Dans ce travail de thèse j’ai étudié la structure et la réactivité des couches minces des phthalocyanine de lutétium déposées sur des surfaces métalliques. La connaissance de la structure des couches minces épitaxées des matériaux organiques est importante pour la conception des dispositifs d’électronique organique. En effet la mobilité des porteurs de charge est très influencée par l’organisation moléculaire et l’ordre de la couche. La deuxième partie de ce travail concerne la réactivité des couches minces de ces molécules avec les gaz atmosphériques, ce qui est essentiel à la stabilité des dispositifs.Les couches minces ont étés préparées par évaporation thermique sous ultra vide et ont étés analysées par Microscopie a scansion de tunnel (STM), diffraction des rayons x (XRD), photoémission x (XPS) et Spectroscopie d’absorption x (NEXAFS). La structure des couches minces des LuPc2 déposées sur Au(111) a été trouvée. Les molécules adoptent une structure β et ressentent de l’effet modèle du substrat, comme prédit par les relations épitaxies. La morphologie de surface a été également trouvée à l’échelle moléculaire, y compris l’empillement et l’orientation des domaines.La faible réactivité de ces couches minces avec des gaz atmosphérique, en particulier oxygène et eau, a été prouvée. Le site d’absorption des molécules des gaz a été localisé non pas sur l’ion central mais plutôt sur le macrocycle organique. Il a été démontré aussi que ces molécules sont plus réactives vers l’oxygène moléculaire que vers l’eau. / In this thesis work I studied the structure and reactivity of Lutetium bis-phthalocyanine (LuPc2) thin films deposited on metallic surfaces. Knowing the structure of epitaxial organic thin films is important to design devices based on organic electronics, because carrier mobility, critically depends on the molecular configuration and thin film ordering. The second part of the work deals with the reactivity of molecular thin films towards atmospheric gases which is crucial for lifetime of the device. We chose LuPc2 because, due to the double decker molecular geometry they should present a different reactivity respect to single decker phthalocyanine, which are widely used in devices.The thin films were prepared by thermal evaporation under ultra-high vacuum conditions and analysed by means of Scanning Tunnelling Microscopy (STM) and X-ray Diffraction (XRD), X-ray Photoemission Spectroscopy (XPS) and Near Edge X-ray Absorption Fine Structure Spectroscopy (NEXAFS).We resolved the structure of a LuPc2 thin film deposited on Au(111), showing that the molecules adopt a β structure and demonstrated the templating effect of the substrate via the epitaxial relations with the overlayer. We then present the surface morphology at the molecular scale, including stacking and domain orientations.We tested the reactivity of these thin films towards atmospheric gases, in particular oxygen and water, showing a low reactivity and managing to demonstrate the adsorption sites, which are not the central cation, but rather on the macrocycle. We showed how oxygen is a greater threat to the film stability than water.

Mes travaux de thèse portent sur la fabrication et la caractérisation électrique et magnétique de jonctions tunnel à base de graphène. C’est autour de l’idée d’apporter une meilleur compréhension des mécanismes d’injection et de détection d’un courant de charge et de spin aux interfaces graphène/ferromagnétique que s’articule ce manuscrit. Après avoir démontré qu’il est possible de faire croître de manière épitaxiée une barrière tunnel de MgO sur graphène, nous avons étudié les mécanismes de transport dépendant en spin dans des jonctions verticales de Co/MgO/Gr/Ni. Nous avons mis en évidence l’interaction du graphène avec l’électrode de nickel à travers les inversions de signe de la magnétorésistance. Celles-ci peuvent être expliquées à l’aide d’un modèle de canaux de conduction assistés par phonons. Enfin du blocage de Coulomb reproductible a été mesuré dans des amas d’aluminium potentiellement mono disperses et auto assemblés sur graphène. / My PhD thesis deals with the fabrication and the electric and magnetic characterizations of magnetic tunnel junctions based on graphene. The interaction of graphene with its close environment opens new possibilities for spintronics applications. The manuscript is focused on the improvement of the understanding of mechanisms involved in the injection and detection of a polarized spin current at the graphene/ferromagnetic interfaces. We show that it is possible to grow epitaxially MgO tunnel barrier on graphene. We study the spin transport mechanisms in vertical junctions of Co/MgO/Gr/Ni. The interaction of graphene with nickel electrode is probed through tunnel magnetoresistance inversions which can be explained by the activation of phonon assisted conduction channel. We also measure in vertical and lateral devices based on alumina barrier on graphene, reproducible Coulomb blockade processes linked to the presence of monodisperse aluminum clusters at the graphene edge.

