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Amorphous and crystalline silicon nanocomposites have been shown to act as effective “sensitizers” for erbium ions. In the present work, a series of erbium-doped (0.2 at.%) SiOx:Er films (x = 1 - 1.8) were synthesized by physical vapor deposition and subsequently annealed at temperatures ranging from 400°C to 1100°C to induce phase separation and cluster growth. Silicon nanocluster (Si-NC) and Er3+ photoluminescence intensity spectra and dynamics were investigated as a function of SiOx composition, annealing temperature, pump wavelength and power, and specimen temperature in order to determine characteristic cross-sections and to map the efficiency of the energy transfer process between Si-NCs and Er3+ ions. Additionally, two types of optical waveguides based on SiOx:Er materials were fabricated using conventional CMOS compatible microfabrication processes. Waveguide propagation losses as well as signal absorption and enhancement were investigated under pumping conditions to evaluate the use of SiOx:Er materials as amplifying media. / Communications and Signal Processing

As propriedades ópticas de nanocristais de silício (Si-ncs) têm sido extensivamente estudadas após a primeira demonstração em 1990 de fotoluminescência altamente eficiente em silício poroso. Apesar dos progressos no entendimento da natureza da alta eficiência da luminescência dos Si-ncs e da enorme versatilidade para aplicações optoeletrônicas, este campo ainda é um tema de controvérsia devido à complexidade destes materiais. Além disso, as condições de preparação ainda afetam as propriedades de emissão destes materiais que são de fundamental importância para as aplicações tecnológicas. O presente trabalho teve como objetivo o estudo das propriedades óticas dos Si-ncs e entender os processos fotofisicos envolvidos na recombinação radiativa de éxcitons altamente confinados nesse sistema. Si-ncs embebidos em matriz amorfa de SiO2 foram preparados a partir de filmes de oxido de silício SiyO1-y subestequiométricos (y≥1/3) depositados em substratos de quartzo utilizando um sistema deposição CVD na fase estimulada por plasma (electron cyclotron resonance-plasma enhanced chemical vapor deposition ou ECR-PECVD). Esta técnica oferece boa passivação e estabilidade interfacial Si/SiO2. O tratamento térmico a altas temperaturas (900°C≤Ta≤1100°C) promove a precipitação do silício dentro da matriz, favorecendo um processo de nucleação e crescimento dos Si-ncs. Foram realizados tratamentos térmicos nos filmes sob atmosferas de Argônio (Ar) ou (Ar+5%H2) por duas horas. As distintas atmosferas promoveram a passivação de defeitos superficiais, principalmente de ligações pendentes pelo Hidrogênio. As propriedades associadas diretamente à fabricação, tais como estrutura cristalina, morfologia, tamanho e química da superfície dos Si-ncs foram correlacionadas com os processos de emissão envolvendo éxcitons. A caracterização estrutural foi realizada por Raio-x (XRD), Microscopia de Transmissão de Alta Resolução (HRTEM), Retroespalhamento de Rutherford e Espectroscopia Raman. As medidas óticas foram basicamente Absorção, Excitação Seletiva, Fotoluminescência CW (PL) e Fotoluminescência Resolvida no Tempo. Os resultados da caracterização indicaram que efeitos de confinamento quântico e de estados de superfície dominam o processo de recombinação no Si-nc/SiO2. Em conclusão, os resultados obtidos neste trabalho mostram uma interessante e uma nova correlação entre as condições de fabricação da amostra e os processos de recombinação de éxcitons em Si-nc/SiO2. Todos estes resultados desafiam modelos anteriores propostos para explicar as propriedades ópticas do sistema de Si-nc/SiO2 e prevê ajudar na futura aplicação tecnológica dos mesmos. / The optical properties of silicon nanocrystals (Si-nc) have been extensively studied after the first demonstration in 1990 of highly efficient photoluminescence in porous silicon. Despite progress in understanding the nature of high luminescence efficiency of Si-ncs and versatility for optoelectronic applications, this field is still a subject of controversy due to its complexity. Furthermore, the preparation conditions still affect the emission properties of these materials that are of fundamental importance for technological applications. This work aimed to study the optical