Copper cleaning in supercritical CO2 for the microprocessor interconnects

In this study we report the efficiency of cleaning process in supercritical CO₂ for the removal of the post-etch residues and oxidized copper formed in the via after SiOC-based porous materials etching and photoresist plasma ashing processes. The cleaning solutions contain a sulfonic acid and chelating agents with different chemical configurations. X-ray reflectometry and scanning electron microscopy are used to estimate the oxidized copper dissolution and copper surface aspect (pitting corrosion and residues). The results show that the sulfonic acid dissolves cuprous oxide (Cu₂O) and copper hydroxide (Cu(OH)₂) and consequently allows to remove the residues located at the oxidized copper surface whereas the symmetric β-diketones remove only the copper hydroxide. The mixture of sulfonic acid and β-diketone does not lead to pits at the copper surface. This phenomenon could be due to a complex formation between copper and β-diketones facilitating the oxidized copper dissolution by the acid or could be due to copper surface protection by the adsorbed β-diketones.