Seit 2002 kam ein neues Interesse an Germanium als Material für CMOS-Bauelemente auf, angetrieben durch die höhere Beweglichkeit der Ladungsträger im Vergleich zu Silizium. Für die Herstellung von Germanium MOSFETs bestehen allerdings noch einige Herausforderungen. Speziell die Problematik der hohen n-Dotierung für die Source- und Draingebiete der PMOS-Transistoren hat sich dabei als potentieller Roadblocker herauskristallisiert. Die geringe Aktivierung und die hohe Diffusivität der Donatoren in Germanium stellen ein Problem für die Herstellung von CMOS-Schaltkreisen aus Germanium dar. Als ursächlich dafür wurden Vakanzen identifiziert (Bracht et.al.). Um das Diffusions- und das Aktivierungsverhalten von Arsen und Phosphor in Germanium zu untersuchen, wurden p-Typ Germaniumwafer durch Ionenimplantation mit beiden Spezies dotiert und anschließend durch Rapid-Thermal-Annealing und/ oder Flash-Lamp-Annealing ausgeheilt. Zusätzlich wurden Experimente mit kodotierten und P-dotierten Proben mit verringerter Schichtkonzentration durchgeführt. Untersuchungen mit Rutherford-Backscattering-Spektroskopie und Transmissions-Elektronen-Mikroskopie werden durchgeführt, um die strukturellen Eigenschaften der Proben infolge der Implantation und der Ausheilung festzustellen. Mittels Sekundärionen-Massen-Spektroskopie wird die Dotandenkonzentration bestimmt. Es folgen elektrische Messungen des Schichtwiderstandes bei Raumtemperatur und in geeigneten Fällen bei Temperaturen unterhalb 10K. An ausgewählten Proben werden Hallmessungen durchgeführt. Die Gesamtheit der Analyseverfahren ermöglicht eine Analyse des Rückwachsverhaltens, der Diffusion und der elektrischen Aktivierung der Dotanden unter den verschiedenen Implantations- und Ausheilbedingungen. Die nach verschiedenen Methoden bestimmten Größen wie die Ladungsträgerkonzentration und -mobilität werden betrachtet und im Hinblick auf die Parameter der Probenpräparation analysiert und mit der Literatur verglichen. Abschließend werden mögliche Mechanismen zur Deaktivierung von Donatoren in Germanium erörtert.

Les supraconducteurs à haute température critique (HTS) sont des systèmes fortement corrélés. Dans ces matériaux, une petite modification du nombre de porteurs peut avoir de grandes conséquences sur leurs propriétés physiques. C'est le cas lorsqu'un matériau ferroélectrique est à proximité immédiate d'un HTS : de manière locale et rémanente, la polarisation ferroélectrique modifie par effet de champ électrostatique le nombre d'électrons dans le HTS, au voisinage de l'interface avec le ferroélectrique. Cet effet peut être exploité dans le but de définir des structures à géométrie variable : dans un premier cas, des jonctions qui consistent en deux électrodes supraconductrices, séparées par une zone où la supraconductivité a été affaiblie par effet de champ. Dans un second cas, des jonctions tunnel ferroélectriques - à nouveau avec des électrodes supraconductrices - où l'épaisseur de la barrière est modulable par effet de champ ferroélectrique. Les travaux menés au cours de cette thèse visent à développer les matériaux et les technologies de lithographie pour fabriquer de telles structures, et à caractériser les propriétés de transport de ces dernières. / In this experimental thesis, we fabricated ferroelectric field-effect devices based on high-Tc superconductors. We grew high-quality epitaxial heterostructures consisting of an ultra-thin (2 to 6 unit cells) film of YBCO and a thin ferroelectric film (BFO-Mn). We fabricated transport measurement microbridges and used a CT-AFM tip to polarise the BFO-Mn outwards or towards the BFO-Mn/YBCO interface. Due to the ferroelectric field-effect, the superconducting properties of the underlying YBCO film were consequently modified. We then used this effect locally in order to design weak links within the microbridges: two regions where the superconducting properties are enhanced are separated by a narrow region where they are depressed. We explored the conditions of existence of a Josephson coupling across this weak link. In parallel, we fabricated ferroelectric junctions. The barrier is an ultra-thin BFO-Mn film sandwiched between a high-Tc superconducting YBCO bottom electrode and a low-Tc superconducting top electrode. Both at room temperature and at low temperature, we characterised the transport properties across the barrier and the resistive switching resulting from the polarisation of the ferroelectric barrier.

