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The unfilled skutterudite ${\mathrm{CoSb}}_{3}$ is a small-gap semiconductor which was predicted to be close to a strain-induced transition to a topological-insulator phase passing through a topological quantum critical point. As a starting point to strain measurements, the aim of this work is to characterize the electronic structure of as-grown samples. Two types of samples, one grown in Sb flux and the other by an inclined rotary Bridgman technique, are compared based on structural properties, resistivity, Hall effect, and magnetization. All samples appear metallic with small growth-dependent hole doping. Measurements of quantum oscillations in magnetization and angle-dependent electronic transport confirm the calculated band structure at ambient pressure. The Fermi surface consists of a single spherical sheet at the $\mathrm{\ensuremath{\Gamma}}$ point, and the purest samples grown by the Bridgman technique have a Fermi energy lying 25 meV below the valence-band edge. Band-structure calculations provide an accurate description of the experimental results. Hence, this compound is suitable for an investigation of topological states under strain.

Combining inelastic neutron and x-ray scattering with atomic scale simulation, we report on a comprehensive study of the lattice dynamics and its relationship with the low thermal conductivity of the o-${\mathrm{Al}}_{13}{\mathrm{Co}}_{4}$ phase, a periodic approximant (about 100 atoms per cell) to a decagonal quasicrystal. The obtained experimental data, phonon lifetimes, and temperature-independent lattice thermal conductivity can only be fully described by molecular dynamics simulations, using oscillating pair potential, when the disorder of 12 Al sites is properly taken into account. Our results pave the way for a detailed understanding of materials where structural complexity and local disorder are at play.

The intermetallic phase FeGa3 belongs to the rare examples of substances with transition metals where semiconducting behavior is found. The necessary electron count of 17 ve/fu can be formally derived from eight Fe-Ga and one Fe-Fe two-center-two-electron bond. The situation is reminiscent of the well-known Fe2(CO)9 scenario, where a direct Fe-Fe two-center-two-electron bond was shown to not be present. Fe-Fe interaction in FeGa3 and its substitution variants represents the crucial point for explanation of electronic, thermal transport, and optical properties of this material. Chemical bonding analysis in position space of FeGa3 and Fe2(CO)9 on the basis of the topology of the electron localizability indicator distribution, QTAIM atoms, two- and three-center delocalization indices, domain natural orbitals, IQA analysis, and an evaluation of the Fe-Fe dissociation energy yields a complete picture of the partially compensated Fe-Fe bond, which is nevertheless strong enough to be of decisive importance. Structural reinvestigation of differently synthesized single crystals leads to the composition Fe1+ xGa3 (0 ≤ x ≤ 0.018), where the additional Fe atoms are predicted from DFT/PBE calculations to yield a magnetic moment of about 2 μB/Fe2 atom and metallic in-gap states. Accompanying magnetization and ESR measurements are consistent with this picture.

The atomic structure of a 0.2 atom % Pt-doped complex metallic alloy, monoclinic Al13Fe4, was investigated using a single crystal prepared by the Czochralski method. High-angle annular dark-field scanning transmission electron microscopy showed that the Pt atoms were dispersed as single atoms and substituted at Fe sites in Al13Fe4. Single-crystal X-ray structural analysis revealed that the Pt atoms preferentially substitute at Fe(1). Unlike those that have been reported, Pt single atoms in the surface layers showed lower activity and selectivity than those of Al2Pt and bulk Pt for propyne hydrogenation, indicating that the active state of a given single-atom Pt site is strongly dominated by the bonding to surrounding Al atoms.

Sb-based compounds such as CoSb 3 and FeSb 2 are interesting materials for thermoelectric applications. Their single crystal growth can be achieved from high-temperature solutions that are strongly enriched in Sb. In Bridgman growth using closed ampoules, effective mixing of the solution is an important prerequisite in order to minimize the high risk of liquid inclusion formation. We have successfully grown inclusion-free single crystal of CoSb 3 and FeSb 2 by rotating the ampoule in a Bridgman-type crystal growth set-up being inclined by 75° with respect to the vector of gravity. Numerical modelling as well as experimental growth studies have demonstrated the strong influence of forced convection that is achieved by this modified directional solidification technique called Inclined Rotary Bridgman method.