properties of Si-ncs and to understand the photophysical processes involved in the radiative recombination of excitons strongly confined in this system. Si-ncs embedded in amorphous SiO2 were prepared from silicon oxide films of substoichiometric SiyO1-y (y≥1/3) deposited on quartz substrates using a CVD deposition system in phase stimulated by plasma (electron cyclotron resonance-plasma enhanced chemical vapor deposition ou ECR-PECVD). This technique provides good passivation and Si/SiO2 interfacial stability. The thermal treatment at high temperatures (900°C≤Ta≤1100°C) promotes the precipitation of silicon within the matrix, favoring a process of nucleation and growth of Si-ncs. The thermal treatments were performed in the films under Argon atmosphere (Ar) or (Ar+5%H2) for two hours. The use of different atmospheres allowed the understand of the passivation process of surface defects, particularly of dangling bonds by Hydrogen. The properties directly related to fabrication such as crystalline structure, morphology, size and surface chemistry of Si-ncs were correlated with emission processes involving excitons. The structural characterization was performed by X-Ray Diffraction (XRD), High resolution transmission electron microscopy (HRTEM), Rutherford Backscattering and Raman spectroscopy. The optical measurements were basically Absorption, Selective excitation, CW photoluminescence (PL) and Time Resolved Photoluminescence. The characterization results indicate that both quantum confinement and surface states effects dominate the recombination process in Si-ncs/SiO2. In conclusion, the results obtained in this work show an interesting and a novel correlation between the sample fabrication conditions and the exciton recombination process in Si-ncs/SiO2. All these results challenges previous models proposed to explain the optical properties of Si-nc systems and are expected to help further technological applications of this system.

Ce travail aborde le sujet des d efauts charg es dans le silicium. Jusqu' a pr esent, les d efauts charg es ont principalement et e etudi es en conditions p eriodiques (PBC). En e et, l'approche PBC est parfaite pour simuler unsolide in ni. Mais, comme je le montre dans ce chapitre, elle apporte aussi des artefacts. En particulier dans le traitement de l' electrostatique, o u des traitements math ematiques important doivent ^etre utilis es pour supprimer les interactions non d esir ees entre r epliques. Notre approche vise a simuler correctement un d efaut charg e, tout en conservant de bonne propri et es pourle mat eriau massif. Elle consiste a simuler le d efaut dans un nano-agr egat. Le traitement de l' electrostatique est correct dans un nano-agr egat et les r esultats obtenus peuvent ^etre extrapol es au mat eriau massif, comme il est montr e dans ce chapitre. Les perspectives de cette m ethode sont aussi abord ees ici. / In this work we have studied Si clusters with point defects in various charged states. Point defects in semiconductors affects the electronic structure of the material introducing new energy levels and consequently new modes of transport.Detailed study of the point defects have been undertaken in various approaches. The most common practice is to usesuper-cell calculations under the framework of Density Functional Theory with Periodic Boundary Conditions (PBC). Inthis formalism there are a lot of factors like defect-defect interactions, image charge interactions, that are to be correctedfor to achieve the " artefact-free" results. In this study we have used Free Boundary Conditions with nano-clusters of Sipassivated with Hydrogen at the surface. Previous works have undertaken in detail the geometrical effects in the nanoclusters. But a complete picture of the electrostatics and its effect on the energy states demand a complete study. Hence inour calculations we take another approach, devoid of the correction factors for cases with PBC, and produce an alternativeway to calculate the formation energy of the defects. We have described the formation and stability of the defects invarious charged states and provided with a detailed analysis of the properties pertaining to the nano-scale size. Finallymigration parameters are provided with respect to the charge states of the defects. Our results are also compared with thePBC calculations with critical discussions.