The importance of infrared (IR) technology (for detection in the 3-5 μm and 8-14 μm atmospheric windows) has spread from military applications to civilian applications since World War II. The commercial IR detector market in these wavelength ranges is dominated by mercury cadmium telluride (MCT) alloys. The use of these alloys has, however, been faced with technological difficulties. One of the materials that have been tipped to be suitable to replace MCT is InAs/InxGa1-xSb strained layer superlattices (SLS’s). Atmospheric pressure metal-organic vapour phase epitaxy (MOVPE) has been used to grow InAs/GaSb strained layer superlattices (SLS’s) at 510 °C in this study. This is a starting point towards the development of MOVPE InAs/InxGa1-xSb SLS’s using the same system. Before the SLS’s could be attempted, the growth parameters for GaSb were optimised. Growth parameters for InAs were taken from reports on previous studies conducted using the same reactor. Initially, trimethylgallium, a source that has been used extensively in the same growth system for the growth of GaSb and InxGa1-xSb was intended to be used for gallium species. The high growth rates yielded by this source were too large for the growth of SLS structures, however. Thus, triethylgallium (rarely used for atmospheric pressure MOVPE) was utilized. GaSb layers (between 1 and 2 μm thick) were grown at two different temperatures (550 °C and 510 °C) with a varying V/III ratio. A V/III ratio of 1.5 was found to be optimal at 550 °C. However, the low incorporation efficiency of indium into GaSb at this temperature was inadequate to obtain InxGa1-xSb with an indium mole fraction (x) of around 0.3, which had previously been reported to be optimal for the performance of InAs/InxGa1-xSb SLS’s, due to the maximum splitting of the valence mini bands for this composition. The growth temperature was thus lowered to 510 °C. This resulted in an increase in the optimum V/III ratio to 1.75 for GaSb and yielded much higher incorporation efficiencies of indium in InxGa1-xSb. However, this lower growth temperature also produced poorer surface morphologies for both the binary and ternary layers, due to the reduced surface diffusion of the adsorbed species. An interface control study during the growth of InAs/GaSb SLS’s was subsequently conducted, by investigating the influence of different gas switching sequences on the interface type and quality. It was noted that the growth of SLS’s without any growth interruptions at the interfaces leads to tensile strained SLS’s (GaAs-like interfaces) with a rather large lattice mismatch. A 5 second flow of TMSb over the InAs surface and a flow of H2 over GaSb surface yielded compressively strained SLS’s. Flowing TMIn for 1 second and following by a flow of TMSb for 4 seconds over the GaSb surface, while flowing H2 for 5 seconds over the InAs surface, resulted in SLS’s with GaAs-like interfacial layers and a reduced lattice mismatch. Temperature gradients across the surface of the susceptor led to SLS’s with different structural quality. High resolution x-ray diffraction (HRXRD) was used to determine the thicknesses as well as the type of interfacial layers. The physical parameters of the SLS’s obtained from simulating the HRXRD spectra were comparable to the parameters obtained from cross sectional transmission electron microscopy (XTEM) images. The thicknesses of the layers and the interface type played a major role in determining the cut-off wavelength of the SLS’s.

No description available.

La croissance localisée de SiC dopé p par un mécanisme Vapeur-Liquide-Solide (VLS) a été effectuée sur substrats SiC-4H (0001) 8°off et diamant (100). Pour ce faire, des motifs constitués d'un empilement silicium-aluminium sont fondus puis alimentés en propane. Dans le cas de l'homoépitaxie de SiC-4H, il a été démontré que la quantité limitée de phase liquide initiale entraine une évolution constante des paramètres de croissance en raison de l'appauvrissement graduel en silicium. Il est toutefois possible de trouver des conditions de croissance satisfaisantes (alliage contenant 40 at% Si, 1100 °C) résultant en un dépôt conforme sur l'ensemble des motifs avec une morphologie step-bunchée. A partir de tels dépôts, des contacts ohmiques de très faible résistivité (jusqu'à 1,3.10-6 Ω.cm2) ont été mesurés et des diodes PiN ont été fabriquées et caractérisées. Dans le cas de la croissance de SiC sur diamant, la forte réactivité entre l'alliage Si-Al liquide et le substrat diamant conduit à la formation d'un dépôt dense et polycristallin de SiC-3C par un mécanisme de dissolution-précipitation. Nous avons montré que la formation préalable d'une couche tampon nanométrique de SiC par siliciuration du substrat de diamant (réaction solide-solide entre une couche de Si et le diamant) permet d'obtenir une croissance épitaxiale de SiC-3C en ilots, avec les relations [110] SiC // [110] diamant et (100) SiC // (100) diamant. Il n'a cependant pas été possible de former une couche complète et épitaxiale de SiC sur diamant par VLS localisée. Nous avons toutefois montré que cela est réalisable par dépôt chimique en phase vapeur (CVD) en utilisant la même étape de siliciuration / The localized growth of p-doped SiC by Vapor-Liquid-Solid (VLS) mechanism was made on (0001) 8°off 4H-SiC and (100) diamond substrates. A silicon-aluminium stacking, localized on top of the substrate, is used after melting as the liquid phase for the growth, carbon being brought by the propane of the gas phase. Regarding the homoepitaxial growth of 4H-SiC, the limited amount of liquid phase leads to a significant consumption of silicon during the growth which is responsible for a continuous variation of the growth parameters. Satisfying growth conditions can therefore be found (40 at% Si alloy, 1100 °C) leading to the formation of a step-bunched layer on the initial Si-Al patterns. Very Low resistivity ohmic contacts (as low as 1.3x10-6 Ω.cm2) and PiN diodes were successfully fabricated from these deposits. Regarding the SiC growth on diamond, the high reactivity between the Si-Al liquid alloy and the diamond substrate leads to the polycrystalline growth of 3C-SiC by a dissolution-precipitation mechanism. It is thus necessary to use a SiC buffer layer in order to achieve an epitaxial growth. This buffer layer, grown by a solid-solid reaction between silicon (deposited by CVD) and the diamond called silicidation, favors the epitaxial growth of 3C-SiC ([110] SiC // [110] diamond and (100) SiC // (100) diamond) during the later VLS growth. Considering the 3D growth mechanism that takes place the formation of a single-crystalline layer from these epitaxial islands seems difficult. Such single-crystalline layer can be achieved using chemical vapor deposition (CVD) after the silicidation step of the diamond substrates

