Diffusion barrier materials, such as TiN, WxN, WNxCy, and their nanolaminates were deposited by atomic layer deposition method. TiN film exhibited excellent properties, but WxN film exhibited high resistivity despite the low residue concentration. Both TiN and WxN films suffered from serious incompatibility with the copper metal. WNxCy film was deposited by introducing triethylboron as a reducing agent for tungsten. Excellent film properties were obtained, including very good compatibility with the copper metal, evident as strong adhesion and no pitting on the copper surface. Nanolaminate barrier stacks of WxN/TiN and WNxCy/TiN were successfully deposited. TiN deposition did not cause copper pitting when thin WNxCy. film was deposited underneath. (C) 2003 Elsevier Science B.V. All rights reserved.