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The synthesis of Si 3 N 4  nanowires from the reaction of silicon nanoparticles with N 2  in the 1200–1440 °C temperature range is reported. The nitridation conditions are such that the reaction with nitrogen is favoured by the presence of silicon oxide in the particles and by the active oxidation of silicon without a catalyst. It is shown that the Si to Si 3 N 4  conversion rate depends on the amount of silicon particles used in the experiments and that, in general, the reaction slows down for greater amounts. This trend is explained by particle stacking, which restricts the exchange of gases between the furnace atmosphere and the atmosphere around the inner particles. In a first stage, local oxygen partial pressure increases around the inner particles and inhibits nitridation locally. If the amount of reactant Si nanoparticles is small enough, this extrinsic effect is avoided and the intrinsic nitridation kinetics can be measured. Experiments show that intrinsic kinetics does not depend on temperature. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Kinetic study of the oxide‐assisted catalyst‐free synthesis of silicon nitride nanowires