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. Ii, Étude vibrationnelle des particules de SiP 2 À notre connaissance, aucune étude n'a concerné, à ce jour, la formation de nanoparticules de SiP 2, Seules des études structurales

. Figure-v, 15: a) Spectres FTIR d'un film mince de SiO 1,5 recuit à 1100?C pendant 5

. De, SiO 2 sans phosphore (en noir) et contenant 10 at.% de phosphore (en rouge), d'un film mince de SiO 1,5 contenant 10 at.% de phosphore sans barrière de SiO 2 (en vert) et spectre FTIR calculé pour une structure de

, SiP 2 orthorhombique (en magenta). b) Zoom des spectres dans la région où doit apparaitre la signature vibrationnelle de SiP 2

. De-la-même-manière-que-dans-le-chapitre and . Iii, La figure V.15 a) présente les spectres d'absorption infrarouge de films minces de SiO 1,5 recuits à 1100?C avec une barrière de SiO 2 sans phosphore (en noir) et contenant 10 at.% de phosphore (en rouge), sans barrière de SiO 2 contenant 10 at.% de phosphore (en vert) et le spectre calculé pour la phase orthorhombique (Pbam (55)) 3 de SiP 2 . La mise en place de la barrière de diffusion est très efficace et supprime totalement l'absorption due aux porteurs libres présents dans le substrat. Ainsi, en zoomant dans la région où il y a des contributions vibrationnelles (figure V.15 b)), les contributions des vibrations Si-O-Si sont observées avec l'élongation asymétrique en phase à 1080 cm -1 , le balancement à 460 cm -1 et l'élongation symétrique à 800 cm -1 . Les spectres avec ou sans phosphore ont exactement les mêmes signatures vibrationnelles, les dépôts ont été réalisés sur substrat de silicium recouvert par une couche barrière de silice de 5 nm afin de supprimer la diffusion du phosphore dans le substrat

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, Pour de faibles teneurs en phosphore, celle-ci augmente ce qui est interprété par une augmentation de la densité des nanocristaux et par un effet de passivation par le phosphore des états électroniques localisés à l'interface nanocristaux/matrice. Les mesures de photoluminescence à basse température ont permis de mettre en évidence un état électronique lié au phosphore situé à 0,6 eV sous la bande de conduction des nanocristaux de Si. Ce résultat montre qu'il est possible d'incorporer des atomes de phosphore électriquement actifs dans des nanocristaux de Si. Pour des teneurs en phosphore supérieures à 0,3 at.%, l'intensité de photoluminescence des nanocristaux de Si diminue puis disparaît totalement. Cela est lié d'une part à la formation de nanocristaux de Si de tailles supérieures au rayon de Bohr de l, Étude de la structure et des propriétés optiques de films minces de SiP et d'oxydes de silicium riches en phosphore Ce travail de thèse concerne l'étude des propriétés structurales et optiques de films minces de SiP et d'oxyde de silicium riches en phosphore. Dans les films de Si riches en phosphore recuits à 1100?C , la formation de cristallites de SiP coexistant avec des polycristaux de Si est observée

, Les spectroscopies associées à la microscopie électronique en transmission confirment la stoechiométrie du composé SiP 2

, Les propriétés vibrationnelles sont en excellent accord avec des calculs DFT pour l'alliage SiP 2

. Mots-clés, Couches minces, évaporation, oxyde de silicium, dopage phosphore, nanocristaux de silicium, alliages SiP x . Structural and optical properties of SiP and phosphorus rich silicon oxide thin films