Electrolyte composition and removal mechanism of Cu electrochemical mechanical polishing

The optimization of electrolytes and the material removal mechanisms for Cu electrochemical mechanical planarization (ECMP) at different pH values including 5-methyl-1H-benzotriazole (TTA), hydroxyethylidenediphosphoric acid (HEDP), and tribasic ammonium citrate (TAC) were investigated by electrochemical techniques, X-ray photoelectron spectrometer (XPS) analysis, nano-scratch tests, AFM measurements, and polishing of Cu-coated blanket wafers. The experimental results show that the planarization efficiency and the surface quality after ECMP obtained in alkali-based solutions are superior to that in acidic-based solutions, especially at pH=8. The optimal electrolyte compositions (mass fraction) are 6% HEDP, 0.3% TTA and 3% TAC at pH=8. The main factor affecting the thickness of the oxide layer formed during ECMP process is the applied potential. The soft layer formation is a major mechanism for electrochemical enhanced mechanical abrasion. The surface topography evolution before and after electrochemical polishing (ECP) illustrates the mechanism of mechanical abrasion accelerating electrochemical dissolution, that is, the residual stress caused by the mechanical wear enhances the electrochemical dissolution rate. This understanding is beneficial for optimization of ECMP processes.