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International audience; Structural investigations of the (2-10) and (100) surfaces of Al5Co2 using experimental ultrahigh vacuum techniques and ab initio computational methods are presented in this work. Both surfaces are identified and show bulk terminations where only specific atoms remain. These atoms can be seen as truncated parts of chemically bonded atomic motifs which have been identified in the bulk in a previous work [M. Meier et al., Phys. Rev. B 91,085414 (2015)]. Whereas the (2-10) surface presents a single termination, the structure of the (100) topmost layers is found to be highly dependent on the preparation conditions, especially on the annealing temperature. This behavior, also observed for the (001) surface studied previously, can be partly explained when considering the bonding strength of the truncated motif parts with the subsurface

International audience; We report the formation of an ordered C60 monolayer on the Al9Co2(001) surface using scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), x-ray and ultraviolet photoelectron spectroscopy (XPS/UPS), and ab initio calculations. Dosing fullerenes at 300 K results in a disordered overlayer. However, the adsorption of C 60 with the sample held between 573–673 K leads to a [4, −2|1,3] phase. The growth of C60 proceeds with the formation of two domains which are mirror symmetric with respect to the [100] direction. Within each domain, the superstructure unit cell contains six molecules and this implies an area per fullerene equal to 91 A^2. The molecules exhibit two types of contrast (bright and dim) which are bias dependent. The adsorption energies and preferred molecular configuration at several possible adsorption sites have been determined theoretically. These calculations lead to a possible scheme describing the configuration of each C60 in the observed superstructure. Several defects (vacancies, protrusions,. . .) and domain boundaries observed in the film are also discussed. If the sample temperature is higher than 693 K when dosing, impinging C60 molecules dissociate at the surface, hence leading to the formation of a carbide film as observed by STM and LEED measurements. The formation of Al4C3 domains and the molecular dissociation are confirmed by XPS/UPS measurements acquired at different stages of the experiment. The cluster substructure present at the Al9Co2(001) surface dictates the carbide domain orientations.

International audience; The Al5Co2 crystal is a complex intermetallic compound, whose structure can be described by a stacking of chemically bonded atomic motifs. It is a potentially new catalytic material for heterogeneous hydrogenation. A single crystal of this phase has been grown by the Czochralski technique in order to study the influence of the three-dimensional bulk substructure on the two-dimensional surface using both experimental ultrahigh vacuum surface techniques and ab initio methods based on the density functional theory. Some bulk properties are first presented, focusing on chemical bond strengths, the determination of the Al and Co chemical potentials in Al5Co2 , the vibrational properties, and the specific heat. Then, the combination of experimental and computational approaches allows the identification of the surface structure, which was found to depend on the surface preparation conditions. In all cases, the surface terminates at specific bulk layers (Al-rich puckered layers) where various fractions of specific sets of Al atoms are missing, identified as Al3 atoms left at the surface resulting from cluster truncation. Finally, electron density of states calculations and spectroscopic measurements were compared and indicate a strong sp-d hybridization of the topmost pure Al layer with subsurface Co atoms. This could influence the surface reactivity and the catalytic performances of this material.

International audience; Complex metallic alloys having isolated transition-metal elements in the surface layer have been reported to work well as selective hydrogenation catalysts. We report an experimental determination of the surface structure of one such compound Al13Fe4(010). The structure was determined using low-energy electron diffraction. The best-fit structure terminates in a layer similar to the puckered bulk layer but lacking some of the Al and Fe atoms. Protruding Fe atoms are located in the middle of adjacent pentagonal Al formations, connected to each other by Al " glue " atoms. The top interlayer spacing is compressed relative to the bulk with oscillating relaxations observed for subsequent layers at the surface.

International audience; We have investigated the structure of the Al13Fe4(010) surface using both experimental and ab initio computational methods. The results indicate that the topmost surface layers correspond to incomplete puckered (P) planes present in the bulk crystal structure. The main building block of the corrugated termination consists of two adjacent pentagons of Al atoms, each centered by a protruding Fe atom. These motifs are interconnected via additional Al atoms referred to as "glue" atoms which partially desorb above 873 K. The surface structure of lower atomic density compared to the bulk P plane is explained by a strong Fe-Al-Fe covalent polar interaction that preserves intact clusters at the surface. The proposed surface model with identified Fe-containing atomic ensembles could explain the Al13Fe4 catalytic properties recently reported in line with the site-isolation concept [M. Armbrüster et al., Nat. Mater. 11, 690 (2012)].