As propriedades ópticas de nanocristais de silício (Si-ncs) têm sido extensivamente estudadas após a primeira demonstração em 1990 de fotoluminescência altamente eficiente em silício poroso. Apesar dos progressos no entendimento da natureza da alta eficiência da luminescência dos Si-ncs e da enorme versatilidade para aplicações optoeletrônicas, este campo ainda é um tema de controvérsia devido à complexidade destes materiais. Além disso, as condições de preparação ainda afetam as propriedades de emissão destes materiais que são de fundamental importância para as aplicações tecnológicas. O presente trabalho teve como objetivo o estudo das propriedades óticas dos Si-ncs e entender os processos fotofisicos envolvidos na recombinação radiativa de éxcitons altamente confinados nesse sistema. Si-ncs embebidos em matriz amorfa de SiO2 foram preparados a partir de filmes de oxido de silício SiyO1-y subestequiométricos (y≥1/3) depositados em substratos de quartzo utilizando um sistema deposição CVD na fase estimulada por plasma (electron cyclotron resonance-plasma enhanced chemical vapor deposition ou ECR-PECVD). Esta técnica oferece boa passivação e estabilidade interfacial Si/SiO2. O tratamento térmico a altas temperaturas (900°C≤Ta≤1100°C) promove a precipitação do silício dentro da matriz, favorecendo um processo de nucleação e crescimento dos Si-ncs. Foram realizados tratamentos térmicos nos filmes sob atmosferas de Argônio (Ar) ou (Ar+5%H2) por duas horas. As distintas atmosferas promoveram a passivação de defeitos superficiais, principalmente de ligações pendentes pelo Hidrogênio. As propriedades associadas diretamente à fabricação, tais como estrutura cristalina, morfologia, tamanho e química da superfície dos Si-ncs foram correlacionadas com os processos de emissão envolvendo éxcitons. A caracterização estrutural foi realizada por Raio-x (XRD), Microscopia de Transmissão de Alta Resolução (HRTEM), Retroespalhamento de Rutherford e Espectroscopia Raman. As medidas óticas foram basicamente Absorção, Excitação Seletiva, Fotoluminescência CW (PL) e Fotoluminescência Resolvida no Tempo. Os resultados da caracterização indicaram que efeitos de confinamento quântico e de estados de superfície dominam o processo de recombinação no Si-nc/SiO2. Em conclusão, os resultados obtidos neste trabalho mostram uma interessante e uma nova correlação entre as condições de fabricação da amostra e os processos de recombinação de éxcitons em Si-nc/SiO2. Todos estes resultados desafiam modelos anteriores propostos para explicar as propriedades ópticas do sistema de Si-nc/SiO2 e prevê ajudar na futura aplicação tecnológica dos mesmos. / The optical properties of silicon nanocrystals (Si-nc) have been extensively studied after the first demonstration in 1990 of highly efficient photoluminescence in porous silicon. Despite progress in understanding the nature of high luminescence efficiency of Si-ncs and versatility for optoelectronic applications, this field is still a subject of controversy due to its complexity. Furthermore, the preparation conditions still affect the emission properties of these materials that are of fundamental importance for technological applications. This work aimed to study the optical properties of Si-ncs and to understand the photophysical processes involved in the radiative recombination of excitons strongly confined in this system. Si-ncs embedded in amorphous SiO2 were prepared from silicon oxide films of substoichiometric SiyO1-y (y≥1/3) deposited on quartz substrates using a CVD deposition system in phase stimulated by plasma (electron cyclotron resonance-plasma enhanced chemical vapor deposition ou ECR-PECVD). This technique provides good passivation and Si/SiO2 interfacial stability. The thermal treatment at high temperatures (900°C≤Ta≤1100°C) promotes the precipitation of silicon within the matrix, favoring a process of nucleation and growth of Si-ncs. The thermal treatments were performed in the films under Argon atmosphere (Ar) or (Ar+5%H2) for two hours. The use of different atmospheres allowed the understand of the passivation process of surface defects, particularly of dangling bonds by Hydrogen. The properties directly related to fabrication such as crystalline structure, morphology, size and surface chemistry of Si-ncs were correlated with emission processes involving excitons. The structural characterization was performed by X-Ray Diffraction (XRD), High resolution transmission electron microscopy (HRTEM), Rutherford Backscattering and Raman spectroscopy. The optical measurements were basically Absorption, Selective excitation, CW photoluminescence (PL) and Time Resolved Photoluminescence. The characterization results indicate that both quantum confinement and surface states effects dominate the recombination process in Si-ncs/SiO2. In conclusion, the results obtained in this work show an interesting and a novel correlation between the sample fabrication conditions and the exciton recombination process in Si-ncs/SiO2. All these results challenges previous models proposed to explain the optical properties of Si-nc systems and are expected to help further technological applications of this system.