Cette thèse se concentre sur la fabrication de cellule solaire IIIN- V sur substrat de GaP (001) et sur la croissance de couche de GaP sur Si (001). Le but est de réaliser des cellules solaires hautes efficacité sur un substrat à faible coût afin de les intégrer dans des centrales solaire photovoltaïque sous concentration. Les principaux résultats obtenus montrent : - L’importance de l’utilisation d’AlGaP en tant que couche de prénucléation pour annihiler les parois d’antiphase à l’interface GaP/ Si (néfaste pour les propriétés optoélectroniques des dispositifs) - De nombreuses similitude entre la croissance de GaAsN et de GaPN ce qui permet d’élaborer une stratégie afin d’optimiser les propriétés optoélectroniques du GaAsPN - De fortes corrélations entre les propriétés optique et éléctriques dans les nitrures dilués - La réalisation préliminaire d’une cellule solaire monojonction sur GaP ayant un rendement encourageant de 2.25% considérant la faible épaisseur de l’absorbeur dans cette cellule (300 nm) / This thesis focuses on optimizing the heterogeneous growth of IIIN- V solar cells on GaP (001) and GaP nanolayers on Si (001). The goal is to build high efficiency solar cells on low-cost substrate for the realization of concentrated photovoltaic powerplant. The main results shows: - AlGaP as prenucleation layer increase the annihilations of anti-phase boundaries at the GaP/Si interface (harmful for the electronic properties of the devices). - Similarities between the growth of GaAsN and GaPN giving strategies to improve the GaAsPN electrical properties - Clear correlations between the optical and electrical properties of dilute nitride solar cells, giving interesting tools to optimize the growth of those materials using optical measurements. - The realization of a GaAsPN solar cell on GaP with a yield of 2.25%. This results is encouraging given the thin GaAsPN absorber used in this cell

