The growth of single and multilayer BN films on several substrates was investigated. A typical atomic layer deposition (ALD) process was demonstrated on Si(111) substrate with a growth rate of 1.1 Å/cycle which showed good agreement with the literature value and a near stoichiometric B/N ratio. Boron nitride films were also deposited by ALD on Cu poly crystal and Cu(111) single crystal substrates for the first time, and a growth rate of ~1ML/ALD cycle was obtained with a B/N ratio of ~2. The realization of a h-BN/Cu heterojunction was the first step towards a graphene/h-BN/Cu structure which has potential application in gateable interconnects.

The method Atomic Layer Deposition, ALD, has been available since the 1970´s and it has opened the possibility to fabricate methods for inorganic thin films on a nanoscale. Later the interest for fabricating organic thin films with Molecular Layer Deposition, MLD, and controlling both the thickness and the composition of the film on a molecular scale. To develop the thin films a bit further a combination of organic and inorganic thin films is fabricated and therefore the best properties of the two types of thin films are combined.  The purpose of this bachelor´s thesis was to fabricate the multilayer thin film AlN-HQ on a silicon substrate. It began with a substantial review of the literature and planning of the approach. Followed by the laboratory work with fabricating the thin film by ALD. The laboratory work ended with analyzing the thin films by ATR-FT/MIR (attenuated total reflectance fourier transform mid-infrared spectroscopy) and XRR (X-ray reflectivity). All data provided where summarized and evaluated. An analysis of the thickness of the thin film was attempted with XRR but was not adequate for these samples. For a development of the method fabrication of the multilayer film AlN-HQ the thickness needs to be known. It could probably be analyzed by Scanning Electron Microscopy, SEM, but that type of analysis was not a part of this study.

Clostridium beijerinckii is a spore-forming, obligate anaerobe that is capable of producing butanol, acetone and isopropanol. These industrial chemicals are traditionally known as solvents. The regulation of solventogenic fermentation is linked to the onset of sporulation, so that by the time the organism begins to produce solvents, it is also entering into spore formation and metabolic slowdown. The goal of this research project was to study the effect of placing the solvent-production genes from C. beijerinckii under the control of constitutive promoters from other genes, in an attempt to allow an earlier start of butanol production during the growth phase than is the case with the wild-type cells. The aldehyde dehydrogenase from C. beijerinckii NRRL B593 (ald) and alcohol dehydrogenase from C. beijerinckii NRRL B592 (adhA) were placed under the control of the promoter from the acid-producing operon (the BCS operon) in one vector, and under the control of the promoter from the ferredoxin gene in another. In both cases, aldehyde dehydrogenase activity was produced earlier in the growth phase in transformed cells, but alcohol dehydrogenase activity was not. The adhA gene from C. beijerinckii NRRL B592 was paired with the adhB gene from the same organism in a third vector, both under the control of the promoter from the BCS operon. In cells transformed with this vector, alcohol dehydrogenase activity was observed earlier in the growth phase than it was in wild-type NRRL B592 cells. / Ph. D.

