Method of catalyzing copper deposition in a damascene structure by plasma treating the barrier layer and then applying a catalyst such as iodine or iodine compounds to the barrier layer

A method of manufacturing a copper metal wiring in a semiconductor device, comprising the step of:

• forming an interlayer insulating film on a substrate in which an underlying structure is formed;
• forming a damascene pattern on the interlayer insulating film to provide a contact hole through the interlayer insulating film to the substrate;
• performing a cleaning process;
• forming a diffusion barrier layer on entire structure;
• performing a plasma process without exposing the interlayer insulating film or substrate disposed beneath the diffusion barrier layer;
• performing a chemical pre process on the diffusion barrier layer using a chemical enhancer selected from the group consisting of:
• an iodine-containing liquid compound, an iodine-containing gas, an iodine-containing water vapor, and a compound comprising at least one group VII element;
• to provide a catalyzed diffusion barrier layer;
• depositing copper on the catalyzed diffusion barrier layer to fill the damascene pattern;
• and
• performing a chemical mechanical polish process forming a copper metal wiring only within the damascene pattern.