| The microelectronics industry is using copper as the interconnect material for microchips. A study of copper electropolishing is important for the process development of a new, low downforce approach, which is being developed to replace chemical mechanical polishing (CMP) of the copper overburden. A promising technology is a combination of electropolishing with conventional CMP.; Electropolishing of copper in phosphoric acid has been studied for, more than 70 years. Previous work has shown that the polishing rate, as measured by current density is directly related to the viscosity of the electrolyte. Also, the limiting species is water. In this study, a multidimensional design of experiments was performed to develop an in-depth model of copper electropolishing. Phosphoric acid was mixed with alcohols of different molecular weight and related viscosity to investigate how the solvents' properties affected polishing. The alcohols used were methanol, ethanol, isopropanol, butanol, ethylene glycol, and glycerol. The limiting current densities and electrochemical behavior of each solution was measured by potentiodynamic and potentiostatic experiments. Also, the kinematic viscosity and density were measured to determine the dynamic viscosity to investigate the relationship of current density and viscosity. Water, methanol, ethanol, and isopropanol solutions were also examined at 20°C to 60°C. Next, the relative percentage of dissociated phosphoric acid was measured by Raman spectroscopy for each polishing solution. Raman spectroscopy was also used to measure the relative dissociation of phosphoric acid inside the polishing film. Additionally, wafers were electropolished and electrochemical mechanically polished to investigate the effects of the different solvents, fluid flow, current, and potential.; The results of these experiments have shown that the molecular mass and the ability of the solvent to dissociate phosphoric acid are the primary electrolyte properties that control copper electropolishing. The dependence of the polishing rate on viscosity seen in previous studies is purely consequential. Therefore, by controlling the type and concentration of alcohol in the electropolishing solution the polishing rate can be controlled. |
