L'objet de cette étude est le dépôt de films minces SiNx à basse température assisté par plasma de haute densité de type DECR (Distributed Electron Cyclotron Resonance) et leur application à la passivation des dispositifs optoélectroniques à base d'InP, tel que le transistor bipolaire à hétérojonction. Dans un premier temps, nous comparons les différentes sources de plasma de haute densité qui sont utilisées pour le dépôt de nitrure de silicium et nous présentons un bilan des diverses méthodes de désoxydation des matériaux semiconducteurs utilisés dans les dispositifs optoélectroniques à base d'InP. Nous avons ensuite choisi de détailler la mise en oeuvre de l'analyse par sondes électrostatiques simple et double, qui constitue l'apport essentiel de ce travail dans l'étude du plasma DECR. Cette méthode nous a permis de mesurer des paramètres cruciaux pour le dépôt, tels que l'énergie des ions lorsqu'ils arrivent sur le substrat ou encore la densité de courant ionique. Ainsi, nous avons pu corréler ces paramètres avec les propriétés des films minces déposés (contrainte, densité, ...). Nous avons également étudié les mécanismes de conduction dans le nitrure de silicium pour différentes épaisseurs de film. La conduction par effet tunnel (mécanisme de Fowler-Nordheim) devient négligeable pour les films d'épaisseur supérieure à 20 nm. Pour ces derniers, la conduction est assistée par les pièges à électrons présents dans le nitrure (mécanisme de Frenkel-Poole). A travers l'étude électrique des structures Al/SiNx/InP, nous avons constaté que le traitement in-situ du substrat d'InP par plasma DECR N2 et/ou NH3 ne permet pas d'optimiser l'interface SiNx/InP. Par contre, nous avons montré que l'utilisation d'un plasma de dépôt riche en hydrogène permettait de réduire l'oxyde présent à la surface de l'InP. L'ensemble de cette étude a permis de définir un procédé de passivation du transistor bipolaire à hétérojonction InP/InGaAs qui a été testé avec succès.

Le travail présenté dans cette thèse s'inscrit dans le cadre de l'étude des propriétés des couches minces de matériaux semi-conducteurs à base de tellurure de cadmium CdTe. L'étude de l'influence de différents paramètres de dépôt sur les propriétés des couches minces de CdTe nous a permis de mettre au point une méthode de préparation d'un nouveau matériau à base de CdTe. Il s'agit du tellurure de cadmium amorphe oxygéné aCddTe:O. Le dépôt de couches minces de a-CdTe:O à partir d'une cible polycristalline de CdTe nécessite l'utilisation d'un plasma à haut pouvoir oxydant. Le plasma que nous avons utilisé est obtenu à partir d'un mélange d'argon Ar, de dioxygène et de diazote soumis à un champ électrique radiofréquence de 13,56 MHz. Nous avons montré que le diazote joue un rôle de catalyseur de l'oxydation de CdTe dans le plasma de déposition dont la composition détermine celle des couches minces de a-CdTe:O. En effet, la teneur en oxygène de ces couches peut avoisiner les 60 % lorsque les conditions d'oxydation sont poussées à l'extrême. Les propriétés optiques des couches minces de a-CdTe:O dépendent beaucoup de la teneur des couches en oxygène. C'est ainsi que l'énergie Eg du gap optique varie entre 1,45 eV et 1,85 eV pour une teneur en oxygène variant entre 0 et 40 % en pourcentage atomique. La valeur extrapolée à l'infrarouge de l'indice de réfraction de ces couches varie, quant à elle, entre 2,15 et 2,75. L'étude par XPS montre que l'oxygène incorporé dans les couches minces de a-CdTe:O se lie aussi bien aux atomes de tellure qu'à ceux de cadmium. En utilisant la réfléctométrie des rayons X, nous avons pu mettre en évidence l'influence du plasma oxydant précédent sur les couches minces de CdTe. Nous avons réussi ainsi à mettre au point une méthode qui permet de réduire considérablement la rugosité de surface des couches minces de CdTe. Lorsque l'on pousse à l'extrême les conditions d'oxydation, on peut obtenir des couches minces amorphes de l'oxyde stable CdTeO3. L'étude des propriétés électriques de ces couches permet de mettre en évidence leur caractère isolant. Nous avons pu ainsi déterminer leur résistivité électrique continue 3x10^6 ohm.m et leur constante diélectrique relative (16). Les mesures de transmission optique ont permis de déterminer leur énergie de gap optique Eg=3,91 eV ainsi que la valeur extrapolée à l'infrarouge de leur indice de réfraction (1,90). Des couches minces amorphes de CdTeO3 ont aussi été déposées sur CdTe en couche mince. Un recuit approprié des structures ainsi obtenues permet de faire croître du CdTeO3 polycristallin sur du CdTe polycristallin.

