A Cl2 gas plasma is generated at a site within a chamber between a substrate and a metal member. The metal member is etched with the Cl2 gas plasma to form a precursor. A nitrogen gas is excited in a manner isolated from the chamber accommodating the substrate. A metal nitride is formed upon reaction between excited nitrogen and the precursor, and formed as a film on the substrate. After film formation of the metal nitride, a metal component of the precursor is formed as a film on the metal nitride on the substrate. In this manner, a barrier metal film with excellent burial properties and a very small thickness is produced at a high speed, with diffusion of metal being suppressed and adhesion to the metal being improved.