Complex intermetallic compounds such as transition metal (TM) aluminides are promising alternatives to expensive Pd-based catalysts, in particular for the semi-hydrogenation of alkynes or alkadienes. Here, we compare the gas-phase butadiene hydrogenation performances of o-Al13Co4(100), m-Al13Fe4(010) and m-Al13Ru4(010) surfaces, whose bulk terminated structural models exhibit similar cluster-like arrangements. Moreover, the effect of the surface orientation is assessed through a comparison between o-Al13Co4(100) and o-Al13Co4(010). As a result, the following room-temperature activity order is determined: Al13Co4(100) < Al13Co4(010) < Al13Ru4(010) < Al13Fe4(010). Moreover, Al13Co4(010) is found to be the most active surface at 110°C, and even more selective to butene (100%) than previously investigated Al13Fe4(010). DFT calculations show that the activity and selectivity results can be rationalized through the determination of butadiene and butene adsorption energies; in contrast, hydrogen adsorption energies do not scale with the catalytic activities. Moreover, the calculation of projected densities of states provides an insight into the Al13TM4 surface electronic structure. Isolating the TM active centers within the Al matrix induces a narrowing of the TM d-band, which leads to the high catalytic performances of Al13TM4 compounds., Graphical abstract

Intermetallic compounds have proved to be interesting alternatives to heterogeneous catalysts prepared from pure noble metals or their alloys. As to study their intrinsic properties, to determine the crystalline structures of specific surfaces and finally to understand elementary processes of heterogeneous catalysis, single crystals of these intermetallics are needed. Inspired by the recent discovery of Ga–Ni catalysts for carbon dioxide reduction to methanol, we have grown for the first time cm3-size single crystals of trigonal Ga3Ni2. We report in detail on the synthesis and Czochralski growth from high-temperature solution using Ga as native solvent. Inclusion formation of Ga-rich fluid proved to be the most severe problem that was minimized by using an extremely low pulling rate down to 25 µm/h.

In order to obtain the local charge disturbance around substituted Ge atom in a prototype system of ferromagnetic quantum criticality, FeGa3−xGex, we have measured 69,71Ga Nuclear Quadrupole Resona...

Intermetallic compounds in the binary Ga-Pd system have proved to be superior as catalysts in the semi-hydrogenation of acetylene. Partial substitution of Ga by Sn even increases the activity. In order to study elementary processes of catalytic reactions, well-oriented surfaces of single-crystalline slaps are needed, i.e. single crystal growth is a prerequisite. For the first time, solid/liquid equilibria including the solid solutions Ga1−xSnxPd and Ga1−xSnxPd2 were studied. Based on these findings single crystal growth of the two solid solution series succeeded using the Czochralski method from (Ga,Sn)-rich solutions. Inclusion-free single crystals of a few cm3 in size could be obtained. Due to different crystal structures of the end members, Sn substitution in Ga1−xSnxPd is restricted to x ≈ 0.15 in the cubic phase. Although a complete solid solution range for Ga1−xSnxPd2 has been reported by Armbruster et al. (2018), mixed crystals of the 1:2 phase can be grown from a native ternary melt only up to approx. x = 0.54 due to missing solid/liquid equilibria at a higher ratio of Sn substitution for Ga.

Background In a routine handling of a catalyst material, exposure to air can usually not be avoided. For noble metal catalysts that are resistant to oxidation, this is not an issue, but becomes important for intermetallic catalysts composed of two or more non-noble chemical elements that possess much different standard enthalpies of the oxide formation. The element with higher affinity to oxygen concentrates on the surface in the oxide form, whereas the element with lower affinity sinks into the subsurface region. This changes the number of active sites and the catalytic performance of the catalyst. We have investigated the instability of the surface composition to oxidation of the Ga3Ni2 noble metal-free intermetallic compound, a new catalyst for the CO2 reduction to CO, CH4 and methanol. Methods The instability of the oxidized Ga3Ni2 surface composition to different heating–annealing conditions was studied by X-ray photoelectron spectroscopy (XPS), used to determine the elemental composition and the chemical bonding in the near-surface region. The dispersion of active sites available for the chemisorption of H2 and CO on the Ga3Ni2 catalyst surface was determined by H2 and CO temperature-programmed desorption. CO2 conversion experiments were performed by using the catalyst material reduced in hydrogen at temperatures of 300 and 600 °C. Results XPS study of the Ga3Ni2 surface subjected to different heating–annealing conditions has revealed that the concentration of Ga at the oxidized surface is strongly enhanced and the concentration of Ni is strongly depleted with respect to the values in the bulk. By annealing the surface at 600 °C in ultra-high vacuum, the oxides have evaporated and thermal diffusion of atoms near the surface has partially reconstructed the surface composition towards the energetically more favorable bulk value, whereas annealing at a lower temperature of 300 °C was ineffective to change the surface composition. Catalytic tests were in agreement with the XPS results, where an increased CO2 conversion for the catalyst reduced with hydrogen at a higher temperature followed an increased Ni/Ga surface concentration ratio. Conclusions The instability of the active surface chemical composition to oxidation in air must be taken into account when considering noble metal-free intermetallic catalysts as alternatives to the conventional catalysts based on noble metals. Ga3Ni2 and other Ga–Ni intermetallic compounds are good examples of binary intermetallic catalysts, whose catalytic performance is strongly affected by exposure to the air.