Engineering new solid propellant materials requires optimization of several factors, to include energy density, burn rate, sensitivity, and environmental impact. Equally important is the need for materials that will maintain their mechanical properties and thermal stability during long periods of storage. The nanoscale materials considered in this dissertation are proposed metal additives that may enhance energy density and improve combustion in a composite rocket motor. Density Functional Theory methods are used to determine cluster geometries, bond strengths, and energy densities. The ground-state geometries and electron affinities (EAs) for MnxO?: x = 3, 4, y = 1, 2 clusters were calculated with GGA, and estimates for the vertical detachment energies compare well with experimental results. It was found that the presence of oxygen influences the overall cluster moment and spin configuration, stabilizing ferrimagnetic and antiferromagnetic isomers. The calculated EAs range from 1.29-1.84 eV, which is considerably lower than the 3.0-5.0 eV EAs characteristic of current propellant oxidizers. Their use as solid propellant additives is limited. The structures and bonding of a range of Al-cyclopentadienyl cluster compounds were studied with multilayer quantum mechanics/molecular mechanics (QM:MM) methods. The organometallic Al-ligand bonds are generally 55-85 kcal/mol and are much stronger than Al-Al interactions. This suggests that thermal decomposition in these clusters will proceed via the loss of surface metal-ligand units. The energy density of the large clusters is calculated to be nearly 60% that of pure aluminum. These organometallic cluster systems may provide a route to extremely rapid Al combustion in solid rocket motors. Lastly, the properties of COOH-terminated passivating agents were modeled with the GPW method. It is confirmed that fluorinated polymers bind to both Al(111) and Al(100) at two Al surface sites. The oligomers HCOOH, CH3CH2COOH, and CF3CF2COOH chemisorb onto Al(111) with adsorption energies of 10-45 kcal/mol. The preferred contact angle for the organic chains is 65-85 degrees, and adsorption energy weakens slightly with increasing chain length. Despite their relatively weak adsorption energies, fluorinated polymers have elevated melting temperatures, making them good passivation materials for micron-scale Al fuel particles.

