Charge density and pH effects on polycation adsorption on poly-Si, SiO2, and Si3N4 films and impact on removal during chemical mechanical polishing

The pH-dependent interactions of five aqueous abrasive-free polycationic solutions, all at a concentration of 250 ppm, with poly-Si, SiO(2), and Si(3)N(4) films and IC1000 polishing pads used in chemical mechanical polishing have been investigated and compared with the interaction of poly(diallyldimethyl ammonium chloride) (PDADMAC) that was investigated recently. Three of the polycationic solutions, poly(dimethylamine-co-epichlorohydrin-co-ethylenediamine), poly(allylamine), and poly(ethylene imine) (PEI) enhance poly-Si removal rates (RRs) to the range of about 500 to 600 nm/min at pH 10. In contrast, poly(acrylamide) (PAA) suppressed poly-Si RRs to about 50 nm/min, whereas with a copolymer of PAA and PDADMAC, the RRs were lower than those obtained with PDADMAC but higher than those obtained with PAA. For all the polycationic solutions, the RRs of both SiO(2), and Si(3)N(4) films were ~0 nm/min. These solutions offer a low-defect option for the processing of emerging FinFET devices. The variation in the RR magnitude and dependence on pH among the different polycations is related to the relative charge density of the polycations as well as the films being polished, consistent with ζ potential data. Based on the ζ potential data and earlier published reports, it is suggested that the strong polycation-mediated bridging interactions between the polarized and weakened Si-Si bonds of the poly-Si surface and the polyurethane IC 1000 pad are responsible for the high poly-Si RRs.