Silicon nitride possesses an attractive combination of thermo-mechanical properties which makes it a strong candidate material for many structural ceramic applications. Unfortunately, many of the conventional processing techniques used to produce Si3N4, such as hot-pressing, sintering, and hot-isostatic pressing, utilize significant amounts of densification aids (Y2O3, Al2O3, MgO, etc.) which ultimately lowers the utilization temperature to well below that of pure Si3N4 and also decreases the oxidation resistance. Chemical vapor deposition (CVD) is an alternative processing method for producing pure Si3N4. However, deposits made at temperatures less than ~1200°C are usually amorphous and at slightly higher temperatures, the deposition of crystalline material requires extremely low deposition rates (~5 μm/h). Niihara and Hirai deposited crystalline α-Si3N4 at 1400°C at a deposition rate of ~730 μm/h. Hirai and Hayashi successfully lowered the CVD temperature for the growth of crystalline Si3N4 by adding TiCl4 vapor to the SiCl4, NH3, and H2 reactants. This resulted in the growth of α-Si3N4 with small amounts of TiN at temperatures as low as 1250°C.