Defects in the functional oxides play an important role in electronic devices like metal oxide semiconductor field effect transistors (MOSFETs) and resistive random-access memories (ReRAMs). The continuous scaling of CMOS has brought the Si MOSFET to its physical technology limit and the replacement of Si channel with Ge channel is required. However, the performance of Ge MOSFETs suffers from Ge/oxide interface quality and reliability problems, which originates from the charge traps and defect states in the oxide or at the Ge/oxide interface. The sub-oxide layers composed of GeII states at the Ge/GeO2 interface seems unavoidable with normal passivation methods like hydrogen treatment, which has poor electrical properties and is related to the reliability problem. On the other hand, ReRAM works by formation and rupture of O vacancy conducting filaments, while how this process happens in atomic scale remains unclear. In this thesis, density functional theory is applied to investigate the defect behaviours in oxides to address existing issues in these electronic devices. In chapter 3, the amorphous atomic structure of doped GeO2 and Ge/GeO2 interface networks are investigated to explain the improved MOSFET reliability observed in experiments. The reliability improvement has been attributed to the passivation of valence alternation pair (VAP) type O deficiency defects by doped rare earth metals. In chapter 4, the oxidation mechanism of GeO2 is investigated by transition state simulation of the intrinsic defect diffusion in the network. It is proposed that GeO2 is oxidized from the Ge substrate through lattice O interstitial diffusion, which is different from SiO2 which is oxidized by O2 molecule diffusion. This new mechanism fully explains the strange isotope tracer experimental results in the literature. In chapter 5, the Fermi level pinning effect is explored for metal semiconductor electrical contacts in Ge MOSFETs. It is found that germanides show much weaker Fermi level pinning than normal metal on top of Ge, which is well explained by the interfacial dangling bond states. These results are important to tune Schottky barrier heights (SBHs) for n-type contacts on Ge for use on Ge high mobility substrates in future CMOS devices. In chapter 6, we investigate the surface and subsurface O vacancy defects in three kinds of stable TiO2 surfaces. The low formation energy under O poor conditions and the +2 charge state being the most stable O vacancy are beneficial to the formation and rupture of conducting filament in ReRAM, which makes TiO2 a good candidate for ReRAM materials. In chapter 7, we investigate hydrogen behaviour in amorphous ZnO. It is found that hydrogen exists as hydrogen pairs trapped at oxygen vacancies and forms Zn-H bonds. This is different from that in c-ZnO, where H acts as shallow donors. The O vacancy/2H complex defect has got defect states in the lower gap region, which is proposed to be the origin of the negative bias light induced stress instability.

O carbeto de silício (SiC) é um semicondutor com propriedades adequadas para substituir o silício em dispositivos eletrônicos em aplicações que exijam alta potência, alta frequência e/ou alta temperatura. Além disso, é possível crescer termicamente um filme de dióxido de silício (SiO2) sobre o SiC de maneira análoga ao silício. Porém, esses filmes apresentam maior densidade de defeitos eletricamente ativos na região interfacial SiO2/SiC que no caso do SiO2/Si, o que limita a qualidade dos dispositivos formados. Assim, compreender a origem da degradação elétrica e desenvolver métodos para passivar os defeitos na região interfacial SiO2/SiC são importantes passos para o desenvolvimento da tecnologia do SiC. Buscando uma melhor compreensão da natureza dos defeitos presentes na região interfacial SiO2/SiC, a interação de estruturas SiO2/SiC com vapor d’água enriquecido isotopicamente (D2 18O) e a interação com monóxido de carbono (CO), um dos subprodutos da oxidação térmica do SiC, foram investigadas. Observou-se que a interação com CO gera cargas positivas na estrutura e que a incorporação de deutério proveniente da água é fortemente dependente da rota de formação do filme de SiO2. Sabendo que a incorporação de nitrogênio e de fósforo na região interfacial SiO2/SiC são eficientes métodos para reduzir o número de defeitos eletricamente ativos nessa região, investigou-se a incorporação de nitrogênio em estruturas de SiC através de tratamentos térmicos em amônia enriquecida isotopicamente (15NH3) e desenvolveu-se um novo método de incorporação de fósforo, fazendo sua deposição por pulverização catódica (sputtering) Os métodos de incorporação propostos resultaram em maiores quantidades de nitrogênio e de fósforo na região interfacial SiO2/SiC do que os encontrados na literatura, tornando-os promissores candidatos na passivação elétrica do SiC. Além da caracterização físico-química utilizando