La diminution du coût ainsi que l'augmentation du rendement des cellules solaires sont devenues les axes principaux de recherche depuis la crise qui a touché le marché du photovoltaïque en 2011. Une des principales stratégies est l’amincissement des cellules solaires dans le but de réduire les coûts des matériaux. Cependant, ceci diminue fortement le rendement de conversion suite à une plus forte influence des défauts structurels et électroniques, présents en surface. Ces défauts peuvent être « passivés » par l’Al2O3 déposé par technique PE-ALD. Ce matériau présente les meilleurs résultats de passivation de surface du silicium cristallin de type p. La couche de passivation nécessite un traitement thermique pour être effective. Ce phénomène se traduit par une augmentation de la durée de vie des porteurs de charge. Cette thèse, encadrée par les deux projets ANR PROTERRA et BIFASOL, ainsi qu’un financement de l’Ecole Centrale de Lille, présente l’optimisation des paramètres de dépôt de la couche de passivation d’Al2O3 ainsi qu’une étude approfondie du phénomène d’activation de la passivation, sur des échantillons avec et sans émetteur. L’analyse de la passivation a été réalisée grâce à des mesures couplées de durée de vie (PCD), électriques (C-V), de potentiel de surface (Sonde de Kelvin) et de spectrométrie (XPS, SIMS). Les sources de la passivation chimique et par effet de champ sont déterminées dans l'empilement Si/SiO2/Al2O3. Le rôle et la dynamique des hydrogènes contenus dans la couche d’alumine sont explicités. L’impact d’une encapsulation par du SiNx ainsi qu’un recuit de diffusion des contacts de 3s à 830°C est étudié / The decrease of solar cell cost as well as the increase in their efficiency are main research topics since the photovoltaic market crisis in 2011. One of the main strategy is to move towards thinner solar cells, in order to decrease raw material consumption. However, the result is a higher impact of surface phenomena on cell characteristics because of a high influence of structure and electronic defects at the surface. These defects can be passivated by Al2O3 coated by PE-ALD (Plasma Enhanced-Atomic Layer Deposition) which has been shown to provide the best surface passivation on p-type silicon. In an as-deposited state, the passivation level of Al2O3 is very low and required an annealing treatment to be "activated". This phenomenon provides an increase of the minority carrier effective lifetime. This thesis founded by the ANR PROTERRA and BIFASOL projects with the financial support of the Ecole Centrale de Lille, focuses on the optimization of the deposition parameters of alumina with a deeper insight on the passivation activation phenomena on samples with and without emitter. The passivation analysis has been performed thanks to coupled lifetime (QSS and micro PCD), surface potential (Kelvin probe), electrical (C-V) and chemical (SIMS, XPS) characterizations. The origin of the chemical and field effect passivation has been determined within the Si/SiO2/Al2O3 stack. The dynamics of the hydrogen contained in bulk alumina is explained. The impact of a SiNx capping layer and a contact alloying anneal at 830°c for 3s is also investigated

Für die Beschichtung von Bauelementen im Bereich der Elektronik erlangt das Beschichtungsverfahren der Atomlagenabscheidung zunehmend an Bedeutung. Dieses Verfahren überzeugt hier durch seine Fähigkeit sehr homogene Schichten mit einer Dicke von wenigen nm auch auf Strukturen mit hohen Aspektverhältnissen zu erzeugen. Diese Arbeit beschäftigt sich mit der Atomlagenabscheidung von Aluminiumoxid unter Verwendung der Präkursoren Trimethylaluminium und Wasser. Hauptaufgabe dieser Arbeit ist die Modellierung eines experimentellen Prozessaufbaus mit kommerzieller Simulationssoftware. Anhand der Simulationsergebnisse können Aussagen zur Optimierung des ALD-Prozesses getroffen werden. Die durchgeführten Untersuchungen zeigen, dass für die Simulation eines ALD-Prozesses sehr lange Rechenzeiten erforderlich sind. Insbesondere konnte ein tieferes Verständnis der automatischen Zeitschrittweitenregulierung der Software bei transienten Simulationen gewonnen werden. Die Dauer der Spülschritte wurde durch die Simulationsergebnisse als ausreichend bestätigt. Des Weiteren kann die Verwendung der zur Anlage gehörigen Gasdusche anhand der Simulationsergebnisse nicht empfohlen werden.

