Electrochemical Studies in Fluoride Based Solutions for Semiconductor Processing Applications

Abstract

Fluoride based chemical systems are widely used at various stages in microelectronic processing, particularly for wet cleaning and etching applications. Some examples include the use of semi aqueous fluoride (SAF) solutions in back end of line cleaning, the use of dilute HF solutions as etchants for SiO2 and HF-HNO3 or HF-H2O2 solutions as isotropic etchants for silicon. In this work, the use of fluoride based solutions for two applications relevant to semiconductor processing are considered.In the first part of the study, cleaning of post plasma etch residues generated during fabrication of copper damascene structures was investigated in semi aqueous fluoride (SAF) formulations based on dimethyl sulfoxide and ammonium fluoride. Formulations designed for residue removal should be able to remove the residue effectively, without causing critical dimension loss during the process cycle. A systematic evaluation of solution variables (solvent content and pH) was conducted and the extent of removal of model copper oxide films and selectivity over copper and carbon doped oxide (CDO) films were used as metrics to evaluate the formulations. Results of the study indicate that the presence of solvent is necessary to achieve reasonable etch selectivity over dielectric films. Additionally, a removal end point detection technique based on electrochemical impedance spectroscopy was developed, which could potentially help in the optimization of cleaning time with minimal dielectric loss. This method was applied to monitor the removal of copper oxide films as well as residue from patterned test structures.In the second part of the study, electrochemical formation of porous silicon films in hydrofluoric acid (HF) solutions was investigated, for potential applications in advanced packaging. Specifically, porous silicon formation in solution mixtures containing HF, acetic acid and peroxide, was studied. The effect of variables including current density, substrate resistivity, HF, acetic acid and peroxide concentration, on key porous film characteristics such as growth rate, porosity and microstructure, was explored. Addition of peroxide was found to significantly increase the porosity and growth rate of the film, as a result of enhanced chemical dissolution and films with porosities as high as 95% were obtained. Additionally, in solutions containing peroxide, a variety of microstructural features, such as nanopores, micron sized pores, truncated pyramidal structures and silicon needles were observed, under various fabrication conditions.