The present invention is generally directed to a method of forming titanium nitride layers. In one illustrative embodiment, the method includes forming a layer of titanium nitride by performing a deposition process, performing an anneal process on the layer of titanium nitride in a chlorine scavenging ambient to define an annealed layer of titanium nitride, and, prior to exposing the annealed layer of titanium nitride to an oxygen-containing ambient, forming a cap layer on the annealed layer of titanium nitride. In another illustrative embodiment, the method includes performing a chemical vapor deposition process in a first process chamber to form a layer of titanium nitride above a semiconducting substrate, transferring the substrate to a second process chamber, performing an anneal process on the layer of titanium nitride in a chlorine scavenging ambient within the second process chamber to produce an anneal layer of titanium nitride, and, prior to exposing the annealed layer of titanium nitride to an oxygen-containing ambient, forming a cap layer on the annealed layer of titanium nitride in the second process chamber.