Le stockage de l’énergie reste une problématique majeure pour le développement d’objets embarqués (Internet of Things) à faible facteur de forme. En effet, pour le stockage et la restitution d’énergie électrique, les dispositifs les plus couramment utilisés sont les batteries, les supercondensateurs et les condensateurs électrochimiques ou céramiques. Toutefois, le contexte de la miniaturisation nécessite de fabriquer des systèmes de stockage à forte densité d’intégration, compatibles avec des techniques d’intégration de type SIP (System in Package) et ultimement SoC (System on Chip). Or, les technologies connues dans l’art antérieur produisent des composants à forte épaisseur, via des filières technologiques exotiques, incompatibles avec une co-intégration directe sur des composants silicium. Pour répondre à ces exigences, nous proposons une nouvelle approche pour l’intégration de condensateurs de très faible épaisseur sur silicium. Ces condensateurs présentent une meilleure fiabilité et de meilleures performances en linéarité que les condensateurs céramiques et peuvent stocker une densité énergétique proche de celle d’un condensateur électrochimique.Cette thèse est axée sur la conception, le développement, la réalisation, la caractérisation électrique et fiabilité de capacités MIM (Métal/Isolant/Métal) à forte densité d’intégration et présentant une forte densité énergétique. Ces condensateurs sont modelés dans une nanostructure poreuse ordonnée et développée par un procédé électrochimique. Cette nanostructure 3D permet de décupler la surface spécifique développée, par rapport à une structure planaire simple ou une microstructure 3D telle qu’actuellement exploitée par la société IPDIA. Ce nanocomposant MIM comportant un isolant à base d’alumine, déposé par ALD (Atomic Layer Deposition) d’une épaisseur variant entre 15nm et 21nm. Pour cette gamme d’épaisseur, une densité de capacité de l’ordre de 200nF/mm² à 300nF/mm² est obtenue sur une simple structure MIM, avec un champ de claquage de l’ordre de 7MV/cm et une densité d’énergie volumique maximale de 1.3mWh/cm3. Cette dernière valeur est supérieure d’une décade aux technologies actuellement exploitées par la société IPDIA. Une attention particulière a été apportée à la réduction des parasites de la structure, et lui permettant ainsi de répondre à des transitions rapide en courant. Pour cela, la résistance série de ces structures a été optimisée par l’amélioration du contact entre les nanostructures MIM et les électrodes externes. La stabilité de la capacité MIM en température et en tension est comparable aux performances des technologies de référence IPDIA (respectivement avec un coefficient thermique de 193ppm/°C et un coefficient de tension de 489 ppm/V2), lesquelles sont basées sur une structure composite de type ONO (multicouche oxyde-nitrure). Elle est par ailleurs meilleure que celle observée pour les condensateurs céramiques multicouches disponibles sur le marché. Notre capacité présente également, une excellente robustesse en température et a été utilisée jusqu’à 375°C. Les performances démontrées sur les prototypes réalisés au cours de ce travail, permettent d’envisager un vaste domaine d’applications, incluant des applications de stockage, de filtrage de rails d’alimentation, de mise en forme de signaux analogiques et de puissance. Le niveau de maturité atteint sur les premiers démonstrateurs permet d’envisager un transfert industriel dans les mois à venir. / The energy storage components remain one of the limiting features for scaling of the Internet of Things objects. Indeed, the storage devices nowadays available as batteries, supercapacitors and electrochemical or ceramic capacitors are still quite bulky and remain incompatible with reduced aspect ratio, while roadmap toward miniaturization requires concept with high integration density compatible with integration techniques like SiP ((System in Package) and on longer term SoC (System on Chip). However, technologies known from the prior art, produce components with too large thickness, inflexible shape (mostly circular or rectangular), through exotic technologies that are incompatible with direct co-integration on silicon components. To overcome those limitations, we have proposed a novel approach for the integration of very low thickness capacitors. Those capacitors have better reliability and stability performances than ceramic capacitors and are able to store energy density approaching electrochemical capacitor.This thesis is focused on the development of the capacitive structure, the processing steps, its electrical and reliability characterization and finally the electrical optimization of MIM (Metal/Isolator/Metal) capacitors. Those capacitive structures are based on a porous and self-arranged nano-template obtained by an electrochemical process. Those nanostructures allow to increase the specific surface density with respect to conventional planar or microstructures that are currently exploited by IPDIA. The MIM structure consists of alumina dielectric, deposited by ALD (Atomic Layer Deposition) with a thickness between 15nm and 21nm. For this thickness, capacitance density is obtained in the range of 200nF/mm² and 300nF/mm² for a simple MIM nanostructure, with a breakdown field about 7 MV/cm and a maximum volumetric energy density of about 1.3mWh/cm3. This last value corresponds to a decade higher with respect to current IPDIA technologies. A specific optimization has been conducted to reduce structure parasitic, and thus enable faster current transition on switching events. For that, a technic to reduce the serial resistance between the MIM nanostructure and the external electrodes has been investigated. The temperature and voltage linearity of this MIM capacitor is on par with actual IPDIA reference technologies (respectively thermal coefficient of 193ppm/°C and quadratic voltage coefficient of 489 ppm/V²), which are based on an ONO composite dielectric (multi-layer nitride oxide). This performance is outperforming the Multi-Layer Ceramic Capacitors that are currently used for equivalent application. Furthermore, demonstration of operation up to 375°C has been demonstrated for this structure. With these capacitors it is envisioned to address a large span of applications, ranging from energy storage, to filtering of power rails, or analogic and power signal conditioning. The maturity obtained on demonstrators allows to envisage an industrial transfer in the coming months.

