Copper CMP Modeling: Millisecond Scale Adsorption Kinetics of BTA in Glycine-Containing Solutions at pH 4

Millisecond scale benzotriazole (BTA) adsorption kinetics in acidic aqueous solution containing 0.01 M glycine and 0.01 M BTA have been investigated. Chronoamperometry was used to measure current densities on the surface of a micro-copper electrode in pH 4 aqueous solutions containing 0.01 M glycine with or without 0.01 M BTA. In the presence of BTA the current density decreased as the inverse of the square root of time for a few seconds due to adsorption of BTA. At potentials above 0.4 V saturated calomel electrode the current leveled off after a second or so due to the formation of a Cu(I)BTA monolayer on the copper surface. Based on these data a governing equation was constructed and solved to determine the initial kinetics of BTA adsorption. Analysis shows that material removal during copper chemical mechanical planarization (CMP) in this slurry chemistry occurs mostly by direct dissolution of copper species into the aqueous solution rather than mechanical removal of oxidized or pure copper species and that each interaction between a pad asperity and a given site on the copper removes only a small fraction of the Cu(I)BTA species present at that site.