In this thesis, colloidal nanocrystalline silicon (ncSi) capped with allylbenzene (AB) groups, is created using a sol-gel method. This novel material, AB-ncSi, is size separated and its optical, structural, and electrical characteristics are investigated in detail. For optical characterization, the photoluminescence (PL) peak is located for each fraction of the nanoparticles to determine its diameter. The AB-ncSi samples have diameters ranging from 2.89 nm to 7.65 nm. Ellipsometry and scanning electron microscopy (SEM) are used to estimate the film thickness and average distance between the particles, respectively, for structural characterization. No correlation was found between AB-ncSi size and film thickness however the estimated average distance between the particles decreased with decreasing diameter. Finally, for electrical characterization, conductivity of size-separated samples is measured and the temperature dependent conductance is analyzed. The results emerging from these analyses suggest that the charge transport mechanism for AB-ncSi is nearest-neighbor hopping (NNH) albeit VRH is also a potential contributor.

In this thesis, colloidal nanocrystalline silicon (ncSi) capped with allylbenzene (AB) groups, is created using a sol-gel method. This novel material, AB-ncSi, is size separated and its optical, structural, and electrical characteristics are investigated in detail. For optical characterization, the photoluminescence (PL) peak is located for each fraction of the nanoparticles to determine its diameter. The AB-ncSi samples have diameters ranging from 2.89 nm to 7.65 nm. Ellipsometry and scanning electron microscopy (SEM) are used to estimate the film thickness and average distance between the particles, respectively, for structural characterization. No correlation was found between AB-ncSi size and film thickness however the estimated average distance between the particles decreased with decreasing diameter. Finally, for electrical characterization, conductivity of size-separated samples is measured and the temperature dependent conductance is analyzed. The results emerging from these analyses suggest that the charge transport mechanism for AB-ncSi is nearest-neighbor hopping (NNH) albeit VRH is also a potential contributor.

Recently extensive efforts have been spent in order to achieve all silicon based photonic devices exploiting the efficient light emission from nanostructured silicon systems. In this thesis, silicon based nanostructures have been investigated for electro-optical and photovoltaic applications. The thesis focused on three application areas of silicon nanostructures: Light emitting diode (LED), light modulation using quantum confined Stark effect (QCSE) and photovoltaic applications. In the context of LED applications, ZnO nanocrystal/silicon heterojunctions were investigated. Contrary to observation of pure ultraviolet photoluminescence (PL) from ZnO nanocrystals that were synthesized through vapor liquid solidification (VLS) method, visible emissions were observed in the electroluminescence (EL) due to defect states of ZnO. The discrepancy between these emissions could be ascribed to both change in excitation mechanisms and the defect formation on ZnO nanocrystals surface during device fabrication steps. EL properties of silicon nanocrystals embedded in SiO2 matrix were also systematically studied with and without Tb doping. Turn-on voltage of the Tb doped LED structures was reduced below 10 V for the first time. Clear observation of QCSE has been demonstrated for the first time in Si nanocrystals embedded in SiO2 through systematic PL measurements under external electric field. Temperature and size dependence of QCSE measurements were consistently supported by our theoretical calculations using linear combination of bulk Bloch bands (LCBB) as the expansion basis. We have managed to modulate the exciton energy as high as 80 meV with field strength below MV/cm. Our study could be a starting point for fabrication of electro-optical modulators in futures for all silicon based photonic applications. In the last part of the thesis, formation kinetics of silicon nanowires arrays using a solution based novel technique called as metal assisted etching (MAE) has been systematically studied over large area silicon wafers. In parametric studies good control over nanowire formation was provided. Silicon nanowires were tested as an antireflective layer for industrial size solar cell applications. It was shown that with further improvements in surface passivation and contact formation, silicon nanowires could be utilized in very efficient silicon solar cells.

<p> The need for higher bandwidth and people's desire to be "always connected" have spurred a new era of silicon photonics. The traditional integrated electrical transmission lines have been an obstacle preventing ultra high speed communication. Using monolithic chips of integrated optoelectronic circuits from silicon provides an economic way to realize Tetra Byte/Second bandwidth in a variety of areas such as "fiber to the home" and the buses linking chips inside computer.</p> <p> The heart of such optoelectronics-silicon laser-is still in pursuit. One of the most promising approaches is the erbium doped silicon nanocrystals embedded in silica system. External photon or hot electrons injection excites the silicon nanocrystals, which then transfer their energies to nearby erbium ions to emit light at 1.55 μm wavelength range.</p> <p> In this thesis, we investigate the effects of cavity and electric field on energy transfer from Si nanocrystals (Si-nc's) to Er ions, and simulate material gain in such systems. Our results show that microcavity can enhance the Forster energy transfer and material gain, reducing the requirements for Si-nc pumping. The electric field will hinder the radiation decay of Si-nc, but we have to further explore the tunneling mechanism before concluding the overall effect of electric field. Some future work needs to be done, which will shine some light on the design of the silicon laser.</p> / Thesis / Master of Applied Science (MASc)

