Tungsten passivation layer (WO3) formation mechanisms during chemical mechanical planarization in the presence of oxidizers

Effects of single and mixed oxidants of Fe(NO3)(3) and H2O2 containing acidic silica slurries were studied to investigate the mechanism of tungsten (W) chemical mechanical planarization (CMP). The W polishing rate obtained from the CMP test depicted high W polishing rate in the presence of mixed oxidants of Fe(NO3)(3) and H2O2 as compared to a single oxidant of either H2O2 or Fe(NO3)(3). The formation of a passive layer of tungsten oxide (WO3) and W dissolution could be the reason for these results as confirmed by XPS. Further investigation revealed that the generation of much stronger oxidants of hydroxyl radicals ((OH)-O-center dot) was solely responsible for WO3 layer formation. Quantitative evaluation of (OH)-O-center dot generation was estimated using a UV-visible spectrophotometer and confirmed that in-situ generation of hydroxyl radicals ((OH)-O-center dot) could be a main driving force for the high W polishing rate by converting a hard W film into a soft passive film of WO3. WO3 film formation was further confirmed using potentiodynamic polarization studies, which showed a smaller value of corrosion current density (Icon) in mixed oxidants of Fe(NO3)(3) and H2O2 as compared to the large values of I-corr observed for H2O2 alone. This study revealed that a single oxidizer of either Fe(NO3)(3) or H2O2 was not capable of achieving a high W removal rate. Rather, only mixed oxidants of Fe(NO3)(3) and H2O2 could cause a high W polishing rate due to excessive in-situ generation of 'OH radicals during the W CMP process.

Automated summary

This study investigates the effects of single and mixed oxidants Fe(NO3)(3) and H2O2 on tungsten (W) CMP, revealing that mixed oxidants lead to a higher W polishing rate due to the in-situ generation of hydroxyl radicals ((OH)-O-center dot). This excessive generation of (OH)-O-center dot results in the formation of a passive WO3 film, converting the hard W film into a soft layer, ultimately enhancing the W removal rate during CMP.