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

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. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

[1]  Enric Bertran,et al.  Si3N4 single-crystal nanowires grown from silicon micro- and nanoparticles near the threshold of passive oxidation , 2005, 0811.3575.

[2]  H. Miao,et al.  Optical properties of single-crystalline α-Si3N4 nanobelts , 2005 .

[3]  B. Sheldon,et al.  Effects of Trace O2 Levels on the Nitriding Kinetics of High‐Purity Silicon Powders , 2004 .

[4]  G. Qin,et al.  Catalystless synthesis of crystalline Si3N4/amorphous SiO2 nanocables from silicon substrates and N2 , 2004 .

[5]  Y. Bando,et al.  Synthesis, structure, and photoluminescence of very thin and wide alpha silicon nitride (α-Si3N4) single-crystalline nanobelts , 2003 .

[6]  Shoushan Fan,et al.  The synthesis of metal oxide nanowires by directly heating metal samples in appropriate oxygen atmospheres , 2003 .

[7]  Jeunghee Park,et al.  Synthesis of silicon nitride nanowires directly from the silicon substrates , 2003 .

[8]  S. T. Lee,et al.  Small-Diameter Silicon Nanowire Surfaces , 2003, Science.

[9]  Jing Zhu,et al.  A Simple Method To Synthesize Nanowires , 2002 .

[10]  Huanchu Chen,et al.  Formation of α-Si3N4 whiskers with addition of NaN3 as catalyst , 2002 .

[11]  Jing Zhu,et al.  A simple method to synthesize Si3N4 and SiO2 nanowires from Si or Si/SiO2 mixture , 2001 .

[12]  Yongge Cao,et al.  Fabrication of β-Si3N4 nano-fibers , 2001 .

[13]  Y. Sun,et al.  Simultaneous growth of α-Si3N4 and β-SiC nanorods , 2001 .

[14]  Jing Zhu,et al.  Reversible bending of Si_3N_4 nanowire , 2000 .

[15]  Zhangjian Zhou,et al.  Combustion synthesis of α–Si_3N_4 whiskers , 1999 .

[16]  Bing-Lin Gu,et al.  SYNTHESIS OF SILICON NITRIDE NANORODS USING CARBON NANOTUBE AS A TEMPLATE , 1997 .

[17]  I. Chen,et al.  A tough SiAlON ceramic based on α-Si3N4 with a whisker-like microstructure , 1997, Nature.

[18]  S. Fan,et al.  Synthesis of Gallium Nitride Nanorods Through a Carbon Nanotube-Confined Reaction , 1997 .

[19]  T. Araki,et al.  Preparation of Microcoiled Si3 N 4 Fibers by Impurity Metal Activated Chemical Vapor Deposition and Their Mechanical Properties , 1995 .

[20]  Enric Bertran,et al.  Preparation of nanoscale amorphous silicon based powder in a square-wave-modulated rf plasma reactor , 1994 .

[21]  P. Ramesh,et al.  Carbothermal reduction and nitridation reaction of SiO_x and preoxidized SiO_x: Formation of α-Si_3N_4 fibers , 1994 .

[22]  P. Gopalakrishnan,et al.  Preparation of fibre-like silicon nitride from silicon powder , 1993 .

[23]  A. Varma,et al.  Quantitative kinetic analysis of silicon nitridation , 1993, Journal of Materials Science.

[24]  J. Szekely,et al.  Formation of Reaction‐Bonded Silicon Nitride from Silane‐Derived Silicon Powders: Macroscopic Kinetics and Related Transport Phenomena , 1992 .

[25]  H. Wada,et al.  Synthesis and characterization of silicon nitride whiskers , 1990 .

[26]  A. Moulson.  Reaction-bonded silicon nitride: its formation and properties , 1979 .

[27]  Y. Inomata,et al.  β-Si3N4 single crystals grown from Si melts , 1974 .