Metal silicides, oxidation

Silicon-containing ceramics include the oxide materials, silica and the silicates the binary compounds of silicon with non-metals, principally silicon carbide and silicon nitride silicon oxynitride and the sialons main group and transition metal silicides, and, finally, elemental silicon itself. There is a vigorous research activity throughout the world on the preparation of all of these classes of solid silicon compounds by the newer preparative techniques. In this report, we will focus on silicon carbide and silicon nitride. 

In many cases, metal silicides may very well be the catalysts. For example, FeSi2 is being considered to be the catalyst in Fe-assisted nanowire synthesis. This is similar to the silicon mono-oxide case, although it is much easier to understand the mechanisms in the FeSi2 case. It is also possible that during the catalytic processes that silicon diffuses relatively freely through the metal catalyst and consequently, the observed silicides at the end of reaction may be different from those during the catalytic reaction. No direct evidence is available to show whether metal or metal silicide nanoparticles are the tme catalyst. 

Silicon carbide is comparatively stable. The only violent reaction occurs when SiC is heated with a mixture of potassium dichromate and lead chromate. Chemical reactions do, however, take place between silicon carbide and a variety of compounds at relatively high temperatures. Sodium silicate attacks SiC above 1300°C, and SiC reacts with calcium and magnesium oxides above 1000°C and with copper oxide at 800°C to form the metal silicide. Silicon carbide decomposes in fused alkalies such as potassium chromate or sodium chromate and in fused borax or cryolite, and reacts with carbon dioxide, hydrogen, air, and steam. Silicon carbide, resistant to chlorine below 700°C, reacts to form carbon and silicon tetrachloride at high temperature. SiC dissociates in molten iron and the silicon reacts with oxides present in the melt, a reaction of use in the metallurgy of iron and steel (qv). The dense, self-bonded type of SiC has good resistance to aluminum up to about 800°C, to bismuth and zinc at 600°C, and to tin up to 400°C a new silicon nitride-bonded type exhibits improved resistance to cryolite. 

Finally, surface analysis has been used in the investigation of metal silicides used to form rectifying Schottky barrier contacts to semiconductors. These silicides are formed by thermal or laser sintering of the metal after deposition onto the substrate. Excess unreacted metal is removed by chemical etching. XPS has been used to show that the metal has been oxidized if the excess metal cannot be removed (52). 

This type of material is commonly used in the production of semiconductor devices.57 The silica layer is used as a starting layer for integrated circuit (IC) build-up. IC layer materials range from single crystals and doped polycrystalline silicon, silicon nitride, thermally-grown oxide to vapour deposited or sputtered metal or metal silicide layers. Structural adhesion of the various layers is obtained by the application of organosilanes, such as AEAPTS, APTS and GPTS. 

Growing a quality tunnel barrier on a silicon surface involves cleaning off this oxide and depositing a metal, such as aluminium for example, that is subsequently oxidized to form a thin insulating layer. Two potential difficulties lurk in the process formation of a conducting metal silicide at... 

Numerous types of materials have been made by CVD techniques, such as metal carbides, borides, silicides, oxides, nitrides, and chalcogenides, as well as films of pure metals.27 For example, thermolysis of Cp PtMe3 deposits films of platinum on glass or silicon wafer substrates,28 while Pd(hfacac)2 (hfacac = 1,1,1,5,5,5-... 

The obtained results on the reaction mechanism can be summarized as follows The metal silicides form cluster structures which represent electron buffer systems. They can be oxidized or reduced easily by surface reactions. The adsorption of SiCl4 molecules at the cluster surface is immediately followed by an electron transfer from the cluster to the silicon atom of SiCl4, the cluster is oxidized. As a result of such a process a silylene species is formed at the surface of the catalyst. Chloride ions act as counter ions to the positive cluster, supporting the redox step (Eq. 4). 

Silicon is highly unstable in aqueous electrolytes due to the formation of an insulating oxide film which prevents the use of n-Si as photoanode. On the other hand, the silicon electrode has poor kinetics for hydrogen evolution which is not desirable for its use as a photocathode. Many methods have been explored to stabilize Si electrodes in aqueous solutions for possible applications as photochemical cells. They include coating the surface with noble metals, metal oxides, metal silicides, or organic materials as shown in Table 6.6. Also, some redox species, the reduction of which can favorably compete with the oxidation of silicon, can be used to stabilize silicon anodes... 

The refractory metal silicides have been used for many years to protect refractory metals from oxidation in very high temperature, but short duration applications [121], These coatings have been highly successful but their use in applications which require long term stability have been limited by problems with accelerated oxidation and... 

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