Kinetics of the low-pressure chemical vapor deposited tungsten nitride process using tungsten hexafluoride and ammonia precursors

Tungsten nitride (WNx) is a hard refractory material with low electrical resistance that can be deposited using multiple methods. This study focuses on the microstructrual development of low pressure chemical vapor deposition grown WNx coatings. Also, the growth kinetics is studied and discussed in terms of the resulting microstructures. Samples of WNx were deposited using WF6, NH3, and Ar at 592–887 K in a hot-wall reactor with variable gas mixture compositions (NH3:WF6 = 0.5–25). The coatings were nitrogen-rich (x ∼ 1.65) and oxygen-free as determined by time-of-flight-elastic recoil detection analysis. X-ray diffraction showed that the coatings transformed from being amorphous to crystallizing as β-W2N at 641–690 K. The morphologies changed with deposition temperature. Being very fine grained and nodular at deposition temperatures 740 K and below, increasing the deposition temperature to 789 K while employing a NH3:WF6 molar ratio of 1, large disc-shaped protrusions were formed. When increasing the NH3:WF6 molar ratio to 25, striped facets became increasingly dominant. Investigating the latter by transmission electron microscopy, a microstructure of smaller ridges formed by twinning, oriented as <211> in the out-of-plane direction, was revealed across the facet surfaces. Transmission Kikuchi diffraction confirmed that <211> was the texture of these coatings. The partial reaction order of WF6 and NH3 at 740 K was determined to be close to 1/6 and 1/2, respectively. The apparent activation energy ranged from 82 to 12 kJ/mol corresponding to deposition temperatures from 592 to 887 K