Patterning Microparticles on a Template of Aggregated Cationic Dye

Abstract

Patternwise aggregation of charged molecules on a surface is potentially a facile approach to generate a template on which to pattern oppositely charged microparticles. We report on the patterning of silica microparticles by a system comprising a photopatternable copolymer and an aggregate forming penta-cationic cyanine dye. A thin film of the copolymer, composed of a molar excess of styrenesulfonic acid oxime ester to cross-linkable glycidyl methacrylate monomomers, was exposed through a mask and neutralized, resulting in a pattern of hydrophobic areas, and where exposed, a hydrophilic cross-linked film with sodium poly(styrenesulfonate) domains. The occurrence and locus of aggregation of an aqueous solution of the dye, applied to the patterned surface was established by absorbance and fluorescence spectroscopy and atomic force microscopy. In exposed areas, dye is imbibed and aggregation induced in sodium styrenesulfonate domains internal to the layer, whereas in the unexposed areas the dye aggregates on the hydrophobic surface. Aqueous anionic silica microparticles applied to the dye treated patterned surface and then rinsed, are retained in the unexposed areas having cationic surface aggregates, but rejected from the exposed areas with internal dye aggregates as these areas retain net negative charge. Mask exposure, absent dye treatment, did not result in patterning as negatively charged microparticles were nowhere retained, and positively charged particles were everywhere retained. The extent of surface coverage by the dye in unexposed areas was deposition time dependent, and ranged from isolated patches covering about 20 percent of the polymer surface to a surface saturated layer, with silica particle patterning robust over the range of dye surface coverages studied. The force requirements to pattern the denser than water silica microparticles are identified, and particle and polymer film surface potentials that meet the critical repulsion force requirement are mapped using an established sphere-to-flat surface electric double layer (EDL) model.