J. Ledieu

Surfaces of Al-based complex metallic alloys: atomic structure, thin film growth and reactivity

Abstract We present a review on recent work performed on periodic complex metallic alloy (CMA) surfaces. The electronic and crystallographic structures of clean pseudo-tenfold, pseudo-twofold, sixfold surfaces will be presented along with the recent findings on CMA of lower structural complexity, i.e. with a smaller unit cell. The use of CMA surfaces as templates for thin film growth and the formation of surface alloy will also be introduced. The reactivity of these complex surfaces and their impact in the field of heterogeneous catalysis will be discussed. Finally, common trends among these systems will be highlighted when possible and future challenges will be examined.

Quasicrystal surfaces: structure and potential as templates

We present a review of recent progress in determining the surface structure of quasicrystals, with emphasis on their connections to mathematical tiling models. The review focusses in particular on the five-fold surface of icosahedral Al-Pd-Mn and the ten-fold surface of decagonal Al-Ni-Co. We also assess their potential as templates for the formation of two-dimensional quasicrystalline overlayers with reference to recent investigations of atomic and molecular adsorption.

Tiling of the fivefold surface of Al70Pd21Mn9

The nature of the five-fold surface of Al(70)Pd(21)Mn(9) has been investigated using scanning tunneling microscopy. From high resolution images of the terraces, a tiling of the surface has been constructed using pentagonal prototiles. This tiling matches the bulk model of Boudard et. al. (J. Phys.: Cond. Matter 4, 10149, (1992)), which allows us to elucidate the atomic nature of the surface. Furthermore, it is consistent with a Penrose tiling T^*((P1)r) obtained from the geometric model based on the three-dimensional tiling T^*(2F). The results provide direct confirmation that the five-fold surface of i-Al-Pd-Mn is a termination of the bulk structure.

Pseudomorphic Starfish: Nucleation of Extrinsic Metal Atoms on a Quasicrystalline Substrate

Abstract Direct observation of extrinsic Al atoms on the fivefold surface of icosahedral Al–Cu–Fe indicates that they form pseudomorphic islands resembling starfish. The starfish occupy specific types of sites on the laterally-bulk-terminated quasicrystalline surface. We postulate that the nucleation event consists of a diffusing Al atom dropping into an empty site at the centre of a substrate pentagon. Growth consists of the addition of five Al atoms (nearly) in lattice sites. These 6-atom starfish do not grow laterally as coverage increases, leading to islands of uniform size, and to early roughening.

C60 adsorption on the quasicrystalline surface of Al70Pd21Mn9

Abstract Room temperature adsorption of C 60 on the flat quasicrystalline surface of Al 70 Pd 21 Mn 9 has been investigated using scanning tunnelling microscopy. A dispersed overlayer is formed at low coverage, with avoidance of step-edges. There is no evidence of island formation or clustering. As the coverage is increased, a higher density layer is formed with no evidence of the formation of hexagonal ordered adsorbate structures seen on other substrates. This is followed by the onset of second layer formation. A range of bonding sites for C 60 molecules is implied from measurements of apparent molecular heights and from thermal effects. Detailed analysis of the surface at a low coverage (∼0.065 ML) provides evidence of adsorbate local order, with Fibonacci ( τ -scaling) relationships between the C 60 molecules. Where this occurs, the preferred adsorption site is tentatively identified as the pentagonal hollow. These local correlations however are not found to extend over larger regions of the surface.

Self-assembly, structure, and electronic properties of a quasiperiodic lead monolayer

A quasiperiodic Pb monolayer has been formed on the fivefold surface of the Al-Pd-Mn quasicrystal. Growth of the monolayer proceeds via self-assembly of an interconnected network of pentagonal Pb stars, which are shown to be

Quasicrystal surfaces: potential as templates for molecular adsorption

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Adsorption of cobalt on the tenfold surface of d-Al72Ni11Co17 and on the fivefold surface of i-Al70Pd21Mn9

inflated compared to similar structural elements of the quasiperiodic substrate. Measurements of the electronic structure of the system using scanning tunneling spectroscopy and ultraviolet photoemission spectroscopy reveal that the Pb monolayer displays a pseudogap at the Fermi level which is directly related to its quasiperiodic structure.

The surface science of quasicrystals

Abstract We report on investigations of the potential for using quasicrystal surfaces as templates for molecular adsorption. The quasicrystalline surfaces of the i -Al–Pd–Mn and the d -Al–Ni–Co quasicrystals have been dosed with various molecules and the surface reactivity characterised by Fourier transform infrared spectroscopy (FTIR). The reflected signal intensities obtained are much weaker than those obtained from other crystals such as metals. Although both quasicrystals are Al-based their surface reactivities are seen to differ. For the Al–Pd–Mn surface, NO and HCOOH both dissociate at the surface and CO does not adsorb. CD 4 O adsorption leads to multilayers as in other crystals. C 6 H 6 molecules stick at low coverages and at low temperatures whilst not affecting the LEED pattern. For the Al–Ni–Co surface, CO molecules stick via activated adsorption to atop sites with vibrational frequencies very similar to CO adsorption on Ni. HCOOH forms multilayers at low temperatures which is reduced to a monolayer upon heating to 173 K; changes in the symmetry of the bonding are observed, which is also seen for HCOOH on Ni surfaces. NO and CD 4 O showed no characteristic spectra, which may be due to dissociation or a very low sticking probability. We summarise these observations and draw some conclusions as to the most favourable route for molecular overlayer formation.

SCALING PARAMETERS FOR GOLD AND COPPER CLUSTER GROWTH ON AN ALUMINA SINGLE CRYSTAL SURFACE

The adsorption behaviour of Co on the tenfold surface of d-Al72Ni11Co17 and on the fivefold surface of i-Al70Pd21Mn9 has been studied using scanning tunnelling microscopy (STM), Auger electron spectroscopy (AES) and low-energy electron diffraction (LEED). The analysis of a distinctive quasiperiodic LEED pattern for coverages from 3–30 ML of Co on d-Al72Ni11Co17 suggests that the Co forms in a pseudomorphic row structure composed of domains of Fibonacci spaced rows having a periodic lattice parameter along the rows of 2.5 ± 0.1 Å. The same structure, though less well-ordered and with a larger lattice parameter, is formed on the fivefold surface of i-Al70Pd21Mn9.