International audience; We report the adsorption of lead adatoms on the pseudo-10-fold Al13Fe4(0 1 0) surface using low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). For the submonolayer regime, Pb adatoms remain highly mobile across the surface at 300K. STM analysis indicates the formation of irregularly shaped islands of monoatomic height. The latter do not coalesce with increasing coverage. At 0.95 MLE coverage, the LEED patterns are consistent with a pseudomorphic growth of the adatoms. This is confirmed by STM measurements which reveal local motifs qualitatively similar to those observed on the clean Al13Fe4(0 1 0) surface, i.e. prior to dosing. Apart from the absence of plasmons, the XPS measurements of Pb 4f and Al 2s core levels are comparable to those observed for the Pb/Al(1 1 1) system.

The atomic structure of the Al13Ru4(010) approximant surface, investigated for annealing temperatures ranging from 873 K to 1143 K, can be described by pentagonal motifs and vacancies. It exhibits an atypical surface reconstruction which manifests itself in real space by well-separated stripes running about 10○ off the [001] direction. Their mutual ordering is drastically improving at high annealing temperature. This is simultaneously accompanied by a filling of the pentagonal hollow sites present in the stripes with atoms or groups of atoms. We provide evidence that these unidirectional features are of true surface origin. The bulk electronic density of states calculated within the density functional theory framework matches the experimental valence band spectra. In addition to step edges, molecular adsorption reveals that stripes are initially the most reactive sites, leading to anisotropic island growth.

The intermetallic semiconductor FeGa$_{3}$ acquires itinerant ferromagnetism upon electron doping by a partial replacement of Ga with Ge. We studied the electron spin resonance (ESR) of high-quality single crystals of FeGa$_{3-x}$Ge$_x$ for $x$ from 0 up to 0.162 where ferromagnetic order is observed. For $x = 0$ we observed a well-defined ESR signal, indicating the presence of pre-formed magnetic moments in the semiconducting phase. Upon Ge doping the occurrence of itinerant magnetism clearly affects the ESR properties below $\approx 40$~K whereas at higher temperatures an ESR signal as seen in FeGa$_{3}$ prevails independent on the Ge-content. The present results show that the ESR of FeGa$_{3-x}$Ge$_x$ is an appropriate and direct tool to investigate the evolution of 3d-based itinerant magnetism., Comment: 12 pages, 7 figures

The atomic structure and composition of a catalyst's surface have a major influence on its performance regarding activity and selectivity. In this respect, intermetallic compounds are promising future catalyst materials, as their surfaces exhibit small and well-defined ensembles of active metal atoms. In this study, the active adsorption sites of the 3-fold-symmetric surfaces of the PdGa interrnetallic compound were investigated in a combined experimental and computational approach using CO as a test molecule. The PdGa(111) and (-1-1-1) surfaces exhibit very similar electronic structures, but have Pd sites with very different, well-defined atomic coordination and separation. They thereby serve as prototypical model systems for studying ensemble effects on bimetallic catalytic surfaces. Scanning tunneling microscopy and Fourier transform infrared spectroscopy show that the CO adsorption on both surfaces is solely associated with the topmost Pd atoms and Ga acts only as an inactive spacer. The different local configurations of these Pd atoms dictate the CO adsorption sites as a function of coverage. The experimental results are corroborated by density functional theory and illustrate the site separation and ensemble effects for molecular adsorption on intermetallic single crystalline surfaces.