Orientadores: Luiz Fernando Zagonel, Mônica Alonso Cotta / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-30T22:54:17Z (GMT). No. of bitstreams: 1 Silva_BrunoCesarDa_M.pdf: 3896391 bytes, checksum: 02a6cadcf24734bcd669293dc473b75e (MD5) Previous issue date: 2016 / Resumo: Neste trabalho, estudamos a dinâmica de crescimento de nanofios de GaP crescidos pelo método VLS (Vapor-Líquido-Sólido) via Epitaxia por Feixe Químico (CBE), usando nanopartículas catalisadoras de ouro. Investigando o efeito da temperatura na dinâmica de crescimento de nanofios de GaP encontramos uma grande variedade de nanofios em cada amostra, caracterizadas por diferentes direções de crescimento e/ou morfologias, apresentando sempre uma população dominante. Com o aumento da temperatura (510°C) observamos uma transição drástica na morfologia da população dominante, de nanofios típicos para uma nova e inesperada morfologia assimétrica. Mostramos ainda que modificando o tamanho da nanopartícula catalisadora de 5nm para 20nm os nanofios assimétricos ainda são favorecidos a alta temperatura. Procurando compreender o mecanismo de formação dos nanofios assimétricos, mostramos que estas estruturas cristalizam-se na fase WZ, com baixa densidade de defeitos, comparadas às outras amostras. Além disso, mostramos que a assimetria destes nanofios não é oriunda de diferenças de polaridade nas facetas laterais ou formação de defeitos cristalográficos que pudessem modificar a dinâmica de crescimento de modo a levar à morfologia assimétrica. Desta forma, propomos um cenário de crescimento simplificado, no qual a estrutura assimétrica é formada pela combinação do crescimento de nanofios ordinários, via VLS, junto com estruturas que crescem livre de catalizador via mecanismo VS (Vapor-Sólido), estas duas estruturas então se juntam, transferindo material e dando lugar a facetas de menor energia, resultando na formação da estrutura assimétrica. Por fim, medidas de fotoluminescência mostram a emissão característica no verde do GaP WZ para os nanofios assimétricos, mesmo com a estrutura não estando passivada, confirmando a boa qualidade cristalina das nossas amostras / Abstract: In this work, we study the growth dynamics of GaP nanowires grown by VLS (Vapor-Liquid-Solid) method via Chemical Beam Epitaxy (CBE) using gold nanoparticles as catalyst. Investigating the effect of temperature on the growth dynamics of GaP nanowires we find a wide variety of nanowires in each sample, characterized by different growth directions and/or morphologies, always having a dominant population. With increasing temperature (510°C), we observed a dramatic transition in the morphology of the dominant population of typical nanowires to a new and unexpected asymmetric morphology. We also show that modifying the size of the catalyst nanoparticle from 5nm to 20mn the asymmetric nanowires are still favored at high temperature. Looking forward to understand the mechanism of formation of the asymmetric nanowires, we show that these structures crystallize in the WZ phase with low defect density when compared to the other samples. Furthermore, we show that the asymmetry of these nanowires is not derived from differences in polarity in side facets or the formation of crystallographic defects which might modify the growth dynamics so as to bring the asymmetric morphology. Thus, we propose a simplified growth scenario, in which the asymmetric structure is formed by growth combination of ordinary nanowires via VLS, along with structures that grow catalyst-free via VS (vapor-solid) mechanism, these two structures joined and by transferring materials facets with lower energy facets appear, resulting in the formation of asymmetrical structure. Finally, photoluminescence measurements show the characteristic emission in the green of WZ GaP for asymmetric nanowires, even with no passivation, which confirms the good crystalline quality of our samples / Mestrado / Física / Mestre em Física

abstract: The first part of this dissertation reports the study of the vertical carrier transport and device application in InAs/InAs1-xSbx strain-balanced type-II superlattice. It is known that the low hole mobility in the InAs/InAs1-xSbx superlattice is considered as the main reason for the low internal quantum efficiency of its mid-wave and long-wave infrared photodetectors, compared with that of its HgCdTe counterparts. Optical measurements using time-resolved photoluminescence and steady-state photoluminescence spectroscopy are implemented to extract the diffusion coefficients and mobilities of holes in the superlattices at various temperatures from 12 K to 210 K. The sample structure consists of a mid-wave infrared superlattice absorber region grown atop a long-wave infrared superlattice probe region. An ambipolar diffusion model is adopted to extract the hole mobility. The results show that the hole mobility first increases from 0.2 cm2/Vs at 12 K and then levels off at ~50 cm2/Vs as the temperature exceeds ~60 K. An InAs/InAs1-xSbx type-II superlattice nBn long-wavelength barrier infrared photodetector has also been demonstrated with a measured dark current density of 9.5×10-4 A/cm2 and a maximum resistance-area product of 563 Ω-cm2 at 77 K under a bias of -0.5 V. The Arrhenius plot of the dark current density reveals a possible high-operating-temperature of 110 K.The second part of the dissertation reports a lift-off technology using a water-soluble sacrificial MgTe layer grown on InSb. This technique enables the seamless integration of materials with lattice constants near 6.5 Å, such as InSb, CdTe, PbTe, HgTe and Sn. Coherently strained MgTe with a lattice constant close to 6.5 Å acts as a sacrificial layer which reacts with water and releases the film above it. Freestanding CdTe/MgxCd1-xTe double-heterostructures resulting from the lift-off process show increased photoluminescence intensity due to enhanced extraction efficiency and photon-recycling effect. The lifted-off thin films show smooth and flat surfaces with 6.7 Å root-mean-square roughness revealed by atomic-force microscopy profiles. The increased photoluminescence intensity also confirms that the CdTe/MgxCd1-xTe double-heterostructures maintain the high optical quality after epitaxial lift-off. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2020