diferentes técnicas, também foi feita a caracterização elétrica de capacitores Metal-Óxido-Semicondutor (MOS) testando filmes de SiO2 obtidos por sputtering ou por crescimento térmico. Adicionalmente, desenvolveu-se uma rota de síntese de padrões de 18O mais estáveis ao longo do tempo para serem utilizados em análises por reação nuclear. Também foi proposta uma metodologia de quantificação de fósforo via análise por reação nuclear. Dos resultados obtidos neste doutorado, uma melhor compreensão da natureza e da origem dos defeitos presentes na região interfacial SiO2/SiC foi alcançada. Também obteve-se uma melhor compreensão de como os elementos passivadores nitrogênio e fósforo interagem nessa região. / Silicon carbide (SiC) is a semiconductor with adequate properties to substitute silicon in electronic devices in applications that require high power, high frequency, and/or high temperature. Besides, a silicon dioxide (SiO2) film can be thermally grown on SiC in a similar way to that on Si. However, these films present higher density of electrical defects in the SiO2/SiC interfacial region when compared to the SiO2/Si interface, which limits the quality of the fabricated devices. Thus, it is important to understand the origin of the electrical degradation and to develop methods to passivate the defects in the SiO2/SiC interfacial region in order to develop the SiC technology. Aiming at a better understanding of the nature of defects at the SiO2/SiC interfacial region, the interaction of SiO2/SiC structures with water vapor isotopically enriched (D2 18O) and the interaction with carbon monoxide (CO), one of the SiC thermal oxidation by-products, were investigated. It was observed that the interaction with CO generates positive charges in the structure and that the deuterium incorporation from the water vapor is strongly dependent on the formation route of the SiO2 film. Knowing that nitrogen and phosphorous incorporation in the SiO2/SiC interfacial region are efficient methods to reduce the number of electrical defects in this region, the nitrogen incorporation in SiC structures by isotopically enriched ammonia (15NH3) annealings was investigated and a new method to incorporate phosphorous, by sputtering deposition was developed The proposed incorporation methods resulted in higher amounts of nitrogen and phosphorous then those found in literature, making them promising candidates to the electrical passivation of SiC. Besides the physico-chemical characterization using different techniques, the electrical characterization of Metal-Oxide-Semiconductor (MOS) capacitors was also performed, testing SiO2 films obtained by sputtering deposition or thermally grown. Additionally, a route to synthesize 18O standards for nuclear reaction analyses that are more stable over time was developed. Besides, a methodology to quantify phosphorous by nuclear reaction analysis was proposed. From the results obtained in this PhD thesis, a better understanding of the nature and the origin of defects present in the SiO2/SiC interfacial region was obtained, as well as a better understanding on how the passivating elements nitrogen and phosphorous interact in this region.

O carbeto de silício (SiC) é um semicondutor com propriedades adequadas para substituir o silício em dispositivos eletrônicos em aplicações que exijam alta potência, alta frequência e/ou alta temperatura. Além disso, é possível crescer termicamente um filme de dióxido de silício (SiO2) sobre o SiC de maneira análoga ao silício. Porém, esses filmes apresentam maior densidade de defeitos eletricamente ativos na região interfacial SiO2/SiC que no caso do SiO2/Si, o que limita a qualidade dos dispositivos formados. Assim, compreender a origem da degradação elétrica e desenvolver métodos para passivar os defeitos na região interfacial SiO2/SiC são importantes passos para o desenvolvimento da tecnologia do SiC. Buscando uma melhor compreensão da natureza dos defeitos presentes na região interfacial SiO2/SiC, a interação de estruturas SiO2/SiC com vapor d’água enriquecido isotopicamente (D2 18O) e a interação com monóxido de carbono (CO), um dos subprodutos da oxidação térmica do SiC, foram investigadas. Observou-se que a interação com CO gera cargas positivas na estrutura e que a incorporação de deutério proveniente da água é fortemente dependente da rota de formação do filme de SiO2. Sabendo que a incorporação de nitrogênio e de fósforo na região interfacial SiO2/SiC são eficientes métodos para reduzir o número de defeitos eletricamente ativos nessa região, investigou-se a incorporação de nitrogênio em estruturas de SiC através de tratamentos térmicos em amônia enriquecida isotopicamente (15NH3) e desenvolveu-se um novo método de incorporação de fósforo, fazendo sua deposição por pulverização catódica (sputtering) Os métodos de incorporação propostos resultaram em maiores quantidades de nitrogênio e de fósforo