Roles of gas and solid components in the direct nitridation of silicon.

摘要

The factors influencing the direct nitridation of silicon, including the effects of the native oxide layer covering the surface of silicon, the effects of hydrogen contained in the nitridation gas and the catalytic effects of metals added to the raw material silicon, were investigated, using a tubular flow reactor and a fluidized-bed reactor operated at temperatures ranging from 1150°C to 1390°C in a stream of nitrogen containing 10% hydrogen.; The nitridation of silicon is not initiated until the native oxide is removed by an assistance of hydrogen contained in argon during the pretreatment or in the nitridation gas mixture. An induction period is observed before the initiation of the nitridation and depends on the nitridation temperature as well as the pretreatment time, which is associated with the removal of the oxide layer.; The presence of hydrogen in the nitridation atmosphere is crucial for the nitridation of silicon. When pretreated silicon grains are exposed to nitrogen without hydrogen for a time period as short as 5 minutes, the subsequent nitridation, even with hydrogen, becomes extremely slow. The concentration of hydrogen as low as 0.3% is effective for sustaining the reactivity of silicon for the nitridation. The results suggest the formation of a protective layer on the surface of silicon when silicon grains are exposed to nitrogen without hydrogen. The protective film is suspected to be silicon oxynitride, or a mixture of silicon oxynitride and silicon dioxide or silicon nitride formed from the reaction of silicon with oxygen and nitrogen, depending on the temperature of its formation. However, the protective film does not form on the native oxide layer, and the reactivity of silicon is resumed upon the removal of the native oxide.; An addition of calcium (as low as 0.125%) or yttrium (1.0–2.0%) to silicon suppresses the formation of β-silicon nitride while iron enhances the formation of β-silicon nitride. Copper promotes not only the nitridation but also the formation of α-silicon nitride at 1200°C, but enhances the β-phase formation at higher temperatures. The role of liquid phases on the formation of α-/β-silicon nitride was also discussed based on the nitridation of silicon impregnated with copper, calcium, silver, chromium and tungsten.