Depuis la fin des années 2000 les capteurs d’images CMOS éclairés par la face arrière (Back-Side-Illuminated) prennent le pas sur les capteurs traditionnels éclairés par la face avant (Front-Side-Illuminated). Cette technologie présente l’avantage de simplifier le chemin optique jusqu’à la photodiode et permet notamment d’accroitre le rendement quantique. Dans le même temps à l’instar des technologies CMOS ce changement permet de réduire la dimension des pixels dans le plan. Ce changement entraine cependant l’apparition d’une nouvelle interface sur la face arrière des pixels qu’il faut maitriser car elle peut être une source de courant d’obscurité, phénomène qu’il faut réduire pour obtenir des capteurs performants. Pour limiter ce phénomène, il faut limiter l’émission d’électrons parasites par les défauts d’interface que l’on cherche à passiver. Deux moyens existent, la passivation chimique qui consiste à réduire la densité de défauts à l’interface et la passivation par effet de champ qui consiste à introduire des charges dans la couche de passivation. Pour ce faire, ce travail de thèse s’inscrit dans le développement d’un empilement SiO2 / HfO2 ou Al2O3 / Ta2O5 dont les oxydes métalliques sont déposés par ALD et PEALD. Les objectifs de ces travaux sont de comprendre l’origine et la nature des défauts dans les oxydes métalliques afin d’améliorer les propriétés de passivation de l’empilement. La nature des couches utilisées, les paramètres de dépôt ainsi que l’impact du recuit sont étudiés en détail à partir de la technique de mesures COCOS permettant d’extraire la densité de défauts d’interface et la charge totale de l’empilement. D’autres techniques de caractérisation physico-chimique complémentaires telles que les mesures infrarouges sont utilisées et permettent d’identifier les modifications chimiques de l’empilement. / Since the late 2000s back-side-illuminated CMOS image sensors have taken precedence over traditional Front-Side Illuminated sensors. This technology has the advantage of simplifying the optical path to the photodiode and particularly increases the quantum efficiency. At the same time, like CMOS technologies, this change allows the reduction of the size of the pixels in the plane. However, this change causes the appearance of a new interface on the back side of the pixels. The presence of an additional interface implies a new source of dark current that must be reduced to the maximum to maintain high performance. This interface has to be passivated to minimize the generation of parasitic electrons. Two means exist, the chemical passivation which consists of reducing the density of defects at the interface and the field effect passivation which consist of introducing charges into the passivation layer. To do this, this thesis work is part of the development of a SiO2 / HfO2 or Al2O3 / Ta2O5 stack whose metal oxides are deposited by ALD and PEALD. The purpose of this work is to understand the origin and the nature of defects in metal oxides in order to improve the passivation properties of the stack. The nature of the layers used, the deposition parameters and the impact of the annealing are studied in detail from the COCOS measurement technique making it possible to extract the density of interface defects and the total charge of the stack. Other complementary physicochemical characterization techniques such as infrared measurements have been used to identify chemical changes in the stack.