na região interfacial SiO2/SiC do que os encontrados na literatura, tornando-os promissores candidatos na passivação elétrica do SiC. Além da caracterização físico-química utilizando diferentes técnicas, também foi feita a caracterização elétrica de capacitores Metal-Óxido-Semicondutor (MOS) testando filmes de SiO2 obtidos por sputtering ou por crescimento térmico. Adicionalmente, desenvolveu-se uma rota de síntese de padrões de 18O mais estáveis ao longo do tempo para serem utilizados em análises por reação nuclear. Também foi proposta uma metodologia de quantificação de fósforo via análise por reação nuclear. Dos resultados obtidos neste doutorado, uma melhor compreensão da natureza e da origem dos defeitos presentes na região interfacial SiO2/SiC foi alcançada. Também obteve-se uma melhor compreensão de como os elementos passivadores nitrogênio e fósforo interagem nessa região. / Silicon carbide (SiC) is a semiconductor with adequate properties to substitute silicon in electronic devices in applications that require high power, high frequency, and/or high temperature. Besides, a silicon dioxide (SiO2) film can be thermally grown on SiC in a similar way to that on Si. However, these films present higher density of electrical defects in the SiO2/SiC interfacial region when compared to the SiO2/Si interface, which limits the quality of the fabricated devices. Thus, it is important to understand the origin of the electrical degradation and to develop methods to passivate the defects in the SiO2/SiC interfacial region in order to develop the SiC technology. Aiming at a better understanding of the nature of defects at the SiO2/SiC interfacial region, the interaction of SiO2/SiC structures with water vapor isotopically enriched (D2 18O) and the interaction with carbon monoxide (CO), one of the SiC thermal oxidation by-products, were investigated. It was observed that the interaction with CO generates positive charges in the structure and that the deuterium incorporation from the water vapor is strongly dependent on the formation route of the SiO2 film. Knowing that nitrogen and phosphorous incorporation in the SiO2/SiC interfacial region are efficient methods to reduce the number of electrical defects in this region, the nitrogen incorporation in SiC structures by isotopically enriched ammonia (15NH3) annealings was investigated and a new method to incorporate phosphorous, by sputtering deposition was developed The proposed incorporation methods resulted in higher amounts of nitrogen and phosphorous then those found in literature, making them promising candidates to the electrical passivation of SiC. Besides the physico-chemical characterization using different techniques, the electrical characterization of Metal-Oxide-Semiconductor (MOS) capacitors was also performed, testing SiO2 films obtained by sputtering deposition or thermally grown. Additionally, a route to synthesize 18O standards for nuclear reaction analyses that are more stable over time was developed. Besides, a methodology to quantify phosphorous by nuclear reaction analysis was proposed. From the results obtained in this PhD thesis, a better understanding of the nature and the origin of defects present in the SiO2/SiC interfacial region was obtained, as well as a better understanding on how the passivating elements nitrogen and phosphorous interact in this region.

Comme dans beaucoup de domaines, la sécurité dépend du développement de méthodes analytiques très sensibles et fiables pour pouvoir détecter des molécules dangereuses. C'est pourquoi il est important de développer des méthodes simples afin de diagnostiquer rapidement un composé dangereux dans notre environnement. Dans ce contexte, les techniques électrochimiques offrent une alternative intéressante puisqu'elles permettent d'atteindre de grandes sensibilités et une bonne sélectivité, elles sont peu coûteuses et facilement adaptables pour la création de dispositifs portables. Récemment, notre équipe a développé un nouveau concept basé sur de la voltammétrie par échantillonnage de courant sur un réseau d'électrodes (EASCV), lequel est compatible avec la miniaturisation. Ce système permet de renouveler la surface et la solution au voisinage de l'électrode pendant l'analyse. Le projet de cette thèse a été d'étendre l'application de cette technique à des méthodes électrochimiques utilisant une étape de préconcentration. Une première étude, appliquée à la détection du phénol, a permis de montrer que l'EASCV offre une solution intéressante pour diminuer les phénomènes de passivation ayant lieu pendant l'analyse. En effet, une étude expérimentale associée à une étude théorique a montré que si un temps d'échantillonnage court était appliqué, le phénomène de passivation pouvait être évité. Enfin, pour la première fois, il a été possible de coupler la voltammétrie par échantillonnage de courant à la redissolution anodique. Cette étude, appliquée