Pulse-Plating of Copper-Silver Alloys for Interconnect Applications

The electrodeposition of Cu-Ag alloys was studied as a possible application for interconnect technology, where Cu-Ag alloys may be less susceptible to electromigration than Cu alone. The presence of chloride in state-of-the-art copper plating electrolytes limited the solubility of Ag. However, pulse-plating approach enabled a wide range of Cu-Ag alloy compositions at substantial chloride concentration levels. The deposition of Ag was driven by the displacement reactions between the metallic copper and ionic silver during the off-time. Measured alloy compositions were consistent with theoretical estimates at various electrolyte concentrations, electrode rotation speeds, pulse frequencies and duty cycles. However, organic additives decreased incorporation of Ag into the alloy. It was also discovered that CuSO4 center dot 5H(2)O from a number of major chemical suppliers contained Ag as an impurity. The roughness of the films was significant when produced by pulsed plating, but was shown to be substantially reduced in the presence of a leveling agent. Additionally, the concentration of chloride in the electrolyte was shown to significantly affect surface quality of the deposited Cu-Ag thin films. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.066211jes] All rights reserved.