Investigations on the corrosion of copper patterns in the course of the “post-CMP cleaning” of integrated electronic microcircuits in oxalic acid aqueous solutions

An unknown corrosion process producing dendrites was recently found to take place at copper patterns immersed in oxalic acid aqueous solutions in the course of the post-chemical–mechanical polishing of integrated microcircuits (ICs). We report here investigations of this corrosion phenomenon in ICs using atomic force microscopy (AFM), cyclic voltammetry and Raman spectroscopy. AFM first allowed an accurate morphological characterisation of the copper patterns and their surroundings while cyclic voltammetry was used to identify their electrochemical reactivity in oxalic acid aqueous solutions. In situ AFM experiments carried out in this same aqueous media in open circuit conditions unambiguously showed a progressive and partial dissolution of copper patterns as well as the formation of a ring type structure. Raman spectroscopy was used on gold supported electrogenerated copper films to identify the precipitation or adsorption products resulting from the electrochemistry of the copper/oxalic acid system as a function of the applied potential and the pH of the oxalic acid aqueous solutions. The collected results rather suggest a two-step galvanic corrosion phenomenon involving the tantalum barrier, copper seed layer and electrodeposited copper.