickel base super alloy, 90Ti.6Al.4V alloy, 25Cr:6Ni stainless steel, 0.7% carbon steel, AISI 304 stainless steel-alumina composites, mould powder used in continuous casting of steel as well as coke used in blast furnace with special reference to the thermal diffusivities. The measurements were carried out in a wide temperature range covering solid, liquid, glassy and crystalline states. For CMSX-4 alloy, the thermal conductivities were calculated from the experimental thermal diffusivities. Both the diffusivities and conductivities were found to increase with increasing temperature. Microscopic analysis showed the presence of intermetallic phases γ´ such as Ni3Al below 1253 K. In this region, the mean free path of the electrons and phonons is likely to be limited by scattering against lattice defects. Between 1253 K and solidus temperature, these phases dissolved in the alloy adding to the impurities in the matrix, which, in turn, caused a decrease in the thermal diffusivity. This effect was confirmed by annealing the samples at 1573 K. The thermal diffusivities of the annealed samples measured at 1277, 1403 and 1531 K were found to be lower than the thermal diffusivities of non-annealed samples and the values did not show any noticeable change with time. It could be related to the attainment of equilibrium with the completion of the dissolution of γ´ phase during the annealing process. Liquid CMSX-4 does not show any change of thermal diffusivity with temperature. It may be attributed to the decrease of the mean free path being shorter than characteristic distance between two neighbouring atoms. Same tendency could be observed in the case of 90Ti.6Al.4V alloy. Since the thermal diffusivity increases with increasing temperature below 1225 K and shows slight decrease or constancy at higher temperature. For 25Cr:6Ni stainless steel, the thermal diffusivity is nearly constant up to about 700 K. Beyond that, there is an increase with temperature both during heating as well as cooling cycle. On the other hand, the slope of the curve increases above 950 K, which can be due to the increase of bcc phase in the structure. 0.7% carbon steel shows a decrease in the thermal diffusivity at temperature below Curie point, where the structure contains bcc+ fcc phases. Above this point the thermal diffusivity increases, where the structure contains only fcc phase. The experimental thermal conductivity values of these alloys show good agreement with the calculated values using Mills model. Thermal diffusivity measurements as a function of temperature of sintered AISI 304 stainless steel-alumina composites having various composition, viz, 0.001, 0.01, 0.1, 1, 2, 3, 5, 7, 8 and 10 wt% Al2O3 were carried out in the present work. The thermal diffusivity as well as the thermal conductivity were found to increase with temperature for all composite specimens. The thermal diffusivity/conductivity decreases with increasing weight fraction of alumina in the composites. The experimental results are in good agreement with simple rule of mixture, Eucken equation and developed Ohm´s law model at weight fraction of alumina below 5 wt%. Beyond this, the thermal diffusivity/ conductivity exhibits a high discrepancy probably due to the agglomeration of alumina particles during cold pressing and sintering. On the other hand, thermal diffusivities of industrial mould flux having glassy and crystalline states decrease with increasing temperature at lower temperature and are constant at higher temperature except for one glassy sample. The thermal diffusivity is increased with increasing crystallisation degree of mould flux, which is expected from theoretical considerations. Analogously, the thermal diffusivity measurements of mould flux do not show any significant change with temperature in liquid state. It is likely to be due to the silicate network being largely broken down. In the case of coke, the sample taken from deeper level of the pilot blast furnace is found to have larger thermal diffusivity. This can be correlated to the average crystallite size along the structural c-axis, Lc, which is indicative of the higher degree of graphitisation. This was also confirmed by XRD measurements of the different coke samples. The degree of graphitisation was found to increase with increasing temperature. Further, XRD and heat capacity measurements of coke samples taken from different levels in the shaft of the pilot blast furnace show that the graphitisation of coke was instantaneous between 973 and 1473 K. / QC 20100629

