, dont la structure est décrite par une maille géante contenant de quelques dizaines à plusieurs milliers d'atomes, généralement regroupés en agrégats de symétrie élevée. Les quasicristaux représentent le cas limite, avec la perte de la périodicité de translation et l'apparition de symétries de rotation "interdites, Les intermétalliques complexes sont des composés définis, formés à partir de plusieurs éléments métalliques

, Les arrangements quasipériodiques ont été découverts dans un grand nombre de composés intermétalliques (> 100

, Des oxydes bidimensionnels présentant un arrangement quasipériodique ont également été observés

, Une approche théorique a montré que les arrangements quasicristallins peuvent émerger de simulations de dynamique moléculaire à partir d'un système de particules à un composant, interagissant via un potentiel de paire isotrope

, Une exploration de l'espace des paramètres a permis d'identifier des composés voisins des phases quasicristallines, comme les clathrates et d'autres phases complexes dont la structure est également décrite par un empilement d'agrégats atomiques de haute symmétrie

, Les propriétés de surface de ces phases complexes sont particulièrement intéressantes. Plusieurs phases quasicristallines ou approximantes présentent des surfaces caractérisées par une grande dureté et un coefficient de frottement faible

, Plus récemment, plusieurs phases complexes ont montré de bonnes performances en catalyse, qu'elles soient utilisées comme telles ou traitées par une attaque chimique, La résistance à l'oxydation de ces matériaux est également citée

, Une autre approche pourrait reposer sur la grande variété de structures atomiques et électroniques des intermétalliques complexes. C'est ce qui a motivé la première partie de cette thèse, c'est-à-dire l'étude des surfaces de bas indice du clathrate Ba-Au-Ge. La structure atomique de ce composé est formée de cages, sa structure électronique peut être contrôlée par sa composition, Le design de surfaces présentant des propriétés spécifiques est un objectif général en nanosciences

, Dans une seconde partie, notre travail s'est orienté vers les propriétés de surface des intermétalliques complexes, en particulier les propriétés de mouillage intrinsèque, Nous nous sommes intéressés à plusieurs intermétalliques à base d'aluminium, un des objectifs étant de discuter le rôle de la com

. Le-clathtrate-ba-au, La possibilité de contrôler sa structure électronique en jouant sur sa composition chimique exacte est également séduisante du point de vue de ses propriétés de surfaces, que l'on peut espérer contrôler via ce levier, Ge est un matériau présentant des propriétés thermoélectriques intéressantes, p.et

. Le-clathrate-ba-au, maille cubique contenant 54 atomes, paramètre de maille égal à 10.7987 Å [18]). Elle peut être décrite par un empilement de deux types de cages: des tetrakaidécaèdres [(Ge,Au) 24 ]) et des dodécaèdres [Ge 20 ], ces derniers étant organisés selon un arrangement cubique centré. Ces cages contiennent chacune un atome de, Ge La structure de ce cristal est illustrée sur la figure 7.1 (groupe d'espace P m ¯ 3n

, Au x Ge 46?x avec x = 5.33 a mis en évidence le caractère covalent des liaisons Ge-Ge et Ge-Au. Une liaison à caractère covalent a également été identifiée entre l'atome de

, Le monocristal que nous avons utilisé a pour composition Ba 8 Au 5.25 Ge 40.75 (croissance réalisée par nos collaborateurs allemands à Dresde et à Francfort sur le Main)

. Expérimentalement, Dans les deux cas, ces mesures sont cohérentes avec le paramètre de maille du crystal. La surface est formée de larges terrasses séparées par des marches d, aucune reconstruction n'est observée par diffraction d'électrons lents

Å. , mettant en évidence une sélection de terminaison à la surface. FIGURE 7.2: Cliché de diffraction lents des surfaces Ba 8 Au 5

. La-fonctionnelle-de-la-densité.-l'approche-décrite-dans-la-ref, Pour chaque orientation, plusieurs modèles de surface ont été élaborés, leur énergie de surface déterminée en fonction du potentiel chimique de deux élements (ici, Au et Ba). Les modèles sont construits de telle sorte à minimiser la corrugation de surface (ce qui requiert généralement de "briser" les cages à la surface)

