The semiconducting silicides offer significant potential for use in optoelectronic devices. Full implementation of the materials, however, requires the ability to tailor the energy gap and band structure to permit the synthesis of heterojunctions. One promising approach is to alloy the silicides with Ge. As part of an investigation into the synthesis of semiconducting silicide heterostructures, a series of β-Fe(Si1−xGex)2 epilayer samples, with nominal alloy content in the range 0 < x < 0.15, have been prepared by molecular beam epitaxy on Si(100). I present results of the epitaxial and crystalline quality of the films, as determined by reflection high-energy electron diffraction, Rutherford backscattering spectroscopy, and double crystal x-ray diffraction, and of the band gap dependence on the alloy composition, as determined by Fourier transform infrared spectroscopy. A reduction in band gap was observed with increasing Ge content, in agreement with previous theoretical predictions. However Ge segregation was also observed in β-Fe(Si1−xGex)2 epilayers when x > 0.04. Osmium silicide films have been grown by molecular beam epitaxy on Si(100). The silicides have been grown using e-beam evaporation sources for both Os and Si onto Si(100) substrates at varying growth rates and temperatures ranging from 600-700ºC. The resulting films have been analyzed using reflection high-energy electron diffraction, Raman spectroscopy, reflectivity measurements, in-plane and out of plane X-ray diffraction and temperature dependent magnetotransport. A change in crystalline quality is observed with an increase in Si overpressure. For a lower silicon to osmium flux ration (JSi/JOs=1.5) both OsSi2 and Os2Si3 occur, whereas with a much larger Si overpressure (JSi/JOs>4), crystalline quality is greatly increased and only a single phase, Os2Si3, is present. The out-of-plane X-ray diffraction data show that the film grows along its [4 0 2] direction, with a good crystal quality as evidenced by the small FWHM in the rocking curve. The in-plane X-ray diffraction data show growth twins with perpendicular orientation to each other.

Le Silicium est le deuxième élément le plus abondant dans la croûte terrestre après l’oxygène. Il est produit par voie métallurgique dans un four à arc électrique, le quartz est réduit en présence de réducteurs (charbon de bois, houille et coke de pétrole). Le silicium métallurgique est principalement utilisé dans la métallurgie comme élément d’alliage, dans la chimie et l’industrie solaire. Le prix du Silicium est fonction de sa pureté. Les travaux de cette thèse se divisent en deux parties l’utilisation du Silicium Métallurgique (99% Si) pour le stockage de l’hydrogène, et la photoluminescence du ferrosilicium (disiliciure de fer) de qualité métallurgique. Des substrats de silicium métallurgique ont été soumis à une anodisation électrochimique dans une solution à base d’acide fluorhydrique. Le silicium poreux nanostructuré obtenu est légèrement différent du silicium poreux issu de substrat de silicium de qualité électronique de même résistivité. L’influence des principaux paramètres sur la génération de l’hydrogène : la porosité, la concentration, le volume et la température ont fait l’objet d’une étude détaillée. Le silicium poreux produit à partir de silicium métallurgique est un matériau de stockage d’hydrogène. Des substrats de disiliciure de fer de qualité métallurgique ont été soumis à une anodisation électrochimique. Le composé obtenu est du disiliciure de fer nanostructuré avec du silicium résiduel, ce produit est recouvert de fluorosilicate de fer hexahydraté qui a la particularité d’être luminescent. Il s’agit à ce jour de la première anodisation du disiliciure de fer, un mécanisme de gravure a été proposé et l’influence des principaux paramètres d’anodisation sur les propriétés de photoluminescence a été évaluée. / Silicon is the second most abundant element in the Earth crust after oxygen. Its use in metallurgy, building and electronic industry requires a huge fabrication level. Depending on the contamination level allowed, the price of this material varies in the orders of magnitude. This thesis focuses on the use of dirtiest metallurgical grade silicon and iron disilicide substrates for hydrogen storage and photoluminescence applications. The initial substrates were subjected to electrochemical etching in hydrofluoric acid-containing solutions. Anodization of metallurgical grade silicon substrate produces nanostructured porous silicon with somewhat shifted parameters (comparing with electronic grade porous silicon with the same resistivity), as it was studied in this thesis in details. It was shown, that metallurgical grade porous silicon can be applied as hydrogen storage material. Hydrogen generation is studied here based on the influences of some technically critical parameters: porosity, alkali concentration, volume and temperature. Electrochemical treatment of metallurgical grade iron disilicide substrates produces luminescent iron fluorosilicate hexahydrate, covering the residual nanostructured iron disilicide/silicon. Here, the influence of anodization parameters on photoluminescent properties is studied. Also, etching mechanism is proposed as for the new material never anodized.