Made available in DSpace on 2015-03-26T13:35:20Z (GMT). No. of bitstreams: 1 texto completo.pdf: 4132930 bytes, checksum: 1169203ed33a5e53252821abccd6cf81 (MD5) Previous issue date: 2013-02-19 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work, ultra-thin layers of oxides grown using the technique of atomic layer deposition were characterized by measurements of x-ray reflectivity. TiO2:Al2O3 samples were grown using titanium isopropoxide (Ti(Hi-Pr)4), trimethylaluminum (Al(CH3)3) and water. The proportion of alumina was changed from 8 to 44% by varying the number of cycles of each precursor. TiO2:NiO samples were also grown using nickelocene (NiCp2) and water as precursors for NiO. The x-ray reflectivity measurements were performed at the Brazilian Synchrotron Light Laboratory and showed a reduction in deposition rate during growth of the TiO2:NiO series of samples, which prevented its use in the remainder of the study. The experimental data of TiO2:Al2O3 samples were analyzed using 03 simulation software: MOTOFIT, a free package designed to run on the IGOR Pro platform, and two MATHEMATICA codes; a first one based on kinematic approximation and another based in the Parrat recursion s method. The fitting procedure was based on two models: single layer, considering alumina as dopant, and multilayer, with sample composed of alternate layers of TiO2 and Al2O3. We conducted a detailed comparison of the results obtained from the softwares and models used and analyzed the influence of various parameters on the fits obtained. The fittings allowed the determination of various sample parameters, such as electron density and thickness of each layer and the roughness of the various interfaces. Comparing the software, we found that the best fits to the experimental data were obtained using the Parrat recursion s method. The multilayer model resulted in a better fit, reflecting the repetitive nature of the growth process, although the interface roughness values obtained were too large compared to layer thickness. Irrespective of software and the model used, the results show that atomic layer deposition can be used to obtain layers with controlled thickness and roughness less than 1 nm, independent of the number of cycles used in the deposition process. / Neste trabalho, camadas ultra-finas de óxidos, crescidas pela técnica de deposição por camada atômica, foram caracterizadas através de medidas de refletividade de raios-x. As amostras de TiO2:Al2O3 foram crescidas utilizando a técnica de deposição por camada atômica (ALD) usando como precursores isopropóxido de titânio (Ti(O-i-Pr)4), trimetilalumínio (Al(CH3)3) e água. A proporção de alumina foi modificada de 8 á 44%, variando a quantidade de ciclos de cada um dos precursores. Foram crescidas, também, amostras de TiO2:NiO, utilizando Niqueloceno (NiCp2) e água como precursores para NiO. As medidas de refletividade de raios-x foram realizadas nas instalações do Laboratório Nacional de Luz Síncrotron e mostraram uma redução na taxa de deposição durante o crescimento da série de amostras de TiO2:NiO, que impediu a sua utilização no restante do estudo. Os resultados experimentais das amostras de TiO2:Al2O3 foram analisados utilizando 03 softwares de simulação: MOTOFIT, um pacote livre desenvolvido para rodar na plataforma IGOR Pro, e dois códigos desenvolvidos para rodar na plataforma MATHEMATICA, o primeiro baseado na aproximação cinemática e o segundo no método de recursão de Parrat. Os ajustes das curvas experimentais foram feitos utilizando dois modelos: o de camada simples, considerando a alumina e o óxido de níquel como dopantes, e o de multicamada. Foi feita uma comparação detalhada entre os softwares e os modelos utilizados, analisando a influência dos vários parâmetros nos ajustes obtidos. Estes ajustes permitiram a determinação de diversos parâmetros característicos das amostras, tais como a espessura e a densidade eletrônica de cada camada e a rugosidade das várias interfaces. Na comparação entre os softwares, observou-se que o melhor ajuste aos dados experimentais foi obtido utilizando o método de recursão de Parrat. Em relação aos dois modelos utilizados, o de multicamada foi o que permitiu um melhor ajuste, refletindo a natureza repetitiva do processo de crescimento, apesar de fornecer valores de rugosidade das interfaces muito grande, comparados à espessura das camadas. Independente do software e do modelo utilizado, os ajustes permitem afirmar que a técnica de deposição por camada atômica permite a obtenção de camadas com espessura controlada e rugosidade menor que 1 nm, independente do número de ciclos utilizados na deposição.