. Au-x-ge, , vol.46

, Le type de cage qui protrude dépend de l'orientation de la surface: dodécaèdres ou tétrakaidécaèdres pour les orientations (110) et (100), respectivement. FIGURE 7.3: Modèles de surface stable observée expérimentalent pour les surfaces (gauche) Ba 8 Au

, Résumé en français

, Les images de microscopie à effet tunnel (STM pour Scanning Tuneling Microscopy) simulées à partir des modèles précédents sont en bon accord avec les images expérimentales (Fig. 7.4), ce qui étaye les conclusions des calculs d'énergie de surface. FIGURE 7.4: Images STM expérimentales et simulées des surfaces (100) et (110) du composé

, de liaisons pendantes, liées aux atomes de germanium sp 2 à la surface. Les liaisons pendantes ont un caractère déstabilisant, et sont à l'origine de reconstructions de surface de nombreux semi-conducteurs

. Ici, aucune reconstruction n'est observée, puisque les atomes de barium, qui protrudent à la surface, experiments FIGURE C.1: SEM micrographs showing Pb droplets on

, Co 2 (001) for a tilt value equal to 60°. Some droplets are curve-fitted (black circles) for contact angle measurements, Al, vol.5

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, Cette thèse a pour objectif, à la fois la détermination de la structure et des propriétés électroniques d'une surface d'un CMA de la famille des clathrates intermétalliques, et des propriétés de mouillage intrinsèques de plusieurs CMAs à base d'aluminium. Dans une première partie, nous nous sommes intéressés aux surfaces de bas indice (100) et (110) du clathrate Ba 8 Au 5.25 Ge 40.75 . Leurs structures atomiques et électroniques ont été déterminées en combinant des expériences de sciences des surfaces et des calculs basés sur la théorie de la fonctionnelle de la densité. La structure tridimensionnelle de Ba 8 Au 5.25 Ge 40.75 , formée d'un réseau de deux types de cages (structure hôte) à base de germanium et d'or, qui emprisonnent les atomes de Ba, induit une nanostructuration de la surface contrôlée par son orientation, puisque le type de cages préservées à la surface diffère pour les surfaces (100) et (110), Propriétés de surface des intermétalliques complexes à l'échelle du nanomètre: du fondamental aux applications Les alliages métalliques complexes (CMAs) sont des composés intermétalliques dont la structure cristallographique diffère de celle des alliages conventionnels par le nombre conséquent d'atomes dans la maille (jusqu'à plusieurs milliers d'atomes), généralement arrangés sous forme d'agrégats atomiques de haute symétrie

, Mots-clés: physique des surfaces, alliages métalliques complexes, mouillage, clathrates, nanoscience, DFT (théorie de la fonctionnelle de la densité) Surface properties of complex intermetallics at the nanoscale: from fundamentals to applications

, Experimental results show no evidence for surface segregation and LEED patterns are consistent with (1x1) bulk terminations with no surface reconstruction. The interplay between the 3D nano-caged structure and 2D surfaces is investigated. We demonstrate that the surface structures of the two surfaces considered preserve the bulk structure cages in addition to an ordered arrangement of surface Ba atoms. The two surfaces are formed by a breakage of highly directional covalent bonds present within the framework, hence leading to destabilizing dangling bonds. Ab initio calculations show that the surface structure is stabilized through electron charge transfer from protruding Ba to surface Ge and Au atoms, saturating the dangling bonds. This charge-balance mechanism lifts the possible surface reconstruction envisaged. We reveal how the surface nanostructuration is surface orientation dependent. The results indicate that the surface electronic structure of BaAuGe(110) is impacted by the Au surface concentration. The surface models for BaAuGe(100) and BaAuGe(110) present a metallic character and low work function values, useful for further applications. Such structurally complex surfaces may also be used as templates for novel nanoscale architectures. Further in this work, we also applied the state-of-the-art surface science techniques to investigate the wetting properties of Al-based CMAs, Ge 40.75 type-I clathrate is one such cage compound, whose bulk properties have been (and still are) extensively explored for thermoelectric applications. In fact, it is possible to tune the compound electronic structure by a fine control of its bulk composition

, Keywords: Surface physics, CMA (Complex Metallic Alloys), wettability, clathrates, nanoscience, DFT (Density Functional Theory