Tandem solar cells are potentially much more efficient than the silicon solar cells that currently dominate the market but require materials with different bandgaps. This thesis presents work on silicon nanocrystals (Si-NC) embedded in silicon carbide (SiC), which are expected to have a higher bandgap than bulk Si due to quantum confinement, with a view to using them in the top cell of a tandem cell. The strong photoluminescence (PL) of precursor films used to prepare Si-NC in SiC (Si-NC/SiC) was markedly reduced upon Si-NC formation due to simultaneous out-diffusion of hydrogen that passivated dangling bonds. This cannot be reversed by hydrogenation and leads to weak PL that is due to, and limited by, non-paramagnetic defects, with an estimated quantum yield of ≤5×10^-7. Optical interference was identified as a substantial artefact and a method proposed to account for this. Majority carrier transport was found to be Ohmic at all temperatures for a wide range of samples. Hydrogenation decreases dangling bond density and increases conductivity up to 1000 times. The temperature-dependence of conductivity is best described by a combination of extended-state and variable-range hopping transport where the former takes place in the Si nanoclusters. Furthermore, n-type background doping by nitrogen and/or oxygen was identified. In the course of developing processing steps for Si-NC-based tandem cells, a capping layer was developed to prevent oxidation of Si-NC/SiC, and diffusion of boron and phosphorus in nanocrystalline SiC was found to occur via grain boundaries with an activation energy of 5.3±0.4 eV and 4.4±0.7 eV, respectively. Tandem cells with a Si-NC/SiC top cell and bulk Si bottom cell were prepared that exhibited open-circuit voltages V_oc of 900 mV and short-circuit current densities of 0.85 mAcm^-2. Performance was limited by photocurrent collection in the top cell; however, the V_oc obtained demonstrates tandem cell functionality.

In the main part of this thesis I study the relaxation mechanisms of charge carriers in silicon nanocrystals in SiO2 matrix. One of the potential applications of these structures lies in photovoltaics, specifically in construction of all-silicon tandem solar cells. I studied the dynamics of carriers in these structures by methods of ultrafast spectroscopy which helped to unravel the microscopic behaviour of carriers, their transport, localization etc. Furthermore I investigated the doping of such structures as the technology of doping is crucial for manufacture of pn- junctions which are the core component of solar cells. At the end I delve into the dissipative Jaynes-Cummings model by mathematical modeling and theoretical calculations which describes among others microlasers and as such comes under a field of cavity quantum electrodynamics.