à la détection du plomb, a permis de mettre en place une courbe d'étalonnage et d'obtenir une intensité élevée de courant, 300 fois plus importante qu'avec les techniques classiques de redissolution anodique. Les premiers essais pour adapter ce nouveau concept aux méthodes pulsés se sont également montrés très encourageants. Afin d'améliorer la sensibilité et la sélectivité du capteur, le réseau d'électrodes a été fonctionnalisé. La modification dépend de la nature de l'espèce cible. Ainsi des polymères à empreintes moléculaires (pour des molécules comme la mélamine) ou des ligands (pour des ions comme le plomb) ont été testés. Dans les deux cas, une méthode d'électrogreffage a été mise au point pour fonctionnaliser la surface. Les premiers résultats obtenus sont encourageants puisqu'une courbe courant-potentiel a pu être tracée montrant une sensibilité 10 fois plus grande pour le plomb que celle obtenue avec une préconcentration par électrodépôt. / As in many fields, safety is primarily based on the development of reliable and highly sensitive analytical methods to detect hazardous molecules. Therefore there is a need for developing simple methods for the diagnosis of harmful molecules in our environment. In this context, electrochemical detection systems seems very promising because they are highly sensitive, require short analysis time, are easy to implement and economic to fabricate. Moreover, our team has recently developed a new concept of device based on sampled-current voltammetry performed on an electrode array (EASCV) which is compatible with miniaturization and portability. The system allows the renewal of the electrode surface and of the analytical solution during the analysis. The present project addresses these issues and aims to extend it to methods involving a preconcentration step. A first study, for the detection of phenol, showed that EASCV offers a versatile solution to decrease fouling effect during the analysis. Indeed experimental and theoretical studies show that the renewable of electrode surface and of the solution in the vicinity of the electrode associated with the use of a short sampled time can avoid electrode fouling. For the first time, it was possible to combine sampled-current voltammetry with anodic stripping voltammetry. In this study, we were able to create a calibration curve, for the detection of lead, and we obtained current intensities 300 times higher than with usual linear stripping voltammetry.First attempts to adapt this new concept to pulse methods were promising.. To increase the sensitivity and selectivity of the sensor, the electrode array is chemically modified. The nature of this modification depends on the nature of the analyte. Thus, molecular imprinted polymer (for molecules) or macrocyclic ligands (for ions) are tested In both cases, an electrografting method is achieved to functionalize the surface. The first results are promising since a current-potential curve is obtained with a sensibility ten times higher than with a preconcentration by electrodeposition.

In order to remove the local openings for contacting PERC Solar cells, one has to introduce passivating contacts. The Al₂O₃-TiOₓ double layer stack is an attractive candidate for this purpose. This study will guide a way to enhance the conductivity of those contacts by doping TiO x with a. Additionally, it is shown, that major parts of the stacks are deposited by sputtering. This demonstrates a higher feasibility for industrial applications than atomic layer deposition as reported earlier [1], [2].

The topic of this work is the passivation of the active layer of perovskite solar cells with an inverted structure. The work is divided into theoretical and experimental part. The theoretical part describes in particular the passivation and modification of the perovskite layer as well as the characteristic properties of perovskite, including structure and stability. The experimental part deals with the preparation of photovoltaic cells with an inverted structure. For the characterization of photovoltaic cells, reference samples were prepared and their active layer was modified by plasma. The most used deposition technique for the preparation of layers was the spin coating method. From the performed experiments it can be concluded that the preparation of samples and their subsequent modification under laboratory conditions does not lead to the improvement of the final parameters of photovoltaic conversion. By transferring the sample preparation and passivation of the active layer to an inert atmosphere, it was possible to produce cells with higher efficiencies (compared to the reference sample), around 10 %. Another advantage of this plasma treatment of the active layer is that it also improves the stability of the prepared structures, which even after a few days in air show almost 80 % of the original efficiency.

No description available.