Cette thèse est focalisée sur la contribution de l'étude couplée de l'organisation multi-échelle et de la composition isotopique de C et N des carbones de météorites différenciées (acapulcoites - lodranites (A-L)), pour mieux comprendre l'histoire de leur corps-parent. Nous avons systématiquement combiné observations des carbones de ces météorites avec des analogues expérimentaux. Nous avons développé une méthodologie originale couplant l'étude de l'organisation des échelles micrométriques à nanométriques (par Microscopie Electronique par Transmission et Microspectrométrie Raman) et l'analyse isotopique des carbones (par SIMS) sur rigoureusement les mêmes plages de dimensions micrométriques. La comparaison avec les mélanges expérimentaux indique que le graphite d'Acapulco s'est formé par un mode de graphitisation "catalysée par le fer". L'absence de graphitisation des carbones de Lodran dans un environnement riche en fer et chaud est apparemment paradoxale. Toutes nos observations peuvent être réconciliées si nous considérons une collision tardive du corps-parent des A-L avec un corps chondritique apportant matière organique insoluble et chaleur d'impact. Ce scénario est conforté par les analyses isotopiques qui indiquent une formation des carbones des A-L par carbonisation d'un précurseur chondritique et une migration d'effluents carbonés au sein du corps-parent

Ce travail de doctorat a été réalisé dans le cadre d'un accord de cotutelle international entre l'Université de Salento (L3, Italie) et l'Université de Paris 13 (LSPM, France). L'objectif principal était la fabrication de contacts ohmiques sur des surfaces de diamant pour des applications telles que les détecteurs et les dispositifs de l’électronique. Les travaux au L3 ont été consacrés à l'étude du processus de graphitisation du diamant induit par laser afin de produire des électrodes de graphite sur des diamants intrinsèques. L'étude se concentre en particulier sur le développement d’un appareil expérimental pour l’écriture laser sur diamant tant sur les aspects matériel que logiciel, et un protocole a ainsi été développé pour la fabrication de contacts graphitiques segmentés sur de larges surfaces de diamant (cm²). Des travaux approfondis de caractérisation ont démontré la transition de phase diamant-graphite et le comportement ohmique pour les contacts électriques avec une résistivité de l'ordre de 10⁻⁵ Ω.m. Des détecteurs tout-carbone ont ainsi été développés et testés avec des faisceaux électroniques et positroniques de 450 MeV. Ils permettent d’ouvrir des perspectives en tant que cible active pour de nouvelles expériences de physique des hautes énergies (PADME) dans le cadre de l’étude de la matière noire. Le travail au LSPM a été consacré au développement d'un protocole permettant d'obtenir des contacts ohmiques sur des films diamant faiblement dopé au bore et terminé oxygène, élaborés par MPACVD. Les procédés de fabrication de contacts métalliques Ti/Au sur une structure mesa ainsi que l’implantation par des ions He, ont été développés afin d'induire une couche de graphite juste en dessous de la surface de diamant. Les mesures électriques sur des diamants légèrement dopés ([B] = 4 × 10¹⁷ cm⁻³) avec seulement des contacts métalliques ou graphitiques / métalliques ont montré que la présence de la couche graphitique rend les contacts ohmiques et conduisent à une résistance spécifique de contact égale à 3.3 × 10⁻⁴ Ω.cm². / This PhD work has been carried out in international cotutelle agreement between the University of Salento (L3, Italy) and the University of Paris 13 (LSPM, France). The main aim was the manufacturing of ohmic contacts on diamond surface for detector and electronic device applications. The work at L3 was dedicated to the laser-induced diamond graphitization process in order to produce graphitic electrodes on intrinsic diamonds. An experimental set-up dedicated to the laser writing