Environmentally Friendly Amino Acid-Based Polishing Slurry with Reduced Galvanic Corrosion at Copper/Cobalt Interface for Advanced Cu Interconnect Applications

Abstract

Chemical mechanical planarization (CMP) is an integral part in semiconductor processing including the back-end-of-line (BEOL) step. A goal of CMP is to uniformly polish the metal interconnects and the liner/barrier materials while minimizing CMP-related defects such as pitting, dissolution, and galvanic corrosion. A variety of azoles are used as corrosion inhibitors such as benzotriazole (BTA) to prevent corrosion defects during polishing. [1,2] These azoles work together with particles in the slurries to polish the overplated metal forming the interconnects. However, azoles are very poorly biodegradable during wastewater treatment and highly toxic to the nitrification process, which requires expensive wastewater treatment challenges.[3,4] Also, it is known that the use of BTA leads to contamination of Cu films by forming undesirable hydrophobic organic residues (e.g., BTA and Cu-BTA complexes),[5] making their removal very difficult during cleaning. To address these challenges aliphatic amino acids were examined as potential corrosion inhibitors to replace problematic azoles in CMP slurries.Three amino acids were considered in a model CMP slurry. These three were chosen for their unique functional groups: methionine, containing a sulfur group, glutamic acid, having an extra carboxylic acid group, and leucine, having a branched hydrocarbon chain. A representative polishing slurry with 35 nm colloidal silica abrasives, 1 wt% hydrogen peroxide as an oxidizer, 0.5wt% arginine as a complexing agent, at pH 8 was used. Three experimental aims were considered (1) corrosion characterization of the three amino acid and BTA electrolytes with linear sweep voltammetry; (2) comparison of the Co and Cu metal removal rate (MRR) in polishing experiments with a proto-type CMP polisher with 8” wafers, and (3) oxidation of the amino acids and BTA in a Fenton assisted electrooxidation reaction. Methionine was most effective in controlling the galvanic corrosion of the Cu-Co couple. The Co and Cu MRR decreased in the presence of three amino acids and showed comparable removal selectivity. The forced degradation of the amino acids under the Fenton-assisted electrooxidation confirmed that they were more readily degraded compared to BTA. Acknowledgments: This work was supported by the Semiconductor Research Corporation grant (Task 3100.001) under the Global Research Collaboration program. References Seo, J., A review on chemical and mechanical phenomena at the wafer interface during chemical mechanical planarization. Journal of Materials Research 2021, 1-23.C. Peethala, H. P. Amanapu, U. Lagudu, and S.V. Babu, J. Electrochem. Soc, 159(6), H582-H588, 2012.D.E. Speed, Chapter 11, Advances in chemical mechanical planarization (CMP) 2nd edition, Babu, S. V., Ed. 2021.G. Li et al. / Chemosphere 241 (2020) 1249932.Seo, J.; Vegi, S. S. R. K. H.; Babu, S.V. ECS Journal of Solid State Science and Technology 2019, 8 (8), P379–P387.