Single crystal growth and characterization of the binary semiconducting compound FeGa3 and its Ge‐substitute FeGa3–xGex are reported. Whereas there have been several investigations on the thermoelectric properties based on small samples grown by the flux method, this study is the first approach using the Czochralski growth technique from well‐oriented single‐crystalline seeds. Problems and solutions of the growth of cm3‐size single crystals are discussed in detail. Ge segregation in FeGa3–xGex is described by a segregation coefficient lower than unity which leads to an axially increasing Ge content along the pulling direction. Consequences with respect to lattice parameter changes and thermoanalytic measurements are reported.

The single crystal deformation behaviour of orthorhombic Al13Co4 hasbeen studied below the brittle-ductile transition temperature observedin bulk material from room temperature to 600 degrees C, usingindentation, microcompression and transmission electron microscopy. Atroom temperature, slip occurred most easily by dislocation motion on the(0 0 1)[0 1 0] slip system, as observed in the ductile regime at hightemperatures. However, as the temperature was increased towards 600degrees C, the slip pattern changed to one consisting of linear defectsrunning perpendicular to the loading axis. Serrated flow was observed atall temperatures, although at 600 degrees C the magnitude of theserrations decreased. Anomalous yielding behaviour was also observedabove 226 degrees C, where both the yield and the 2\% flow stressincreased with temperature, almost doubling between 226 and 600 degreesC. It has been suggested that this might arise due to the increasingstability of orthorhombic Al13Co4 with respect to the monoclinic formwith increasing temperature. This is shown to be consistent with thetheoretical predictions that exist.

$^{71}\mathrm{Ga}$ NQR, magnetization, and specific-heat measurements have been performed on polycrystalline Ge-doped ${\mathrm{FeGa}}_{3}$ samples. A crossover from an insulator to a correlated local moment metal in the low-doping regime and the evolution of itinerant ferromagnet upon further doping is found. For the nearly critical concentration at the threshold of ferromagnetic order, ${x}_{C}=0.15, ^{71}(1/{T}_{1}T)$ exhibits a pronounced ${T}^{\ensuremath{-}4/3}$ power law over two orders of magnitude in temperature, which indicates three-dimensional quantum critical ferromagnetic fluctuations. Furthermore, for the ordered $x=0.2$ sample (${T}_{C}\ensuremath{\approx}6$ K), $^{71}(1/{T}_{1}T)$ could be fitted well in the frame of Moriya's self-consistent renormalization theory for weakly ferromagnetic systems with $1/{T}_{1}T\ensuremath{\sim}\ensuremath{\chi}$. In contrast to this, the low-doping regime nicely displays local moment behavior where $1/{T}_{1}T\ensuremath{\sim}{\ensuremath{\chi}}^{2}$ is valid. For $T\ensuremath{\rightarrow}0$, the Sommerfeld ratio $\ensuremath{\gamma}=(C/T)$ is enhanced $(70\phantom{\rule{0.16em}{0ex}}\mathrm{mJ}/\mathrm{mole}\phantom{\rule{0.28em}{0ex}}{\mathrm{K}}^{2}$ for $x=0.1)$, which indicates the formation of heavy $3d$ electrons.

Scratching the surface: The high selectivity of PdGa catalysts towards the partial hydrogenation of acetylene was previously attributed to the separation of Pd atomic sites at the surfaces. The atomic structures of PdGa surfaces are determined by means of a combined experimental and computational approach allowing investigation of the catalytic dissociation of hydrogen. The two opposite (111) and {{\left( {\bar 1\bar 1\bar 1} \right)}} surfaces show a very different arrangement of catalytic centers.

The intermetallic PdGa is a highly selective and potent catalyst in the semihydrogenation of acetylene, which is attributed to the surface stability and isolated Pd atom ensembles. In this context PdGa single crystals of form B with (111) orientation were investigated by means of X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), scanning tunneling microscopy (STM), X-ray photoelectron diffraction (XPD), and low-energy electron diffraction (LEED) to study the electronic and geometric properties of this surface. UPS and thermal desorption spectroscopy (TDS) were used to probe the chemisorption behavior of CO. The PdGa(111) surface exhibits a (1 × 1) LEED and a pronounced XPD pattern indicating an unreconstructed bulk-truncated surface. Low-temperature STM reveals a smooth surface with a (1 × 1) unit cell. No segregation occurs, and no impurities are detected by XPS. The electronic structure and the CO adsorption properties reveal PdGa(111) to be a bulk-truncated intermetallic compound with Pd-Ga partial covalent bonding.

