We evaluated PECVD WNx as a potential copper barrier. Ultrathin (100 Å) PECVD WNx films were deposited utilizing WF6/N2/H2 chemistry. Films with N/W stoichiometries ranging from 0.1 to 1.0 and resistivities between 200 – 1000 μΩ-cm were deposited by varying pressure, deposition temperature, N2 flow, and H2 flow. The thermal stability of the films was evaluated by annealing Si/WNx /Cu stacks for 1 hour at temperatures up to 700°C. Barrier failure was detected by sheet resistance change and surface SIMS. The thermal stability was correlated with N/W ratio and free fluorine content as determined by temperature programmed desorption mass spectroscopy. The tests showed that films with N/W ratios between 0.3 and 0.4 had optimal barrier properties, while fluorine was seen to have a detrimental effect on barrier stability. Moreover, tests showed that the substrate affects fluorine concentration as WNx deposited on silicon dioxide has a higher interfacial fluorine content than WNx on silicon. Thus, fluorine contamination at the WNx /Si02 interface led to poor electrical reliability as measured by leakage current vs. time on MOS capacitors.