Ce travail de thèse concerne la réalisation et l'analyse des propriétés optiques de nanocristaux de silicium. Ces objets de taille nanométrique possèdent des propriétés optiques remarquables, en particulier de photoluminescence. Les propriétés de confinement quantique qui les caractérisent permettent d'obtenir un signal de luminescence intense dans le domaine du visible. Des composants optoélectroniques et photoniques ont été envisagés à base de nanocristaux de silicium. Les raisons physiques du fort signal de luminescence en revanche sont encore mal comprises. Les nanocristaux de silicium sont élaborés par évaporation. L'élaboration et le recuit thermique de multicouches SiO/SiO2 permet d'obtenir des nanocristaux de silicium de diamètre moyen bien contrôlé. Ceux-ci sont issus de la démixtion de la couche de SiO selon la réaction SiOx --> Si + SiO2. Le contrôle du diamètre des nanocristaux de silicium permet de maîtriser la région spectrale de luminescence dans la région du visible.La première partie de ce travail de thèse vise à isoler un ou quelques nanocristaux de silicium. L'objectif est de remonter à la largeur homogène de ces nano-objets. Dans un premier temps, une étude centrée sur le matériau SiOx est réalisée afin de réduire la densité surfacique de nanocristaux de silicium. Dans un deuxième temps, des moyens de lithographie ultime sont mis en oeuvre afin de réaliser des masques percés de trous de diamètres de l'ordre de la centaine de nanomètre. Des expériences de spectroscopie optique sont réalisées sur ces systèmes.La deuxième partie de ce travail vise à contrôler l'émission spontanée de lumière issue des nanocristaux de silicium. Ceci se fait en couplant les modes électroniques aux modes optiques confinés d'une microcavité optique. Le manuscrit détaille les moyens développés afin d'obtenir une microcavité optique dont les modes optiques puissent se coupler efficacement aux nanocristaux de silicium. Les propriétés optiques de ces systèmes sont finalement analysées. / This work concerns the implementation and analysis of optical properties of silicon nanocrystals. These nanoscaled objects have remarkable optical properties, especially in photoluminescence. The properties of quantum confinement that characterize them allow obtaining an intense luminescence signal in the visible range. Optoelectronic and photonic devices have been proposed based on silicon nanocrystals. The physical reasons of the strong luminescence signal, however, are still poorly understood. The silicon nanocrystals are prepared by evaporation. The preparation and thermal annealing of multilayers SiO/SiO2 leads to silicon nanocrystals with a well controlled average diameter. They are created during the demixing of the SiO layer by the reaction SiO ? Si + SiO2. The control the diameter of the silicon nanocrystals influences directly the spectral region of luminescence in the visible region.The aim of first part of this work is to isolate one or a few silicon nanocrystals. The intent is to trace the homogeneous width of these nano-objects. Initially, a study focusing on the SiOx material is conducted to reduce the surface density of silicon nanocrystals. In a second step, lithography is implemented to make masks with holes with diameters of about one hundred nanometers. Optical spectroscopy experiments were performed on these systems.The second part of this work aims controlling the spontaneous emission of light from silicon nanocrystals. This is done by coupling the electronic transmission to optical modes confined in an optical microcavity. The manuscript describes the methods developed to obtain an optical microcavity whose optical modes can be coupled effectively to the silicon nanocrystals. The optical properties of these systems are finally analyzed

Les mémoires à nanocristaux de silicium sont considérées comme l'une des solutions les plus intéressantes pour remplacer les grilles flottantes dans les mémoires Flash pour des applications de mémoires non-volatiles embarquées. Ces nanocristaux sont intéressants pour leur compatibilité avec les technologies de procédé CMOS, et la réduction des coûts de fabrication. De plus, la taille des nanocristaux garantie un faible couplage entre les cellules et la robustesse contre les effets de SILC. L'un des principaux challenges pour les mémoires embarquées dans des applications mobiles et sans contact est l'amélioration de la consommation d'énergie afin de réduire les contraintes de design de cellules. Dans cette étude, nous présentons l'état de l'art des mémoires Flash à grille flottante et à nanocristaux de silicium. Sur ce dernier type de mémoire une optimisation des principaux paramètres technologiques a été effectuée pour permettre l'obtention d'une fenêtre de programmation compatible avec les applications à faible consommation d'énergie. L'étude s'attache à l'optimisation de la fiabilité de la cellule à nanocristaux de silicium. On présente pour la première fois une cellule fonctionnelle après un million de cycles d'écriture et effacement dans une large gamme de températures [-40°C;150°C], et qui est capable de retenir l'information pendant dix ans à 150°C. Enfin, une analyse de la consommation de courant et d'énergie durant la programmation montre l'adaptabilité de la cellule pour des applications à faible consommation. Toutes les données expérimentales ont été comparées avec les résultats d'une cellule standard à grille flottante pour montrer les améliorations apportées. / The silicon nanocrystal memories are one of the most attractive solutions to replace the Flash floating gate for nonvolatile memory embedded applications, especially for their high compatibility with CMOS process and the lower manufacturing cost. Moreover, the nanocrystal size guarantees a weak device-to-device coupling in an array configuration and, in addition, for this technology it has been shown the robustness against SILC. One of the main challenges for embedded memories in portable and contactless applications is to improve the energy consumption in order to reduce the design constraints. Today the application request is to use the Flash memories with both low voltage biases and fast programming operation. In this study, we present the state of the art of Flash floating gate memory cell and silicon nanocrystal memories. Concerning this latter device, we studied the effect of main technological parameters in order to optimize the cell performance. The aim was to achieve a satisfactory programming window for low energy applications. Furthermore, the silicon nanocrystal cell reliability has been investigated. We present for the first time a silicon nanocrystal memory cell with a good functioning after one million write/erase cycles, working on a wide range of temperature [-40°C; 150°C]. Moreover, ten years data retention at 150°C is extrapolated. Finally, the analysis concerning the current and energy consumption during the programming operation shows the opportunity to use the silicon nanocrystal cell for low power applications. All the experimental data have been compared with the results achieved on Flash floating gate memory, to show the performance improvement.