Transition from monolayer-thick 2D to 3D nano-clusters on α-Al 2 O 3 (0001)
Résumé
This paper reports on the long-standing puzzle of the atomic structure of the Ag/α-Al 2 O 3 (0001) interface by combining x-ray absorption spectroscopy, to determine Ag local environment [i.e. average Ag-Ag (d Ag−Ag) and AgO (d Ag−O) interatomic distances and Ag coordination numbers (CN)], and numerical simulations on nanometric-sized particles. The experimental key was the capability of a structural study of clusters involving only a few atoms. The concomitant decrease of d Ag−Ag and CN with decreasing cluster size provides unambiguous ngerprints for the dimensionality of the Ag clusters in the subnanometric regime leading to a series of unexpected results regarding the sizedependent interface structures. At low coverage, Ag atoms sit on surface Al sites to form buckled monolayer-thick islands associated with a Ag-Ag distance (2.75 Å) which ts the alumina lattice. Upon increasing Ag coverage, as 3D clusters appear, the Ag interface atoms tends to leave Al sites to sit atop O atoms as d Ag−Ag increases. The then highlighted size-dependent evolution, is built on structural models which seemed so far contradictory in a static vision of the interface. Theory generalizes the case as it predicts the existence of alumina-supported 2D clusters of Pd and Pt at small coverage and a similar 2D-3D transition upon increasing the size. The structural transformation from 2D Ag clusters to macroscopic 3D islands is accompanied by a noticeable reduction of adhesion energy at Ag/α-Al 2 O 3 (0001) interface.
Domaines
Physique [physics]Origine | Fichiers produits par l'(les) auteur(s) |
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