Cette thèse est consacrée à l'étude approfondie de formes exotiques de matériaux nano-structurés qui pourraient conduire à une avancée significative dans les nano-composants. Deux thèmes distincts ont été ainsi abordés. Le premier concerne les nano-clusters aromatiques de silicium synthétisés par plasma (SiNCs), tandis que le second est dédié aux structures silicium et germanium bi-dimensionnelles. Grâce à des simulations de type dynamique moléculaire et des calculs ab initio, ainsi que sur des recherches expérimentales, nous nous proposons d’explorer les propriétés intrigantes, mais à fort potentiel, de ces matériaux exotiques.Dans la première partie, nous commençons par des études théoriques et montrons qu'il est possible d'obtenir un comportement aromatique pour des SiNCs hydrogénés ayant une taille de ~1nm. Nous démontrons que les plasmas silane/hydrogène à basse température, proches de la formation de particules de poussière, présentent l'environnement idéal pour exploiter la tendance naturelle du silicium à la sur-coordination et donc pour la synthèse de structures à liaisons déficitaires en électrons. Ces nano-clusters qui se forment spontanément par auto-assemblage dans le plasma, ne possèdent pas de structure tétraédrique, sont plus stables que tous les autres SiNCs connus de cette taille et ont de fortes propriétés aromatiques dues à leur forte délocalisation électronique. Nous montrons également que les SiNCs non tétraédriques, présentent des modes de liaison à caractère métallique qui ressemblent fortement à celui d'un gaz d'électrons homogène dans des nano-clusters de métaux. Les SiNCs tétraédriques standards de cette taille ne peuvent absorber que dans l'ultraviolet, alors que nos calculs ont montré que des SiNCs purs, mais sur-coordonnés, absorbent dans la région spectrale ultraviolette, mais aussi dans le visible et l’infrarouge. Nous présentons ensuite une première preuve expérimentale pour nos prédictions théoriques. Nous avons mesuré in situ, dans un réacteur plasma l'absorption de la lumière visible des SiNCs. De plus, nos mesures réalisées en présence d'un champ électrique ont prouvées clairement que les SiNCs aromatiques possèdent un moment dipolaire permanent, que nous avons estimé entre 2 et 2,5 Debye, en excellent accord avec les calculs ab initio. Enfin, nos images de microscopie électronique à transmission des SiNCs, déposés dans des conditions de plasma optimisées, ont révélé la présence d'une autre forme exotique de silicium à structure hexagonale. Une telle structure se forme habituellement à des pressions extrêmement élevées appliquées sur des structures cubiques (diamant) de silicium. Nous souhaitons affirmer que c’est grâce à la «chimie au marteau» que ces conditions ont été atteintes.Dans la seconde partie, nous avons entrepris des études théoriques et expérimentales approfondies sur la croissance d'une nouvelle forme allotropique de silicium et de germanium: le silicène et le germanène, à savoir, une mono-couche d'atomes intégrée dans un réseau hexagonal qui ressemble fortement au graphène. Afin d'exclure tout mélange entre les atomes de silicium ou de germanium avec le substrat et de conserver leurs caractéristiques prometteuses comme de nouveaux matériaux de Dirac, nous avons effectué nos dépôts, sur un substrat de graphite chimiquement inerte. Une de nos découvertes cruciales est que les mono-couches de silicène ou de germanène interagissent avec le substrat de graphite uniquement via des forces de van der Waals. Cette interaction est suffisamment forte pour stabiliser les mono-couches, déposées même au-dessus de la température ambiante, mais suffisamment faible pour empêcher toute hybridation ou alliage entre le silicium ou le germanium et les atomes de carbone du substrat. Par conséquent, les propriétés électroniques exceptionnelles du silicène et du germanène, tels que les cônes de Dirac et les électrons sans masse, sont préservées même après leur dépôt sur les surfaces de graphite. / This thesis is devoted to the study of advanced, exotic forms of nanostructured materials that could lead to the next big advance for nanodevices. Two distinct topics have been considered. The first one is related to plasma-born aromatic silicon nanoclusters (SiNCs), while the second is dedicated to two-dimensional silicon and germanium materials. Based on molecular dynamics simulations and ab initio calculations, as well as, on experimental investigations, we explore a variety of intriguing properties of those exotic materials that are expected to be far superior to those of their conventional counterparts.In the first part of the thesis, we begin with theoretical studies and show that it is possible to obtain aromatic behavior in simple hydrogenated SiNCs with size of ~1nm. We demonstrate that low-temperature silane/hydrogen plasmas close to dust formation present the ideal environment to exploit the natural