Investigation of organic impurities adsorbed on and incorporated into electroplated copper layers

At room temperature electroplated copper layers exhibit changes in resistivity, residual stress, and microstructure. This process, known as self-annealing, is intimately linked to the release of organic impurities, which stem from the incorporation of organic additives into the Cu layer in the course of the electroplating process. The behavior of these impurities during self-annealing, represented by the carbon content, could be detected by analytical radio frequency glow discharge optical emission spectrometry (GD-OES) and carrier gas hot extraction (CGHE). The precondition of a quantitative determination is a surface cleaning procedure to remove adsorbed organics from the copper surface. It was observed that at first almost all impurities have to leave the Cu metallization before an accelerated abnormal grain growth can start. The small amount of remaining organic species after self-annealing could be quantified by both examination techniques, GD-OES and CGHE.