Chemically dominant alkaline slurry, which is free of BTA(benzotriazole) and other inhibitors, was investigated. The synergic effect of the chelating agent and oxidant on the chemical mechanical planarization(CMP)was taken into consideration. Copper CMP slurry is mainly composed of an oxidizer, nonionic surfactant, chelating agent and abrasive particles. The effect of different synergic ratios of oxidant with chelating agent on the polishing removal rate, static etch rate and planarization were detected. The planarization results reveal that with the increase of oxidant concentration, the dishing value firstly diminished and then increased again. When the synergic ratios is 3, the dishing increases the least. A theoretical model combined with chemical-mechanical kinetics process was proposed in the investigation, which can explain this phenomenon. Based on the theoretical model, the effect of synergic ratios of oxidant with chelating agent on velocity D-value(convex removal rate minus recessed removal rate) was analyzed. The results illustrate that when the synergic ratio is between 2.5–3.5, the velocity D-value is relatively higher, thereby good planarization can be achieved in this interval. This investigation provides a new guide to analyze and study copper line corrosion in the recessed region during copper clearing polishing.
There is a lot of hydroxyl on the surface of nano SiO2 sol used as an abrasive in the chemical mechanical planarization(CMP) process, and the chemical reaction activity of the hydroxyl is very strong due to the nano effect.In addition to providing a mechanical polishing effect, SiO2 sol is also directly involved in the chemical reaction.The stability of SiO2 sol was characterized through particle size distribution, zeta potential, viscosity, surface charge and other parameters in order to ensure that the chemical reaction rate in the CMP process, and the surface state of the copper film after CMP was not affected by the SiO2 sol. Polarization curves and corrosion potential of different concentrations of SiO2 sol showed that trace SiO2 sol can effectively weaken the passivation film thickness. In other words, SiO2 sol accelerated the decomposition rate of passive film. It was confirmed that the SiO2 sol as reactant had been involved in the CMP process of copper film as reactant by the effect of trace SiO2 sol on the removal rate of copper film in the CMP process under different conditions. In the CMP process, a small amount of SiO2 sol can drastically alter the chemical reaction rate of the copper film, therefore, the possibility that Cu/SiO2 as a catalytic system catalytically accelerated the chemical reaction in the CMP process was proposed. According to the van't Hoff isotherm formula and the characteristics of a catalyst which only changes the chemical reaction rate without changing the total reaction standard Gibbs free energy, factors affecting the Cu/SiO2 catalytic reaction were derived from the decomposition rate of Cu(OH)2 and the pH value of the system, and then it was concluded that the CuSiO3 as intermediates of Cu/SiO2 catalytic reaction accelerated the chemical reaction rate in the CMP process.It was confirmed that the Cu/SiO2 catalytic system generated the intermediate of the catalytic reaction(CuSiO3/in the CMP process through the removal rate of copper film, infrared spectrum and AFM diagrams in d
