Coverage-dependent structural phase transformations in the adsorption of pentacene on an aperiodically modulated Cu film.

Surface ordering of pentacene molecules adsorbed on an aperiodic Cu surface has been studied with density functional theory (DFT) and scanning tunnelling microscopy as a function of coverage. Below 0.73 ML (5.3 × 1013 molecules cm-2), the adsorbate structure is row-like with the molecular axes aligned with the rows in the Cu structure. Between this coverage and 1 ML (7.3 × 1013 molecules cm-2), a structural phase with a checkerboard structure is seen. At this coverage region, the molecules are very close to each other which leads to unusual bending. At higher coverages, a further phase transition to a high-density row structure is seen for most of the film. DFT with van der Waals functionals is employed to study how the molecule-molecule and molecule-surface interactions evolve as a function of coverage.

Templated quasicrystalline molecular ordering.

Quasicrystals are materials with long-range ordering but no periodicity. We report scanning tunneling microscopy (STM) observations of quasicrystalline molecular layers on 5-fold quasicrystal surfaces. The molecules adopt positions and orientations on the surface consistent with the quasicrystalline ordering of the substrate. Carbon-60 adsorbs atop sufficiently separated Fe atoms on icosahedral Al-Cu-Fe to form a unique quasicrystalline lattice, whereas further C60 molecules decorate remaining surface Fe atoms in a quasi-degenerate fashion. Pentacene (Pn) adsorbs at 10-fold symmetric points around surface-bisected rhombic triacontahedral clusters in icosahedral Ag-In-Yb. These systems constitute the first demonstrations of quasicrystalline molecular ordering on a template.

Crystalline and quasicrystalline allotropes of Pb formed on the fivefold surface of icosahedral Ag-In-Yb.

Crystalline and quasicrystalline allotropes of Pb are formed by evaporation on the fivefold surface of the icosahedral (i) Ag-In-Yb quasicrystal under ultra-high vacuum. Lead grows in three dimensional quasicrystalline order and subsequently forms fivefold-twinned islands with the fcc(111) surface orientation atop of the quasicrystalline Pb. The islands exhibit specific heights (magic heights), possibly due to the confinement of electrons in the islands. We also study the adsorption behavior of C60 on the two allotropes of Pb. Scanning tunneling microcopy reveals that a high corrugation of the quasicrystalline Pb limits the diffusion of the C60 molecules and thus produces a disordered film, similar to adsorption behavior of the same molecules on the clean substrate surface. However, the sticking coefficient of C60 molecules atop the Pb islands approaches zero, regardless of the overall C60 coverage.

The surface science of quasicrystals.

The surfaces of quasicrystals have been extensively studied since about 1990. In this paper we review work on the structure and morphology of clean surfaces, and their electronic and phonon structure. We also describe progress in adsorption and epitaxy studies. The paper is illustrated throughout with examples from the literature. We offer some reflections on the wider impact of this body of work and anticipate areas for future development.

Templated three-dimensional growth of quasicrystalline lead.

Quasicrystals, materials with aperiodic long-range order, have been found in intermetallics, soft materials such as colloids and supermolecules, and also in two-dimensional monolayer films. Here we present the first example of three-dimensional growth of a single-element quasicrystalline film. Using a hitherto unexplored template, the icosahedral Ag-In-Yb quasicrystal, and various experimental techniques combined with theoretical calculations of adsorption energies, we find that lead atoms deposited on the surface occupy the positions of atoms in the rhombic triacontahedral cluster, the building block of the substrate, and thus grow in layers with different heights and adsorption energies. We show that the adlayer-adlayer interaction is crucial for stabilizing this epitaxial quasicrystalline structure. The finding opens an avenue for further investigation of the impact of the aperiodic atomic order over periodic order on the physical and chemical properties of materials.

The memory of surfaces: epitaxial growth on quasi-crystals.

If crystal structures can be viewed as repositories of information, then crystal surfaces offer a pathway by which this information can be used to grow new structures through the process of epitaxy. The information transfer process is one of self-organization, and the kinetic and energetic factors influencing this are complex. They include the relative strengths of the adsorbate-adsorbate and adsorbate-substrate interactions, the flux of incoming species and the temperature of the system. In this brief review, we explore how the interplay of these factors influences the degree to which the epitaxial structures retain the 'memory' of the template, illustrating the discussion with examples from epitaxy on quasi-crystal surfaces.

Epitaxial Bi allotropes on quasicrystal surfaces as templates for adsorption of pentacene and fullerene.

The growth of Bi on surfaces of Al-based quasicrystals yields a quasicrystalline monolayer which is followed by the formation of crystalline islands of various forms depending on coverage, deposition flux and substrate temperature. We have used the Bi thin films consisting of both crystalline and quasicrystalline allotropes as substrates to study the deposition of C(60) and pentacene molecules. Scanning tunneling microscopy (STM) reveals substrate-dependent differences in molecular adsorption.

The various modes of growth of metals on quasicrystals.

Quasicrystals are fascinating intermetallic compounds composed of two or more elements. They differ from conventional crystals in that they possess long-range order, but no translational symmetry--that is, they are aperiodic. Much effort has been expended on identifying routes towards exploiting and exploring the properties of such systems due to their aperiodic nature. One such route is concerned with the deposition of thin films, particularly of metals, to investigate how their growth progresses in this inherently frustrated scenario. This topical review will examine the various epitaxial relationships observed in quasicrystal research with particular emphasis on single-element metallic films deposited under ultrahigh-vacuum conditions.

Structure and reactivity of Bi allotropes on the fivefold icosahedral Al-Pd-Mn quasicrystal surface.

The growth of Bi on a pseudomorphic Bi monolayer on the fivefold surface of the icosahedral Al-Pd-Mn quasicrystal has been investigated using low energy electron diffraction and scanning tunnelling microscopy. Initially randomly oriented pseudocubic islands are formed with a preference for an even number of layers. Subsequently a morphological transformation takes place to hexagonal Bi islands, which align along high symmetry directions of the substrate. The Bi flux is found to have a strong effect on which island structure is preferred. When C(60) is adsorbed on the three different allotropes of Bi present in this system, hexagonal C(60) islands are formed in each case. On the pseudocubic and hexagonal islands, the C(60) islands are aligned with the substrate. We discuss the energetic, kinetic and geometrical factors which influence the morphological transformation referred to above.

Surface geometry of C(60) on Ag(111).

The geometry of adsorbed C(60) influences its collective properties. We report the first dynamical low-energy electron diffraction study to determine the geometry of a C(60) monolayer, Ag(111)-(2 square root of 3 x 2 square root of 3) 30 degrees -C(60), and related density functional theory calculations. The stable monolayer has C(60) molecules in vacancies that result from the displacement of surface atoms. C(60) bonds with hexagons down, with their mirror planes parallel to that of the substrate. The results indicate that vacancy structures are the rule rather than the exception for C(60) monolayers on close-packed metal surfaces.

Pseudomorphic growth of a single element quasiperiodic ultrathin film on a quasicrystal substrate.

An ultrathin film with a periodic interlayer spacing was grown by the deposition of Cu atoms on the fivefold surface of the icosahedral Al70Pd21Mn9 quasicrystal. For coverages from 5 to 25 monolayers, a distinctive quasiperiodic low-energy electron diffraction pattern is observed. Scanning tunneling microscopy images show that the in-plane structure comprises rows having separations of S=4.5+/-0.2 A and L=7.3+/-0.3 A, whose ratio equals tau=1.618... within experimental error. The sequences of such row separations form segments of terms of the Fibonacci sequence, indicative of the formation of a pseudomorphic Cu film.