A simple and most promising oxide-assisted catalyst-free method is used to prepare silicon nitride nanowires that give rise to high yield in a short time. After a brief analysis of the state of the art, we reveal the crucial role played by the oxygen
partial pressure: when oxygen partial pressure is slightly below the threshold of passive oxidation, a high yield inhibiting the formation of any silica layer covering the nanowires occurs and thanks to the synthesis temperature one can control nanowire dimensions.
The synthesis of Si3N4 nanowires from the reaction of silicon nanoparticles with N2 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 Si3N4 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.