tendency of silicon to over-coordination for the construction of structures with electron-deficient bonds. Those nanoclusters form spontaneously by self-assembly in plasmas, do not possess tetrahedral structures, are more stable than any other known SiNCs of this size, and have strong aromatic-like properties due to their high electron delocalization. We demonstrate that non-tetrahedral SiNCs exhibit metallic-like bonding schemes that strongly resemble the one of a homogeneous electron gas in small metal clusters. Standard tetrahedral SiNCs of this size can absorb light only in the ultraviolet, while our calculations have shown that pure, but over-coordinated SiNCs absorb light in the ultraviolet, visible, and infrared spectral region. In this thesis, we present first experimental evidence that supports our theoretical predictions. Using incoherent broadband cavity enhanced absorption spectroscopy, we have measured the absorption of SiNCs, in situ, in a plasma reactor and found that they do absorb light in the visible region. In addition, our absorption measurements in the presence of an applied electric field have provided clear evidence that aromatic SiNCs possess a permanent dipole moment, and we have measured it to be between 2 and 2.5 Debye, in excellent agreement to prior ab initio calculations. Finally, our transmission electron microscopy images of such SiNCs, after their deposition under optimized plasma conditions, have revealed the presence of another exotic form of silicon with a primitive hexagonal structure. Such a structure usually forms after exposing diamond-cubic silicon to extremely high pressures. We tentatively claim that those conditions were, actually, achieved in our experiments due to the “chemistry with a hammer”.In the second part of the thesis, we have undertaken in-depth theoretical and experimental studies on the growth of a new allotropic form of silicon and germanium: a single layer of silicon or germanium atoms, only one atom thick and packed in a hexagonal lattice that closely resembles the lattice of graphene, namely silicene and germanene. In order to rule out any intermixing between silicon or germanium atoms and the underneath substrate atoms, as it was the case for metallic substrates, and to maintain their promising features to be new Dirac materials, we have performed our depositions on a chemically inert graphite substrate. One of our crucial findings is that the silicene or germanene monolayers interact with the graphite substrate via van der Waals forces only. The van der Waals interaction is strong enough to stabilize the deposited monolayers even above room temperature, but weak enough to prevent any hybridization or alloying between silicon or germanium and carbon atoms. Consequently, the outstanding electronic properties of free-standing silicene and germanene, such as Dirac cones and massless electrons, are preserved even after their deposition on graphite surfaces.

<p>Silicon nanostructures formed in silicon-rich silicon nitride (SRSN) and cerium and terbium doped silicon oxide thin films grown using different types of plasma-enhanced chemical vapour deposition have been studied through photoluminescence (PL) and synchrotron-based X-ray absorption spectroscopies to determine the effects of deposition and processing parameters on the luminescent and structural properties of these materials. The SRSN films exhibited bright PL attributed to quantum confinement effects in the silicon nanoclusters (Si-ncs) as well as radiative defects in the silicon nitride host matrix. The peak emission energy could be tuned from the near-infrared across the entire visible spectrum by controlling the film composition and the post-deposition annealing temperature and time to change the size of the Si-ncs. Preliminary experiments on cerium doped SRSN samples indicated that although the cerium ions coordinate in the optically active trivalent oxidation state, they were not effectively sensitized by Si-ncs in the films tested, most likely due to the nanoclusters having bandgap energies that were unsuitable for this purpose. In cerium and terbium co-doped silicon oxide films, cerium disilicate (Ce₂Si₂O₇) nanocrystallites were formed by annealing at temperatures of 900°C and higher. The A-Ce₂Si₂O₇, G-Ce₂Si₂O₇, and Ce₆[Si₄O₁₃][SiO₄]₂ phases of cerium disilicate were observed to form under different deposition and annealing conditions. All three phases exhibited extremely bright violet-blue PL and were found to efficiently sensitize green emission from co-dopant Tb³⁺ ions in the films. The Tb³⁺ luminescence predominantly corresponded to the ⁵D₄→⁷F_3–6 emission lines, although weak ⁵D₃→⁷F_2–6 emission lines were also observed in films containing relatively high concentrations of terbium indicating that the sensitization of Tb³⁺ ions occurred through the ⁵D₃, ⁵L₁₀, or ⁵D₂ energy levels.</p> / Doctor of Philosophy (PhD)