Adhesion of silica abrasive nanoparticles to a poly(vinyl alcohol) (PVA) brush surface in a post-CMP (chemical mechanical planarization) cleaning leads to serious 1 problems in yield enhancement of semiconductor fabrication. However, the nanoscale adhesion mechanism and its correlation with process conditions have hardly been understood. In this study, we investigated the influence of ammonia in the cleaning solution on silica nanoparticle adhesion to a PVA surface. By atomic force microscopy (AFM), we directly measured adhesion forces between a nanoscale silica probe and a PVA brush surface in various solutions and found that ammonia has a significant inhibitory effect against silica nanoparticle adhesion to a PVA surface. Importantly, we found that this effect cannot be explained by the electrostatic interactions alone, but also involves steric repulsion between silica and hydrated PVA. We also performed molecular-scale three-dimensional scanning force microscopy (3D-SFM) imaging and contact angle measurements, and found that ammonia promotes hydration and swelling of PVA. Furthermore, we performed molecular dynamics simulations and found that ammonia promotes dynamic rearrangements of hydrogen bonding networks (HBNs) at a PVA-water interface, giving extra flexibility to the PVA chains. Such flexibility promotes local swelling of PVA and inhibits silica nanoparticle adhesion to a PVA surface. This provides important guidelines for optimizing nanoscale structures and interactions of brush surfaces and abrasive nanoparticles in post-CMP cleaning.

Anti-freezing surfactants form an adsorption layer at the solid–water interface to inhibit the nucleation and growth of ice. However, this mechanism has not been elucidated at the molecular scale because of the difficulties in visualizing such adsorption structures. In this study, we overcome this limitation by directly visualizing the three-dimensional (3D) adsorption structures of anti-freezing surfactants, hexadecyltrimethylammonium bromide (C16TABs), on sapphire (0001) surfaces through 3D scanning force microscopy. We present molecularly resolved two-dimensional/3D images of the adsorption structures in solutions of 1, 10, and 100 ppm. At 1 ppm, the molecules form a monolayer with a flat-lying configuration. At 10 ppm, the molecular orientation is closer to the upright configuration, with a relatively large tilt angle. At 100 ppm, the molecules form a bilayer with almost upright configurations, providing excellent screening of the sapphire surface from water. Owing to the steric and electrostatic repulsion between adjacent molecular head groups, the surface of the bilayer exhibits relatively large fluctuations, inhibiting the formation of stable ice-like structures. The understanding of molecular-level mechanisms provides important guidelines for improving the design of anti-freezing surfactants for practical applications such as car coolants.

Stimuli-responsive polyelectrolyte brushes adapt their physico-chemical properties according to pH and ion concentrations of the solution in contact. We synthesized a linear poly (acrylic acid) functionalized bearing cysteine side chains...