International audience; The intermetallic compound InPd (CsCl type of crystal structure with a broad compositional range) is considered as a candidate catalyst for the steam reforming of methanol. Single crystals of this phase have been grown to study the structure of its three low-index surfaces under ultra-high vacuum conditions, using low energy electron diffraction (LEED), X-ray photoemission spectroscopy (XPS), and scanning tunneling microscopy (STM). During surface preparation, preferential sputtering leads to a depletion of In within the top few layers for all three surfaces. The near-surface regions remain slightly Pd-rich until annealing to ∼580 K. A transition occurs between 580 and 660 K where In segregates towards the surface and the near-surface regions become slightly In-rich above ∼660 K. This transition is accompanied by a sharpening of LEED patterns and formation of flat step-terrace morphology, as observed by STM. Several superstructures have been identified for the different surfaces associated with this process. Annealing to higher temperatures (≥750 K) leads to faceting via thermal etching as shown for the (110) surface, with a bulk In composition close to the In-rich limit of the existence domain of the cubic phase. The Pd-rich InPd(111) is found to be consistent with a Pd-terminated bulk truncation model as shown by dynamical LEED analysis while, after annealing at higher temperature, the In-rich InPd(111) is consistent with an In-terminated bulk truncation, in agreement with density functional theory (DFT) calculations of the relative surface energies. More complex surface structures are observed for the (100) surface. Additionally, individual grains of a polycrystalline sample are characterized by micro-spot XPS and LEED as well as low-energy electron microscopy. Results from both individual grains and “global” measurements are interpreted based on comparison to our single crystals findings, DFT calculations and previous literature.

Oxidation of the Al 9 Co 2 (0 0 1) and Al 13 Co 4 (1 0 0) surfaces has been performed in a wide range of temperatures at 2 × 10 −8 or 1 × 10 −7 mbar oxygen pressure. Only Al O bonding is observed. The oxidation kinetics are controlled by the quantity of oxygen sticking on the surface. Oxidation results from a competition between several effects: formation of an oxide film, dissolution of the film, oxygen desorption and oxygen dissolution into the bulk. For temperatures lower than 710 K for the Al 9 Co 2 (0 0 1) surface and 925 K for the Al 13 Co 4 (1 0 0) surface, a ∼5 A thick oxide film is formed which does not show any long-range order and desorbs upon annealing. When oxidation is performed at higher temperatures, oxygen diffusion into the bulk is observed. A poorly ordered oxide film having a sixton structure is formed on the Al 9 Co 2 (0 0 1) surface when oxidation is performed at 775 K, which is dissolved when annealing at higher temperatures. On the Al 13 Co 4 (1 0 0) surface, only a weak streaky polar circle is observed following annealing at 925 K the film formed at room temperature, which corresponds to an hexagonal network of O atoms into small ultrathin oxide layers domains. The oxidation behaviour of the Al 9 Co 2 (0 0 1) and Al 13 Co 4 (1 0 0) surfaces has been ascribed to the strong covalent character of bonds present in these Al Co phases, which prevents aluminium diffusion. C 2 H n molecules ( n = 2, 4, 6) do not adsorb on the Al 13 Co 4 (1 0 0) surface in the experimental conditions used in this study, thus suggesting that this surface might not be the active one in the semi-hydrogenation of acetylene.

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. Armbruster et al., Nat. Mater. 11, 690 (2012)].

International audience; Atomic oxygen adsorption on the pure aluminium terminated Al9Co2 (001) surface is studied by first principle calculations coupled with STM measurements. Relative adsorption energy of oxygen atoms have been calculated on different surface sites along with the associated STM images. The local electronic structure of the most favourable adsorption site is described. The preferential adsorption site is identified as a "bridge" type site between the cluster entities exposed at the (001) surface termination. The Al-O bonding between the adsorbate and the substrate presents a covalent character, with s − p hybridization occuring between the states of the adsorbed oxygen atom and the aluminium atoms of the surface. The simulated STM image of the preferential adsorption site is in agreement with experimental observations. This work shows that oxygen adsorption generates important atomic relaxations of the topmost surface layer and that sub-surface cobalt atoms strongly influence the values of the adsorption energies. The calculated Al-O distances are in agreement with those reported in Al2O and Al2O3 oxides and for oxygen adsorption on Al(111).