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In dieser Arbeit werden verschiedene Prozesse zur Atomlagenabscheidung (ALD) von TiO2 und HfO2 experimentell untersucht. Die Untersuchungen schließen eine experimentelle Charakterisierung des Schichtwachstums sowie eine massenspektrometrische Analyse der Reaktionsprodukte ein. Im Detail wurden der ALD-Prozess mit Cp*Ti(OMe)3 und Ozon zur Abscheidung von TiO2 sowie der ALD-Prozess mit TEMAHf und Ozon zur Abscheidung von HfO2 untersucht. Der theoretische Teil der Arbeit beginnt mit einer Methode zur Bestimmung des absoluten Haftkoeffizienten. Anschließend werden numerische Modelle entwickelt, welche die Adsorption von Präkursormolekülen durch strukturierte Substrate beschreiben. Diese Modelle enthalten die Substratstruktur und den absoluten Haftkoeffizienten. Es wird eine statistische numerische Methode entwickelt, mit der der Gastransport in dem ALD-Reaktor statistisch beschrieben wird. Die statistischen Größen, welche die Gasdynamik im Reaktor beschreiben, werden mit der Discrete Simulation Monte Carlo (DSMC) Methode bestimmt. Mit dieser Methode und den Modellen der Adsorption kann der komplette ALD-Prozess simuliert werden. Die neu entwickelte Methode wird verwendet um die Effizienz verschiedener ALD-Reaktoren in Abhängigkeit des absoluten Haftkoeffizienten, der Substratstruktur sowie der Prozessbedingungen zu untersuchen. Die Geometrie des Reaktors wird variiert und mit der Referenzgeometrie verglichen. / This dissertation is divided into an experimental part and a theoretical part. The experimental part describes the atomic layer deposition (ALD) of TiO2 and HfO2. TDMAT and Cp*Ti(OMe)3 were used as titanium precursors, while TEMAHf was used as the hafnium precursor. Ozone was used as the oxygen source. The self limiting film growth and the temperature window of these ALD processes were investigated. The reaction by-products of the Cp*Ti(OMe)3/O3 process were identified by quadrupol mass spectrometry (QMS). The QMS analysis of the TEMAHf/O3 process revealed that water is formed during the metal precursor pulse. The theoretical part of this thesis describes the development of models and numerical methods to simulate the ALD as a whole. First of all, a model for the adsorption of precursor molecules by planar substrates was developed. This model was extended to describe the adsorption of precursor molecules inside a cylindrical hole with an aspect ratio of 20, 40 and 80. The adsorption of precursor molecules is dominated by the absolute sticking coefficient (SC), i.e., the reactivity of the precursor molecules. From the numerical model the saturation profiles along the wall of a cylindrical hole can be determined. From the comparison of the simulated profile with an experimentally determined thickness profile the SC can be determined. This method was used to determine the SC of the precursors examined in the experimental part. The SC of TEMAHf increases exponentially with the substrate temperature. A discrete particle method (DSMC) was used to derive a statistical description of the gas kinetics inside an ALD reactor. Combining the statistical description of the gas transport and the numerical models of the adsorption, it is possible to simulate the ALD for any combination of reactor, substrate and SC. It is possible to distinguish the contribution of the reactor geometry, the process parameters and the process chemistry (SC) to the process efficiency. Therefore, the ALD reactor geometry can be optimized independently of the process chemistry. This method was used to study a shower head ALD reactor. The reactor geometry, the composition of the gas at the inlet and the position of the inlet nozzles was varied in order to find more efficient ALD reactors. The efficiency of the reference geometry is limited by the inlet nozzles close to the exhaust and the decrease of the pressure on the substrate near the exhaust. The efficiency of ALD processes with different SCs was simulated for planar and structured substrates with a diameter of 300 mm and 450 mm.