Contamination and galvanic corrosion in metal chemical-mechanical planarization

Abstract

Chemical mechanical planarization (CMP) of metals is a critical process in the manufacturing of ultra-large scale integrated (ULSI) circuit devices. The overall success of a CMP process requires minimal particulate and metallic contamination of the structures subjected to CMP. The objective of this study was to investigate alumina particle contamination during tungsten CMP, copper contamination in copper CMP, and galvanic corrosion between metal films and adhesion layers during the final stages of tungsten and copper CMP. Particular attention was paid to the use of short chain organic carboxylic acids in reducing the contamination. Both electrokinetic and uptake measurements showed that citric acid and malonic acid interact with alumina particles by electrostatic as well as specific adsorption forces. Systematic immersion contamination and polishing experiments were carried out to demonstrate the effectiveness of the acids in controlling alumina particulate contamination on wafer surfaces. The difference in the surface cleanliness was interpreted using the electrokinetic data and the calculated interaction energy between alumina particles and the wafer surface. Electrochemical tests showed no severe attack on tungsten films by the acids. Copper ions were found to adsorb onto the silicon dioxide surface, leading to copper contamination levels of upto 10¹³ atoms/cm². The extent of copper contamination was found to depend on the solution pH and the presence of additives such as hydrogen peroxide. Both electrokinetic measurements and immersion contamination experiments showed that citric acid can reduce the copper contamination on the silicon dioxide surface. TiN is more noble than tungsten in the solutions containing oxidants used in tungsten CMP slurries. The most significant corrosion of tungsten was found in the presence of hydrogen peroxide. Copper was found to be more noble than tantalum in acidic solutions. However, in alkaline ammonium hydroxide solutions, the relative nobility of copper and tantalum can be reversed by adding hydrogen peroxide. The corrosion of tungsten and copper appears to be very minimally affected by coupling with TiN and tantalum, respectively.