Diffusion Barrier Layers and Methods Comprising for Depositing Metal Films by CVD or ALD Processes

A process for forming a substantially continuous metal layer on a surface of a diffusion barrier layer, the process comprising:

• providing the surface of the diffusion barrier layer wherein the diffusion barrier layer comprises at least one material selected from the group consisting of a metal, a metal carbide, a metal nitride, a metal carbonitride, a metal silicon carbide, a metal silicon nitride, a metal silicon carbonitride, and mixtures thereof, wherein the diffusion barrier layer is not substantially free of elemental metal because either (i) the at least one material is the metal, (ii) the diffusion barrier layer has an orientation other than a substantially (111) preferred orientation, or (iii) the diffusion barrier layer has less than 95% of a (111) preferred orientation;
• exposing the at least one surface of the diffusion barrier layer to an at least one adhesion promoting agent selected from the group consisting of a nitrogen, a nitrogen-containing compound, a carbon-containing compound, a carbon and nitrogen containing compound, a silicon and carbon containing compound, a silicon, carbon, and nitrogen containing compound or a mixture thereof, is conducted at a temperature of from 40° C. to 400° C. such that the at least one surface becomes substantially free of an elemental metal;
• growing a metal halide layer on the surface of the diffusion barrier layer by contacting the surface with a halogen-containing precursor and an organometallic precursor wherein the halogen and the metal within the precursors react to form the metal halide layer, and wherein the organometallic precursor comprises a metal selected from the group consisting of copper, platinum, nickel, cobalt, palladium, ruthenium, rhodium, irridium, gold, and silver;
• and
• exposing the metal halide layer to a reducing agent to provide the metal layer.