ABSTRACT
In this study, the chemical decomposition of a polyimide-film (i.e., a PI-film)-surface into a soft-film-surface containing negatively charged pyromellitic dianhydride (PMDA) and neutral 4,4'-oxydianiline (ODA) was successfully performed. The chemical decomposition was conducted by designing the slurry containing 350 nm colloidal silica abrasive and small molecules with amine functional groups (i.e., ethylenediamine: EDA) for chemical-mechanical planarization (CMP). This chemical decomposition was performed through two types of hydrolysis reactions, that is, a hydrolysis reaction between OH- ions or R-NH3+ (i.e., EDA with a positively charged amine groups) and oxygen atoms covalently bonded with pyromellitimide on the PI-film-surface. In particular, the degree of slurry adsorption of the PI-film-surface was determined by the EDA concentration in the slurry because of the presence of R-NH3+, that is, a higher EDA concentration resulted in a higher degree of slurry adsorption. In addition, during CMP, the chemical decomposition degree of the PI-film-surface was principally determined by the EDA concentration; that is, the degree of chemical composition was increased noticeably and linearly with the EDA concentration. Thus, the polishing-rate of the PI-film-surface increased notably with the EDA concentration in the CMP slurry.
ABSTRACT
For scaling-down advanced nanoscale semiconductor devices, tungsten (W)-film surface chemical mechanical planarization (CMP) has rapidly evolved to increase the W-film surface polishing rate via Fenton-reaction acceleration and enhance nanoscale-abrasive (i.e., ZrO2) dispersant stability in the CMP slurry by adding a scavenger to suppress the Fenton reaction. To enhance the ZrO2 abrasive dispersant stability, a scavenger with protonate-phosphite ions was designed to suppress the time-dependent Fenton reaction. The ZrO2 abrasive dispersant stability (i.e., lower H2O2 decomposition rate and longer H2O2 pot lifetime) linearly and significantly increased with scavenger concentration. However, the corrosion magnitude on the W-film surface during CMP increased significantly with scavenger concentration. By adding a scavenger to the CMP slurry, the radical amount reduction via Fenton-reaction suppression in the CMP slurry and the corrosion enhancement on the W-film surface during CMP performed that the W-film surface polishing rate decreased linearly and notably with increasing scavenger concentration via a chemical-dominant CMP mechanism. Otherwise, the SiO2-film surface polishing rate peaked at a specific scavenger concentration via a chemical and mechanical-dominant CMP mechanism. The addition of a corrosion inhibitor with a protonate-amine functional group to the W-film surface CMP slurry completely suppressed the corrosion generation on the W-film surface during CMP without a decrease in the W- and SiO2-film surface polishing rate.
ABSTRACT
Face-centered-cubic crystallized super-fine (~ 2 nm in size) wet-ceria-abrasives are synthesized using a novel wet precipitation process that comprises a Ce4+ precursor, C3H4N2 catalyst, and NaOH titrant for a synthesized termination process at temperature of at temperature of 25 °C. This process overcomes the limitations of chemical-mechanical-planarization (CMP)-induced scratches from conventional dry ceria abrasives with irregular surfaces or wet ceria abrasives with crystalline facets in nanoscale semiconductor devices. The chemical composition of super-fine wet ceria abrasives depends on the synthesis termination pH, that is, Ce(OH)4 abrasives at a pH of 4.0-5.0 and a mixture of CeO2 and Ce(OH)4 abrasives at a pH of 5.5-6.5. The Ce(OH)4 abrasives demonstrate better abrasive stability in the SiO2-film CMP slurry than the CeO2 abrasives and produce a minimum abrasive zeta potential (~ 12 mV) and a minimum secondary abrasive size (~ 130 nm) at the synthesis termination pH of 5.0. Additionally, the abrasive stability of the SiO2-film CMP slurry that includes super-fine wet ceria abrasives is notably sensitive to the CMP slurry pH; the best abrasive stability (i.e., a minimum secondary abrasive size of ~ 130 nm) is observed at a specific pH (6.0). As a result, a maximum SiO2-film polishing rate (~ 524 nm/min) is achieved at pH 6.0, and the surface is free of stick-and-slip type scratches.
