REAuAl4Ge2 and REAuAl4(AuxGe1−x)2 (RE=rare earth element): Quaternary intermetallics grown in liquid aluminum

The two families of intermetallic phases REAuAl₄Ge₂ (1) (RE=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb) and REAuAl₄(Au_xGe_1−x)₂ (2) (x=0.4) (RE=Ce and Eu) were obtained by the reactive combination of RE, Au and Ge in liquid aluminum. The structure of (1) adopts the space group R-3m (CeAuAl₄Ge₂, , ; NdAuAl₄Ge₂, , ; GdAuAl₄Ge₂, , ; ErAuAl₄Ge₂, , ). The structure of (2) adopts the tetragonal space group P4/mmm with lattice parameters: , for EuAuAl₄(Au_xGe_1−x)₂ (x=0.4). Both structure types present slabs of “AuAl₄Ge₂” or “AuAl₄(Au_xGe_1−x)₂” stacking along the c-axis with layers of RE atoms in between. Magnetic susceptibility measurements indicate that the RE atoms (except for Ce and Eu) possess magnetic moments consistent with +3 species. The Ce atoms in CeAuAl₄Ge₂ and CeAuAl₄(Au_xGe_1−x)₂ (x=0.4) appear to be in a mixed +3/+4 valence state; DyAuAl₄Ge₂ undergoes an antiferromagnetic transition at 11 K and below this temperature exhibits metamagnetic behavior. The Eu atoms in EuAuAl₄(Au_xGe_1−x)₂ (x=0.4) appear to be in a 2+ oxidation state.     

ACu9X4 ‐ Neue Verbindungen mit der CeNi8, 5Si4, 5‐Struktur (A: Sr,Ba; X: Si,Ge)

ACu₉X₄ ‐ New Compounds with CeNi_{8, 5}Si_{4, 5} Structure (A: Sr, Ba; X: Si, Ge) The new compounds SrCu₉Si₄ (a = 8.146(1), c = 11.629(2)Å), BaCu₉Si₄ (a = 8.198(2), c = 11.735(2)Å), SrCu₉Ge₄ (a = 8.273(2), c = 11.909(5)Å), and BaCu₉Ge₄ (a = 8.338(4), c = 12.011(7)Å) are formed by reaction of the elements at 1000° ‐ 1100 °C. They are isotypic (I4/mcm, Z = 4) and crystallize in an ordered variant of the cubic NaZn₁₃ type structure, also built up by the binary phase BaCu₁₃. In the ternary compounds the positions of Cu2 are orderly occupied by copper and silicon and germanium, respectively. This results in a lowering of symmetry and a distortion of the polyhedra. The metallic conductivity of the compounds was confirmed by measurements on BaCu₉Si₄.     

Ion beam mixing of α-MoSi2

Abstract

Using molecular dynamics simulation, we study the mixing of an α-MoSi₂ crystal by 1 keV Ar ions. The observed order of magnitude of the mixing is compatible with a spike model of ion beam mixing. The influence of the target surface and of chemical effects are discussed.     

Growth process and structure of Fe/Si(1 1 1) ultrathin film: Transition from single-domain Fe(1 1 1)/Si(1 1 1) to β-FeSi2

The growth processes and structures of Fe/Si(1 1 1) ultrathin films grown by solid-phase reactive epitaxy were investigated by coaxial impact-collision ion scattering spectroscopy (CAICISS). It has been revealed that the Fe(1 1 1) thin films with a bcc-type structure were epitaxially grown on a Si(1 1 1) crystal, even at room temperature, and formed a single-domain structure: Fe(1 1 1)∥Si(1 1 1). After annealing at above 600 °C, the Fe(1 1 1) films were transformed into β-FeSi₂ via the collapse of the bcc-type structure to an amorphous or polycrystalline structure. On the basis of the thickness dependences of the growth processes, this phenomenon was discussed in terms of the diffusion of Si into Fe thin films.     

Formation of the Si/Ti interface

The formation of the Si/Ti interface during the deposition of silicon on titanium polycrystalline substrates has been studied at room temperature (RT) using X-ray photoelectron spectroscopy (XPS), angle-resolved XPS (ARXPS), ultraviolet photoelectron spectroscopy (UPS) and ion scattering spectroscopy (ISS). The experimental results are consistent with a two-stage mechanism for Si growth: a first stage characterized by the simultaneous formation of a uniform titanium silicide layer, that reaches a limiting thickness of ∼3 monolayer (ML), and pure silicon islands 1 ML thick that grow on top of this layer up to coalescence, followed by a second stage in which pure silicon islands, with an average thickness of 9 ML, grow on top of the uniform titanium silicide layer + pure silicon ML structure formed during the first stage. As a whole, pure silicon species grows according to a Stranski-Krastanov mechanism, where the first ML is formed during the first stage and the islands during the second stage. The comparison of Ti/Si and Si/Ti interfaces shows that the structure and composition of the interface do not depend substantially on the deposition sequence, suggesting that the bulk chemistry of the compound formed at the interface dominates over the surface kinetics and the bulk substrate chemistry in determining the composition and structure of the interface.     