International audience; The growth and stability of Bi thin films on the Al13Co4(100) surface has been investigated from the submonolayer to high-coverage regime by scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) for temperatures ranging from 57 to 633 K. Initially, Bi adsorption leads to the formation of a pseudomorphic monolayer, followed by the growth of islands of different heights with increasing coverage. The in-plane structure, island height, and island morphology indicate that these islands adopt either a pseudocubic (110) or hexagonal (111) orientation normal to the surface. The (110)-oriented islands correspond to bilayer stacking (either two or four monolayers in height) while the (111)-oriented islands correspond to either three- or four-layer stacking. The in-plane orientation of (110) islands with respect to the substrate is random, while (111) islands adopt one of four possible orientations. In addition, the (111) islands show a moiré structure. The fact that Bi islands grow with either (110) or (111) orientation simultaneously on the same substrate relates to a subtle energy balance between both orientations according to ab initio calculations, allowing both structures to coexist. The island density dependence versus both deposition temperature and flux, their most frequent structure type, reshaping effects, and chemical reactivity of the different allotropes are also discussed in this paper.

International audience; In a combined scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and density functional theory (DFT) study of the surface of Al13Co4(100), all techniques have found that after annealing to 1165 K, the surface structure is consistent with a dense Al-rich plane with surface Co atom depletion. Various structure models were considered, and in the LEED study, the best agreement was found with a model that consists of Al-rich terminating planes with no Co atoms, and otherwise a structure similar to the bulk puckered layers. This structure was also found to be stable in the DFT study. The best-fit structural parameters are presented for the two domains of this structure, which contain bipentagons that can be related to the pentagonal bipyramidal structures in the bulk, plus additional glue atoms between them. These domains are not strictly related to each other by symmetry, as they have different surface relaxations. The STM study found significant differences in the surfaces of samples grown by different methods and is able to explain a different interpretation made in an earlier study.

International audience; We present a detailed study of the (110) surface of the γ-Al4Cu9 crystal using both experimental methods and first-principles calculations based on density-functional theory. Our experimental approach, using low-energy electron diffraction, scanning tunneling microscopy (STM) images, and x-ray photoelectron spectroscopy highlights the presence of two types of surface terminations. Combining experimental results and simulations provides many arguments to match the two observed surfaces with the two puckered terminations built from bulk truncation: (i) calculations show that these two puckered terminations present lower surface energies compared to another conceivable flat termination obtained also from bulk truncation, (ii) step height measurements are consistent with calculated interlayer spacings and (iii) simulated STM images are in reasonable agreement with the experimental ones and mirror the experimental voltage dependence.

The atomic and electronic structures of the (010) surface of the T-Al-3(Mn,Pd) complex metallic alloy is investigated by means of low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), x-ray and ultraviolet photoelectron spectroscopy (XPS and UPS), x-ray photoelectron diffraction (XPD), and ab initio calculations. While structural imperfections are observed at the surface and out of the various possible terminations, the puckered P2 layer is identified as the only surface termination, thus pointing out the existence of a well-defined minimum in the surface energy landscape. The measured step heights correspond to distances between identical planes along the [010] direction in the bulk model, i.e., b/2. A bias dependency of the STM topography is found. The XPD and LEED patterns confirm the pseudotenfold symmetry of the sample. XPS and UPS show a more metallic signature of the T phase compared to Al-based quasicrystalline phases.

International audience; We present a detailed study of the (100) surface of the orthorhombic Al13Co4 crystal using both experimental and ab initio computational methods. This complex metallic alloy is an approximant of the decagonal Al-Ni-Co quasicrystalline phase. After sputter-annealing preparation of the surface at 1073 K, the low-energy electron diffraction pattern recorded exhibits a pseudotenfold symmetry with lattice parameters consistent with those of the bulk model. At this stage, scanning tunneling microscopy (STM) measurements reveal two different types of surface terminations. A comparison between these two surface structures and the bulk planes indicate that the terminations correspond either to an incomplete puckered layer (P) or to an incomplete flat layer (F). At 1173 K, the majority of the surface consists of P layer terminations. STM images calculated from our proposed surface model are in good agreement with experimental images. X-ray photoelectron diffraction patterns and single scattering cluster calculations further confirm that the local atomic arrangements present in the bulk model are preserved within the near-surface region.