Mechanistic Investigations of Ruthenium Polishing Enabled by Heterogeneous Catalysis With Titania-based Slurries

Abstract

Difficulties and challenges have been widely encountered in the chemical mechanical planarization (CMP) of noble metals used as diffusion barrier films due to hardness, chemical inertness and toxic oxidation products, in particular for Ru polishing. A commercial CMC Ru polishing slurry that successfully addressed the safety concerns was based on a high pH (8.4) polymer-treated-alumina-based multi-additive slurry containing complexing reagents (carboxylic acids and salts), corrosion inhibitors, surfactants, and hydrogen peroxide as a mild, non-aggressive oxidizer. Recently, our efforts had been redirected towards the development of a new generation of low pH barrier slurries based on an entirely new concept employing unique Lewis acid type abrasives. This class of materials is well known to be highly reactive in dielectrics polishing (ceria, zirconia, titania), but far less is known about their interactions with Ru, Cu or Ta.

In this presentation, we will elaborate the unexpected discovery that hard, chemically inert, noble metals such as ruthenium can be polished easily by virtually abrasive-free and/or oxidizer-free TiO₂ based slurries. Of particular importance is the finding that the polymorphic phase of TiO₂ (anatase or rutile), its surface chemistry (functional groups, Lewis acid/base character), pH induced surface modification and reactivity, can all mediate the abrasive particle's adsorption properties, catalytic activity and ultimately, its slurry polishing performance.