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.

We present a detailed study of the (001) surface of the Al9Co2 crystalusing both experimental methods and first-principles calculations basedon the density functional theory. Experimentally, the (1 x 1) low-energyelectron diffraction pattern combined with the composition determinedusing X-ray photoemission spectroscopy is consistent with a bulkterminated surface. In addition, scanning tunneling microscopy (STM)measurements highlights the presence of only one type of surfacetermination. Combining experimental results with electronic structurecalculations provides many arguments to correlate the observed surfacetermination with the dense pure aluminum layer present in the Al9Co2bulk structure: (i) calculations show that this termination presents alower surface energy compared to another conceivable terminationobtained also from bulk truncation, (ii) step height measurements areconsistent with calculated interlayer spacings, (iii) calculatedbroadened densities of states and simulated STM images are qualitativelyin agreement with the experimental photoelectron spectra and theexperimental STM images.

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.

International audience; We present a study of the anisotropic electrical, magnetic and thermal transport properties of a single-crystalline Al80Cr15Fe5 approximant to the decagonal quasicrystal. Temperature-dependent electrical resistivity along the b and c crystalline directions shows nonmetallic behavior with a broad maximum, whereas it shows metallic positive temperature coefficient along the a direction perpendicular to the (b,c) atomic planes. The resistivity can be treated with the model of slow charge carriers, where the increased electron-phonon scattering upon raising the temperature induces transition from dominant Boltzmann (metallic) to dominant non-Boltzmann (insulatinglike) regime. Magnetic susceptibility and thermal conductivity show small anisotropy as well.

We present a comprehensive study of Bi thin-film growth on quasicrystal surfaces. The substrates used for the growth are the fivefold surface of icosahedral $(i)$-Al-Cu-Fe and $i$-Al-Pd-Mn and the tenfold surface of decagonal $(d)$-Al-Ni-Co quasicrystals. The growth is investigated at 300 and 525 K substrate temperatures and at different coverage $(\ensuremath{\theta})$ ranging from submonolayer to ten monolayers. The film is characterized by scanning tunneling microscopy, reflection high-energy electron diffraction, and x-ray photoelectron spectroscopy. At 300 K, the deposited Bi yields a quasicrystalline film for $\ensuremath{\theta}\ensuremath{\le}1$. For $1l\ensuremath{\theta}l5$, it forms nanocrystallites with (100) surface orientation. The islands have magic heights, which correspond to the stacking of four atomic layers (predominantly). The selection of magic heights is interpreted in terms of quantum size effects arising from the electron confinement within the film thickness. The islands establish rotational epitaxial relationship with the substrate. For higher coverage, the film grows with monatomic height, not with magic heights, and reflects the symmetry of the bulk Bi. When deposition is performed at 525 K, terrace diffusion is more effective, resulting in the aggregation of Bi adatoms developing into a smooth monolayer with quasiperiodic order. At this temperature, multilayers do not adsorb.

International audience; Large single crystals of the decagonal AlCoNi phase were reproducibly grown by the Czochralski method from Al-rich melts. By using native seeds, it was possible to grow crystals with well-defined orientations, e.g. along the 10-fold periodic axis or parallel to one of the 2-fold axes. Quasicrystals, that had been pulled in periodic or quasiperiodic directions, were characterized by X-ray transmission topography at the synchrotron source (ESRF) and at laboratory sources using the Lang technique. Because of the metallurgical homogeneity of the grown quasicrystals, lattice parameter differences did not contribute to the topographic contrast, instead, orientation contrast dominated. A column-like substructure along the periodic direction could be revealed. From this it is concluded, that crystal growth along a two-fold direction might be favourable with respect to minimizing defect spreading.

Low-energy electron diffraction (LEED) and scanning tunneling microscopy (STM) results are used to study the pseudo-6-fold nature of the (100) surface of the orthorhombic quasicrystal approximant Al4(Cr, Fe). LEED patterns are also presented from the pseudo-10-fold (010) surface of this material. In each case the results are compared with the known bulk structure of this complex metallic alloy.