Copper Contamination Mechanism of Silicon Substrates from HF Solutions

The contamination of silicon wafers from dilute HF solutions containing ultratrace levels of metallic ion impurities is a subject of constant interest. The mechanism of copper electroless deposition from HF onto monocrystalline silicon was investigated using a new electrochemical cell, which proved to be a very sensitive detector for in situ characterization of silicon surfaces. Upon addition of copper trace amounts, the open-circuit potential was observed to shift rapidly towards more positive values at a rate nearly proportional to the copper concentration. All potential/ time curves tend to reach a limiting value of the potential, while quantitative measurements of radioactive tracers revealed that during a few tens of minutes, copper ions were continuously reduced on the silicon surface. Electrochemical potentials and voltammetric measurements were interpreted in terms of the mixed potential theory and led to the conclusion that copper nuclei act as a catalyst which enhances the cathodic activity for protons reduction. The model was supported by AFM observations which demonstrated the initiation of corrosion pits around the nuclei.