Ternary silicides M2Cr4Si5 (M=Ti, Zr, Hf): filled variants of the Ta4SiTe4 structure type

The isostructural ternary silicides M₂Cr₄Si₅ (M=Ti, Zr, Hf) were prepared by arc-melting of the elemental components. The single-crystal structure of Zr₂Cr₄Si₅ was determined by X-ray diffraction (Pearson symbol oI44, orthorhombic, space group Ibam, Z=4, a=7.6354(12) Å, b=16.125(3) Å, c=5.0008(8) Å). Zr₂Cr₄Si₅ adopts the Nb₂Cr₄Si₅-type structure, an ordered variant of the V₆Si₅-type structure. It consists of square antiprisms that have Zr and Cr atoms at the corners and Si atoms at the centers; they share opposite faces to form one-dimensional chains _∞¹[Zr_4/2Cr_4/2Si] surrounded by additional Si atoms and extending along the c direction. In a new interpretation of the structure, additional Cr atoms occupy interstitial octahedral sites between these chains, clarifying the relation between this structure and that of Ta₄SiTe₄. The formation of short Si-Si bonds in Zr₂Cr₄Si₅ is contrasted with the absence of Te-Te bonds in Ta₄SiTe₄. The compounds M₂Cr₄Si₅ (M=Ti, Zr, Hf) exhibit metallic behavior and essentially temperature-independent paramagnetism. Bonding interactions were analyzed by band structure calculations, which confirm the importance of Si-Si bonding in these metal-rich compounds.     

Synthesis and structure of ternary transition-metal silicides Zr3Mn4Si6 and Hf3Mn4Si6

The isostructural ternary transition-metal silicides Zr₃Mn₄Si₆ and Hf₃Mn₄Si₆ can be prepared by direct reaction of the elemental components or by arc-melting. The single-crystal structure of Zr₃Mn₄Si₆ was determined by X-ray diffraction (Pearson symbol tP104, tetragonal, space group P4₂/mbc, Z=8, , ). Zr₃Mn₄Si₆ is isostructural to Nb₃Fe₃CrSi₆ and contains an essentially ordered arrangement of the transition-metal atoms. Square antiprismatic clusters with Zr and Mn atoms at the corners and Si atoms at the center share opposite faces to form one-dimensional columns extending along the c direction. These columns occupy channels that are outlined by a framework of edge- and face-sharing MnSi₆ octahedra. The extensive metal-metal interactions in the structure are complemented by Si-Si bonding in the form of dumbbells, linear chains, and zigzag chains.     

Crystal structures of three intermetallic phases in the Mo-Pt-Si system

The crystal structures of three ternary Mo-Pt-Si intermetallic compounds have been determined ab initio from powder X-ray diffraction data. All three structures are representative of new structure types. Both the X (MoPt₂Si₃, Pmc2₁, oP12, a=3.48438(6), b=9.1511(2), c=5.48253(8) Å) and Y (MoPt₃Si₄, Pnma, oP32, a=5.51210(9), b=3.49474(7), c=24.3090(4) Å) phases derive from PtSi (FeAs type) structure while the Z phase (ideal composition Mo₃₂Pt₂₀Si₁₆, refined composition Mo_29.9(2)Pt_21.0(3)Si_17.1(1), Cc, mC68, a=13.8868(3), b=8.0769(2), c=9.6110(2) Å, β=100.898(1)°) present similarities with the group of Frank-Kasper phases.     

Crystalline silicon films sputtered on molybdenum: A study of the silicon–molybdenum interface

Polycrystalline silicon films were grown on molybdenum (Mo)-coated substrates at high deposition rate using the pulsed magnetron sputtering technique. Our study investigates the silicon–molybdenum interface of these films to elucidate stimulating mechanisms for an ordered crystalline silicon thin film growth. Both Auger electron spectroscopy and Rutherford backscattering reveal that at a substrate temperature as low as T_S=450 °C during the deposition process intermixing of Si and Mo at the Si–Mo interface takes place leading to a compositional ratio Mo:Si of about 1:2. By Raman spectroscopy hexagonal β-MoSi₂ could be identified as the dominant phase in this intermixed region. The dependence of the resulting thickness of the reacted interface layer on the deposition conditions is not fully understood yet.     

Portraits of some representatives of metal boride carbide and boride silicide compounds

Different ternary alkaline-earth and rare-earth metal boron carbide and silicide compounds are examined using the solid-state language of Zintl-Klemm concept, band structures, and density of states, in order to show that the topology of the non-metal sub-lattice is highly dependent on the electron count. It is also shown that the chemistry of rare-earth metal-boron-silicon does not parallel that of rare-earth metal-boron-carbon. B-C bonds are easily formed in the latter, leading to a large variety of different structural arrangements, whereas Si-B bonds are hardly observed in the former, except in insertion compounds.     

