Chemical Systems for Electrochemical Mechanical Planarization of Copper and Tantalum Films

Abstract

Electro-Chemical Mechanical Planarization (ECMP) is a new and highly promising technology just reaching industrial application; investigation of chemistries, consumables, and tool/control approaches are needed to overcome technological limitations. Development of chemical formulations for ECMP presents several challenges. Unlike conventional CMP, formulations for ECMP may not need an oxidant. Organic additives, especially inhibitors used to control planarity (i.e. to protect recessed regions), need to be stable under applied anodic potential. To have a high current efficiency, the applied current should not induce decomposition of the formulations. In addition, to enable clearing of the copper film, the interactions between multiple exposed materials (barrier material as well as copper) must be considered. Development of a full sequence ECMP process would require the removal of the barrier layer as well. Chemical systems that exhibit a 1:1 selectivity between the barrier layer and copper would be ideal for the barrier removal step of ECMP. The main goal of this research is to investigate the chemistries suitable for ECMP of copper and tantalum films. Copper was electroplated onto the gold electrode of quartz crystals, and its dissolution/passivation behavior in hydroxylamine solutions was studied at different applied potential values. The dissolution rate of copper is pH dependent and exhibits a maximum in the vicinity of pH 6. Copper dissolution increases with respect to overpotential (η) and dissolution rates as high as 6000 Å/min have been obtained at overpotential of 750mV. While both benzotriazole (BTA) and salicylhydroxamic acid (SHA) serve as good inhibitors at lower overpotentials, their effectiveness decreases at higher overpotentials. A fundamental study was undertaken to evaluate the usefulness of a sulfonic acid based chemical system for the removal of tantalum under ECMP conditions. Tantalum as well as copper samples were polished at low pressures (~0.5 psi) under galvanostatic conditions in dihydroxy benzene sulfonic acid (DBSA) solutions maintained at different pH values. At a current density of 0.5 mA/cm² and a pH of 10, tantalum removal rate of 200 Å/min with a 1:1 selectivity to copper was obtained in 0.3M DBSA solutions containing 1.2M H₂O₂. The presence of a small amount (~ 0.1%) of colloidal silica particles was required to obtain good removal rates. A comparison of DBSA and methane sulfonic acid (MSA) based chemical system was studied for the removal of tantalum. The performance of DBSA is better than that of MSA. Additionally, DBSA solution has been used for tantalum nitride removal under ECMP conditions. However, DBSA is not as effective for tantalum nitride as it is for tantalum. Polishing of the patterned test structure in optimized solution containing 0.01M BTA results in complete removal of barrier layer and surface planarity is achieved.