Thickness Gradient in Polymer Coating by Reactive Layer-by-Layer Assembly on Solid Substrate

[Image: see text] The study describes a simple yet robust methodology for forming gradients in polymer coatings with nanometer-thickness precision. The thickness gradients of 0–20 nm in the coating are obtained by a reactive layer-by-layer assembly of polyester and polyethylenimine on gold substrates. Three parameters are important in forming thickness gradients: (i) the incubation time, (ii) the incubation concentration of the polymer solutions, and (iii) the tilt angle of the gold substrate during the dipping process. After examining these parameters, the characterization of the anisotropic surface obtained under the best conditions is presented in the manuscript. The thickness profile and nanomechanical characterization of the polymer gradients are characterized by atomic force microscopy. The roughness analysis has demonstrated that the coating exhibited decreasing roughness with increasing thickness. On the other hand, Young’s moduli of the thin and thick coatings are 0.50 and 1.4 MPa, respectively, which assured an increase in mechanical stability with increasing coating thickness. Angle-dependent infrared spectroscopy reveals that the C–O–C ester groups of the polyesters exhibit a perpendicular orientation to the surface, while the C≡C groups are parallel to the surface. The surface properties of the polymer gradients are explored by fluorescence microscopy, proving that the dye’s fluorescence intensity increases as the coating thickness increases. The significant benefit of the suggested methodology is that it promises thickness control of gradients in the coating as a consequence of the fast reaction kinetics between layers and the reaction time.