Ordered polyelectrolyte multilayers. 4. Internal structure of clay-based multilayers

We report on the growth and structure of hybrid clay-based multilayers obtained by electrostatic self-assembly (also known as layer-by-layer assembly) of poly(didllylpyrrolidinium bromide) and a synthetic hectorite (Laponite). By combining ellipsometry, atomic force microscopy, and specular and off-specular grazing angle X-ray scattering measurements, we show that platelets pack in the vertical direction according to a distribution of distances between nearest neighbors of about 3 Angstrom standard deviation. The accumulation of such random fluctuations in the vertical direction results in the loss,of layering of the platelets farther than about 75 Angstrom from the substrate. In this respect, most of the film should be considered as a nanocomposite with preferential orientation of the platelets, rather than as a real multilayer. The model is quantitatively supported by simulations of the specular and off-specular scattering of such multilayers.