Investigations in the initial build-up stages of polyelectrolyte multilayers by laser reflectometry and atomic force microscopy

This work aims to investigate the initial build-up stages of polyelectrolyte multilayers formed by the successive deposition of the weakly charged Poly(Allyl amine, HCl), PAH and the strong acid Poly(Styrene Sulfonate), PSS, on silica at pH = 9. Two complementary tools were used: laser reflectometry to determine the step-by-step deposited weight of each polymer and Atomic Force Microscopy (AFM) to characterize the topography and measure the thickness of the film. The experiments show that the deposited weight of PAH is the same at each step (around 0.5 mg.m− 2), whereas that of PSS increases more or less linearly along with the step number. Starting at the second polymer deposit (PSS), the structure of the film is very heterogeneous, with a thin polymer layer and bumps that are attributed to the presence of PSS/PAH hydrophobic complexes. The amount of bumps and their height were determined at each of the ten first polymer deposits. The film thickness between the bumps was evaluated by scratching small areas with an AFM tip. Our results support a former description of film growth, based on the electrostatic interactions between the two polymers and the substrate. They also reveal different the roles of the two polymers in the growth of the films: PAH is responsible for the progressive bi-dimensional coverage of the surface area and PSS for the increase in the thickness of the film.