Sc Solid State NMR studies of the silicides ScTSi (T=Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt)

The silicides ScTSi (T=Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt) were synthesized by arc-melting and characterized by X-ray powder diffraction. The structures of ScCoSi, ScRuSi, ScPdSi, and ScIrSi were refined from single crystal diffractometer data. These silicides crystallize with the TiNiSi type, space group Pnma. No systematic influences of the ⁴⁵Sc isotropic magnetic shift and nuclear electric quadrupolar coupling parameters on various structural distortion parameters calculated from the crystal structure data can be detected. ⁴⁵Sc MAS-NMR data suggest systematic trends in the local electronic structure probed by the scandium atoms: both the electric field gradients and the isotropic magnetic shifts relative to a 0.2 M aqueous Sc(NO₃)₃ solution decrease with increasing valence electron concentration and within each T group the isotropic magnetic shift decreases monotonically with increasing atomic number. The ⁴⁵Sc nuclear electric quadrupolar coupling constants are generally well reproduced by quantum mechanical electric field gradient calculations using the WIEN2k code.     

Submonolayer Au on Si(111) phase diagram

Based on a review of the current literature, a surface phase diagram is proposed for the submonolayer Au on Si(111) system. Kinetic considerations are reviewed and key surface phase diagram features such as the Θ < 0.4 ML metastable structure and the high temperature to Si(111)-(1 × 1)Au second order phase transition are discussed. Experiments to verify certain portions of the phase diagram are proposed.     

Energy surfaces of rare-earth silicide films on Si(1 1 1)

We report on angle-resolved photoelectron spectroscopy results of thin dysprosium-silicide layers formed on Si(1 1 1), taken with a toroidal analyzer allowing to image the energy surfaces in k_||-space. At monolayer dysprosium coverages, where hexagonal DySi₂ grows with a 1×1 superstructure, electron pockets are observed at the points with highly anisotropic effective masses, and around a hole pocket at the point also an anisotropic dispersion is found. The band filling of these two bands amounts to one, indicating an even number of electrons assigned to the surface unit cell. Similar features are found for multilayer coverages, where hexagonal Dy₃Si₅ layers are formed with a superstructure. Here, the influence of zone folding effects due to the reconstructed layers in the bulk silicide is only weak because of the high surface sensitivity of the experiments.     

Kann man die Arten von Zintl-Anionen steuern?? Variationen über das Thema Si2− im System Sr/Mg/Si

Can One Design Zintl Anions? Contributions from the System Sr/Mg/Si to the Topic Si^2? Two novel ternary silicides, SrMgSi₂ (Pnma, Z = 8, a = 14.374, b = 4.4512, c = 11.398 Å) and Sr₁₁Mg₂Si₁₀, (C2/m, Z = 2, a = 19.744, b = 4.754, c = 14.84 Å, β = 112.47°) have been established in the ternary system Sr/Mg/Si. The compounds are synthezised from the elements under inert conditions. Single crystal structure determinations yield the novel Zintl anions, [Si(Si₃)^8?] a branched chain, and the zig-zag chain piece [Si₈]^18?, both of which exhibit significant correlations and differences with respect to the linear chains in [Si^?] in the binary MSi phases (M = Ca, Sr, Ba) which have been reinvestigated in this context. The variations of the Zintl anions can be traced back mainly to the differences of Mg? Si and Sr? Si interactions. From these findings a functional relationship between Mg content and the formation of endgroup members in Zintl anions of silicon is anticipated.     

Synthese,Struktur und Eigenschaften der tantalreichen Silicidchalkogenide Ta15Si2QxTe10–x (Q = S,Se)

Synthesis, Structure, and Properties of the Tantalum‐rich Silicide Chalcogenides Ta₁₅Si₂Q_xTe_10–x (Q = S, Se) The quaternary tantalum silicide chalcogenides Ta₁₅Si₂Q_xTe_10–x (Q = S, Se) are accessible from proper, compacted mixtures of the respective dichalcogenides, silicon and elemental tantalum at 1770 K in sealed molybdenum tubes. The structures were determined from the strongest X‐ray intensities of fibrous crystals with cross sections of about 3 μm and confirmed by fitting the profile of single phase X‐ray diffractograms. The phases Ta₁₅Si₂S_3.5Te_6.5 and Ta₁₅Si₂Se_3.5Te_6.5 crystallize in the monoclinic space group C2/m with two formula units per unit cell, a = 2393.7(1) pm, b = 350.08(2) pm, c = 1601.2(1) pm, β = 124.700(4)°, and a = 2461.3(2) pm, b = 351.70(2) pm, c = 1601.7(1) pm, β = 124.363(5)°, respectively. Tri‐capped trigonal prismatic Ta₉Si clusters stabilized by encapsulated Si atoms can be seen as the characteristic unit of the structure. The clusters are fused into twin columns which are connected by additional Ta atoms, thus forming corrugated layers. The remaining valences at the surfaces of the layered Ta–Si substructure are saturated by those of chalcogen atoms which are coordinated only from one side by three, four or five Ta atoms. Few bridging covalent Ta–S–Ta and Ta–Se–Ta bonds and, otherwise, dispersive interactions between the Q atoms hold these nearly one nanometer wide slabs together. The phases are moderate metallic conductors. There is no evidence for any electronic instability within 10–310 K in spite of the high anisotropy of the structures.