technique on diamond has been developed in both hardware and software aspects and a protocol for the manufacturing of segmented graphitic contacts on diamond surface of large scale (cm²) has been implemented. An extensive characterization work has demonstrated the diamond-graphite phase transition and an ohmic electrical behaviour for the contacts with a resistivity of the order of ≈ 10⁻⁵ Ω.m. Eventually, an all-carbon detector has been developed and tested with 450 MeV electron and positron beams proving to be a good candidate in the role of active target for a new high-energy experiment (PADME) in the framework of the dark matter. The work at LSPM has been dedicated to the development of a protocol allowing reaching ohmic contacts on lightly boron doped diamond with oxygenated surface grown by MPACVD. The fabrication of Ti/Au metallic contact above a mesa structure has relied on a He ion implantation treatment to induce a graphitic layer underneath the diamond surface. The electrical measurements on lightly doped diamonds ([B] = 4 × 10¹⁷ cm⁻³) with metal or graphite / metal contacts have shown that the graphitic layer makes ohmic the contacts leading to a specific contact resistance as low as 3.3 × 10⁻⁴ Ω.cm². / Questo dottorato di ricerca è stato svolto in convenzione di cotutela internazionale tra l’Università del Salento (L3, Italia) e l’Università di Parigi 13 (LSPM, Francia). Il principale obiettivo è stato la fabbricazione di contatti ohmici su superficie di diamante per applicazioni come rivelatori e dispositivi elettronici. Il lavoro a L3 è stato dedicato allo studio del processo di grafitizzazione del diamante indotto da laser al fine di produrre elettrodi grafitici su diamanti intrinseci. In particolare, è stato sviluppato un apparato sperimentale dedicato alla tecnica di scrittura laser su diamante sia nelle componenti hardware che software, ed è stato realizzato un protocollo per la fabbricazione di contatti grafitici segmentati su superfici di diamante di grande scala (cm²). Un ampio lavoro di caratterizzazione ha dimostrato la transizione di fase diamante-grafite e il comportamento ohmico per i contatti elettrici con una resistività dell’ordine di 10⁻⁵ Ω.m. Pertanto, un rivelatore costituito solo di carbonio è stato sviluppato e testato con fasci elettronici e positronici di 450 MeV risultando essere un buon candidato nel ruolo di bersaglio attivo per un nuovo esperimento di fisica delle alte energie (PADME) nel contesto della materia oscura. Il lavoro a LSPM è stato dedicato allo sviluppo di un protocollo che ha consentito di ottenere contatti ohmici su diamanti leggermente drogati con boro e con superficie terminata con ossigeno, cresciuti mediante MPACVD. I processi di fabbricazione di contatti metallici Ti/Au sopra una struttura mesa sono stati sviluppato così come un trattamento di impiantazione a base di ioni di He al fine di indurre uno strato grafitico appena sotto la superficie del diamante. Le misure elettriche su diamanti leggermente drogati ([B] = 4 × 10¹⁷ cm⁻³) con contatti o solo metallici o grafitici / metallici hanno dimostrato che la presenza dello strato grafitico rende i contatti ohmici e comporta una resistenza specifica di contatto pari a 3.3 × 10⁻⁴ Ω.cm².

Les interconnexions des circuits intégrés sub-0.25µm nécessitent l'intégration d'isolants «low-K» à plus faible permittivité diélectrique que SiO2 (~ 4.4) tel que le SiLK™ (~ 2.65), un matériau organique prometteur. Mais sa gravure plasma conduit à l'obtention de structures en forme de tonneau («bow»), alors que les profils gravés doivent rester anisotropes pour les étapes ultérieures d'intégration. Afin de réduire le bow, cette étude montre que la passivation des flancs des structures gravées est nécessaire, et fortement corrélée à la dégradation («graphitisation») du SiLK et à la présence de résidus carbonés peu volatils dans le plasma. La présence de sources carbonées autres que le SiLK™ permet aussi d'améliorer la passivation. L'étude du phénomène à l'origine du bow montre enfin que les charges électrostatiques jouent un rôle majoritaire dans la déflexion des ions sur les flancs. Ces résultats intéressent également tous les low-Ks à faible seuil de gravure ionique réactive.