Layer-by-layer self-assembly of multilayer films based on humic acid

Multilayer films consisting of negatively charged humic acid and positively charged polyelectrolyte have been fabricated on various substrates using the layer-by-layer self-assembly technique. The thickness (linearly increasing with the square root of NaCl concentration) and refractive index of the films determined by ellipsometry can be regulated by ionic strength through adjusting the coiling of the polyelectrolyte chains for assembly. The cone-shaped features on surface obtained by atomic force microscope are derived from the negatively charged colloidal humic acid binding with polyelectrolyte cation. The smooth features are corresponding to the dissociated humic acid with carboxylate ion (―COO−) electrostatically attracted on polyelectrolyte cation. These results are verified by Fourier transform infrared spectra. The linear dependence of the peak current on the square root of the scan rate revealed by the cyclic voltammetry indicates that the redox process at the electrode surface is diffusion-limited and the charge transport does not involve the film itself.