XRD-Studies of SiC/Si layers on carbon substrates

Structural investigations of thin films of SiC, SiC with free silicon and various titanium suicides (TiSi₂, TiSi and Ti₅Si₃) are described. The crystal phases have been identified using X-ray diffractometry. The growth of reaction products from surface reactions between silicon and deposited titanium can be observed.Dedicated to Professor Dr. rer.nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Investigations on Chemical Vapour Transport of Intermetallic Phases in the System Co/Fe/Si

The ternary phases existing on the quasi binary section CoSi/FeSi and CoSi₂/β‐FeSi₂ have been investigated by solid state reactions and chemical transport. The solid solution serie Co_xFe_1‐xSi can be described as a regular solution. The transport behaviour calculated is in good agreement with the experiments. The phases have been characterized by X‐ray powder diffraction, EDX and ICP‐OES. The temperature dependence of the resistivity has been measured from 20 K up to room temperature on single crystals.     

Photon and Ion-Beam Induced Processes in Materials Studied by Hyperfine Interactions

Laser nitriding and laser cementation are investigated by Mössbauer spectroscopy and complementary methods. It is demonstrated how the backscattering versions of Conversion Electron and Conversion X-ray Mössbauer spectroscopy can contribute to the investigation of surface processes, like the laser-induced formation of nitrides and carbides. Additionally, the formation of semiconducting iron disilicide can be achieved by ion-beam mixing and pulsed laser irradiation of Fe/Si bilayers. The results of both processes are compared.

     

The ternary system cerium-rhodium-silicon

Phase relations have been established in the ternary system Ce-Rh-Si for the isothermal section at 800 °C based on X-ray powder diffraction and EPMA on about 80 alloys, which were prepared by arc melting under argon or by powder reaction sintering. From the 25 ternary compounds observed at 800 °C 13 phases have been reported earlier. Based on XPD Rietveld refinements the crystal structures for 9 new ternary phases were assigned to known structure types. Structural chemistry of these compounds follows the characteristics already outlined for their prototype structures: τ₇—Ce₃RhSi₃, (Ba₃Al₂Ge₂-type), τ₈—Ce₂Rh_3−xSi_3+x (Ce₂Rh_1.35Ge_4.65-type), τ₁₀—Ce₃Rh_4−xSi_4+x (U₃Ni₄Si₄-type), τ₁₁—CeRh₆Si₄ (LiCo₆P₄-type), τ₁₃—Ce₆Rh₃₀Si_19.3 (U₆Co₃₀Si₁₉-type), τ₁₈—Ce₄Rh₄Si₃ (Sm₄Pd₄Si₃-type), τ₂₁—CeRh₂Si (CeIr₂Si-type), τ₂₂—Ce₂Rh_3+xSi_1−x (Y₂Rh₃Ge-type) and τ₂₄—Ce₈(Rh_1−xSi_x)₂₄Si (Ce₈Pd₂₄Sb-type). For τ₂₅—Ce₄(Rh_1−xSi_x)₁₂Si a novel bcc structure was proposed from Rietveld analysis. Detailed crystal structure data were derived for τ₃—CeRhSi₂ (CeNiSi₂-type) and τ₆—Ce₂Rh₃Si₅ (U₂Co₃Si₅-type) by X-ray single crystal experiments, confirming the structure types. The crystal structures of τ₄—Ce₂₂Rh₂₂Si₅₆, τ₅—Ce₂₀Rh₂₇Si₅₃ and τ₂₃—Ce_33.3Rh_58.2−55.2Si_8.5−11.5 are unknown. High temperature compounds with compositions Ce₁₀Rh₅₁Si₃₃ (U₁₀Co₅₁Si₃₃-type) and CeRhSi (LaIrSi-type) have been observed in as-cast alloys but these phases do not participate in the phase equilibria at 800 °C.     

X-ray structural study of intermetallic alloys RT2Si and RTSi2 (R=rare earth, T=noble metal)

Two series of intermetallic alloys, RT₂Si and RTSi₂, have been synthesized from stoichiometric compositions. The crystal structures of EuPt_1+xSi_2−x (CeNiSi₂-type), CeIr₂Si (new structure type), YbPd₂Si and YbPt₂Si (both YPd₂Si-type) have been elucidated from X-ray single crystal CCD data, which were confirmed by XPD experiments. The crystal structures of LaRh₂Si and LaIr₂Si (CeIr₂Si-type), {La,Ce,Pr,Nd}AgSi₂ (all TbFeSi₂-type), and EuPt₂Si (inverse CeNiSi₂-type) were characterized by XPD data. RT₂Si/RTSi₂ compounds were neither detected in as-cast alloys Sc₂₅Pt₅₀Si₂₅, Eu₂₅Os₂₅Si₅₀ and Eu₂₅Rh₂₅Si₅₀ nor after annealing at 900 °C. Instead, X-ray single crystal data prompted Eu₂Os₃Si₅ (Sc₂Fe₃Si₅-type) and EuRh_2+xSi_2−x (x=0.04, ThCr₂Si₂-type) as well as a new structure type for Sc₂Pt₃Si₂ (own type).     

Water splitting as a tool for obtaining insight into metal–support interactions in catalysis

This review is focused on the use of the water splitting reaction for characterizing oxygen vacancies in supported metal catalysts and more generally to get insight into the high-temperature modifications of metal–support interactions. Three supports widely used in catalysis are considered, namely alumina, silica and ceria. The catalysts were reduced at temperatures T_R ranging from 200 to 1000 °C. The reaction with water was carried out at temperatures T_OX ranging from 100 to 1000 °C. In every case, the metal (Rh or Pt) was chosen among those which are not oxidizable by water. Extensive investigations of the reactivity of water with unsupported metals and films confirmed this choice. The reaction is then selective for the titration of O vacancies, generally associated with reduced cations of the support. On alumina-supported catalysts, reduction at T_R > 600 °C leads to the formation of oxygen vacancies strictly confined to the periphery of metal particles. The amount of hydrogen produced Q_H is coherent with the peripheral oxygen density. Reduction of silica-supported catalysts at T_R > 600 °C generates metal silicides that can be selectively destroyed by water with reformation of silica and metal nanoparticles. Oxygen vacancies are formed on ceria catalysts at 200 °C. These oxygen vacancies are confined to the surface up to 600 °C. At higher temperatures, oxygen vacancies are formed in the bulk: about 50% of CeO₂ would be reduced at 900 °C. The amount of H₂ produced by reaction with water is thus very high on metal-ceria catalysts. At T_R > 900 °C, metal cerides start to form. Remarkably, a significant reactivity of H₂O on a Rh/CeO₂ catalyst reduced at 850 °C is recorded as of 100 °C. However, the quantitative titration of oxygen vacancies required temperatures T_OX > 500 °C. As a rule, the technique of water splitting allows the detection of 1 μmol g⁻¹ of oxygen vacancies, i.e. a few 0.1% of the surface in the case of reducible oxides of 10–20 m² g⁻¹.     

Electromigration of Aluminium through Quasi Bamboo‐Like Grain Blocked Silicide Interconnects

MoSi₂ interconnects between electrical aluminium contact pads were exposed to a high direct current density of 1 MA cm^‐2 during 2000 hours. Thermal annealing of the interconnects prior to the experiment generated grains of almost the width of the line, providing for bamboo‐like grain blocked polycrystalline clusters along the line acting as migration stopping sites. Aluminium migration out of the cathode contact pad is observed with pronounced precipitations on the interconnect side walls. SEM and EDX are applied to identify sites and nature of the electromigration product.