Roughness and Salt Annealing in a Polyelectrolyte Multilayer

The surface roughness of polyelectrolyte multilayers made from poly­(diallyldimethylammonium chloride), PDADMAC, and poly­(styrene sulfonate), PSS, was measured as a function of film deposition conditions. For dry multilayers, the significant roughness which builds up for thicker films is much more apparent for multilayers terminated with PSS. Corresponding roughness for PDADMA-capped multilayers may be seen by imaging in situ under electrolyte. Roughness may be substantially reduced, but not eliminated, by annealing in salt. Annealing does not lead to loss of polyelectrolyte from the film, even under conditions where the salt concentration is high enough to place the film properties beyond the glass transition. Roughness does not correlate with the molecular weight of the polyelectrolyte and is thus not caused by solution or film polymer chain conformations. The wavelength of the roughness features is approximately proportional to film thickness, which supports a mechanism whereby roughness is generated by anisotropic swelling due to water and polyelectrolyte addition in a manner similar to water uptake in hydrogels. Roughness is preserved by the glassy PSS layer and probably incorporated within the film as it grows.