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The role of additives in copper electroplating baths in the damascene process has been investigated. We proposed a bottom-up filling model and confirmed it by comparing the experimental and simulation results. Janus Green B and Basic Blue 3 which absorb on the copper surface and suppress copper deposition were examined for additive use to improve filling capability. Damascene copper grew uniformly in the bath that contained Basic Blue 3. But it grew preferentially from the bottom of the trench for Janus Green B. Addition of Janus Green B produced a continuous concentration gradient in the sub-micron trench when the additive’s diffusion rate and consumption rate on the copper surface were well balanced. We estimated filling profiles from numerical simulation using parameters that were determined by an electrochemical method. These profiles agreed well with the experimental results.

Electrochemical and Simulative Studies of Trench Filling Mechanisms in the Copper Damascene Electroplating Process