Modification by H-termination in growth process of titanium silicide on Si(0 0 1)-2 × 1 observed with scanning tunneling microscopy

Formation processes of titanium silicide on hydrogen-terminated H/Si(0 0 1)-2 × 1 surface are studied at the atomic scale with a scanning tunneling microscopy (STM). Square-shaped nanoislands were observed on the Ti/H/Si(0 0 1) surface after annealed at 873-1073 K. These are the epitaxial nanoislands moderately grown due to the local orientation relationship between C49-TiSi₂ and Si(0 0 1), because passivation by surface hydrogen on Si(0 0 1) suppresses active and complex bond formation of Ti-Si.     

The growth of manganese layers on Si(1 0 0) at room temperature: A photoelectron spectroscopy study

The combination of spin-and charge based electronics in future devices requires the magnetic doping of group IV semiconductors, and the formation of ferromagnetic contacts. The doping of Mn with Si is one of the material systems which is discussed in this context. The present study focuses on the growth of Mn on a Si(100)(2x1) surface, and the evolution of the surface was observed as a function of Mn coverage with synchrotron-based photoelectron spectroscopy. The reaction of Mn with the Si(100) surface at room temperature leads the formation of silicide at the boundary between the Si substrate and the Mn-overlayer, presumably with MnSi stoichiometry. The residual sub-oxide reacts with the Mn and therefore incorporates a few percent of Mn-O-Si at the interface. The analysis of the sub-oxide composition indicates that the Si⁺¹ component is the most reactive oxidation state. The overlayer is dominated by Mn, either as Mn-metal or as a Mn-rich silicide phase, and the metallic layer introduces a band bending in Si. As a consequence of our observations, including information from a recent STM study, the formation of ferromagnetic contacts which require ideally a flat and compositionally homogenous overlayer, cannot be achieved through room temperature deposition of Mn on the Si(100) (2x1) surface. The influence of residual oxides and surface defects on the growth process will be further investigated.     

Effects of Ag addition on phase transformation and resistivity of TiSi2 thin films

In this study, the effects of adding Ag to TiSi₂ thin films are examined. It is demonstrated that both the C49 → C54 transformation temperature and the electric resistivity are appreciably lowered with Ag addition. Due to the presence of Ag nanocrystals precipitated at the C49 grain boundaries, the overall grain boundary density would increase to result in the higher nucleation rate of C54 and the lower transformation temperature. The precipitation of pure Ag network can provide another electric current conductive path except for the TiSi₂ grains. Due to the lower vacuum condition and the higher oxygen content in the current sputtered and annealed films, the C49 → C54 transformation temperature and the resistivity of the TiSi₂-20 at%Ag films can only be reduced by ∼100 °C and 10 μΩ cm, as compared with the non-Ag additive films. With better fabrication vacuum, the transformation temperature and resistivity might be lowered to a level below 700 °C and 15 μΩ cm, which are highly applausive for engineering applications.     

On the Reactivity of NHCtBuAuCl towards Rb6Cs6Si17: The First Gold-Silicon Cluster [(NHCtBuAu)6(η2-Si4)]Cl2·7NH3 and an Imide Capped Gold Triangle (NHCtBuAu)3NHCl

Crystals of the two new compounds (NHC^tBuAu)₃NHCl and [(NHC^tBuAu)₆(η²-Si₄)]Cl₂ · 7NH₃ could be isolated from the reaction of Rb₆Cs₆Si₁₇ with NHC^tBuAuCl in the presence of [2.2.2]-cryptand in liquid ammonia. Both compounds were characterized by single-crystal X-ray diffraction and crystallize trigonally without any alkali metals or chelating ligands. Additionally, the crystal of [(NHC^tBuAu)₆(η²-Si₄)]Cl₂ · 7NH₃ was further interpreted by means of ELF and NBO calculations. In the case of (NHC^tBuAu)₃NHCl, NMR experiments provided an exceptional insight into the reaction processes in solution and allowed for the detection of sequential precursors. In the class of capped gold triangles (NHC^tBuAu)₃NHCl impresses with its unique characteristics of being capped by an imide and bound to N-heterocyclic carbenes as ligands instead of the ubiquitously employed phosphines. The gold capped silicon tetrahedron [(NHC^tBuAu)₆(η²-Si₄)]Cl₂ · 7NH₃ represents the first known silicide-gold compound, as well as the first known functionalized Zintl anion, crystallized with a cationic central moiety.