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.

A Fenton reaction and a corrosion inhibition strategy were designed for enhancing the polishing rate and achieving a corrosion-free Ge1Sb4Te5 film surface during chemical-mechanical planarization (CMP) of three-dimensional (3D) cross-point phase-change random-access memory (PCRAM) cells and 3D cross-point synaptic arrays. The Fenton reaction was conducted with 1,3-propylenediamine tetraacetic acid, ferric ammonium salt (PDTA–Fe) and H2O2. The chemical oxidation degree of GeO2, Sb2O3, and TeO2 evidently increased with the PDTA–Fe concentration in the CMP slurry, such that the polishing rate of the Ge1Sb4Te5 film surface linearly increased with the PDTA–Fe concentration. The addition of a corrosion inhibitor having protonated amine functional groups in the CMP slurry remarkably suppressed the corrosion degree of the Ge1Sb4Te5 film surface after CMP; i.e., the corrosion current of the Ge1Sb4Te5 film surface linearly decreased as the corrosion inhibitor concentration increased. Thus, the proposed Fenton reaction and corrosion inhibitor in the Ge1Sb4Te5 film surface CMP slurry could achieve an almost recess-free Ge1Sb4Te5 film surface of the confined-PCRAM cells, having an aspect ratio of 60-nm-height to 4-nm-diameter after CMP.

Recently, as an alternative solution for overcoming the scaling-down limitations of logic devices with design length of less than 3 nm and enhancing DRAM operation performance, 3D heterogeneous packaging technology has been intensively researched, essentially requiring Si wafer polishing at a very high Si polishing rate (500 nm/min) by accelerating the degree of the hydrolysis reaction (i.e., Si-O-H) on the polished Si wafer surface during CMP. Unlike conventional hydrolysis reaction accelerators (i.e., sodium hydroxide and potassium hydroxide), a novel hydrolysis reaction accelerator with amine functional groups (i.e., 552.8 nm/min for ethylenediamine) surprisingly presented an Si wafer polishing rate >3 times higher than that of conventional hydrolysis reaction accelerators (177.1 nm/min for sodium hydroxide). This remarkable enhancement of the Si wafer polishing rate for ethylenediamine was principally the result of (i) the increased hydrolysis reaction, (ii) the enhanced degree of adsorption of the CMP slurry on the polished Si wafer surface during CMP, and (iii) the decreased electrostatic repulsive force between colloidal silica abrasives and the Si wafer surface. A higher ethylenediamine concentration in the Si wafer CMP slurry led to a higher extent of hydrolysis reaction and degree of adsorption for the slurry and a lower electrostatic repulsive force; thus, a higher ethylenediamine concentration resulted in a higher Si wafer polishing rate. With the aim of achieving further improvements to the Si wafer polishing rates using Si wafer CMP slurry including ethylenediamine, the Si wafer polishing rate increased remarkably and root-squarely with the increasing ethylenediamine concentration.

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