Properties of thin film silicon nitride deposited by hot wire chemical vapor deposition using silane, ammonia, and hydrogen gas mixtures

The structure of thin film SiN, deposited by the hot wire chemical vapor deposition (HWCVD) technique using SiH4 and NH3 gas mixtures, is examined as H2 dilution is added to the gas flow mixture. For NH3/SiH4 gas flow ratios greater than 1/2, all films are a-SiN:H for H2/SiH4 gas dilution ratios as high as 20/1. While H2 dilution does not change the basic film structure, it does increase the efficiency of NH3 dissociation in the gas phase, and causes a further reduction in the already small amount of N-H bonding in a-SiN:H films deposited by HWCVD. Differences in local N bonding sites are observed when the nitrogen source gas is changed from NH3 to N2. For NH3/SiH4 gas ratios less than 1/2 and with high H2 dilution, deposition of μc-SiN by HWCVD is demonstrated. X-ray diffraction measurements show that the structure of these films consists of silicon crystallites embedded in an a-SiN:H matrix. An upper limit for N incorporation with the preservation of microcrystallinity is found, beyond which the films again become amorphous. The existence of this limit is explained in terms of structural disorder in the a-SiN:H tissue brought about by N incorporation.