We have mimicked the layer-by-layer self-assembling process of monodisperse colloidal particles at a solid-liquid interface using the extended random sequential adsorption model of hard spheres. We have studied five multilayer structures of similar thickness, each created at a different single-layer surface coverage. For each multilayer, we have determined its particle volume fraction as a function of distance from the interface. Additionally, we have characterized the film structure in terms of 2D and 3D pair-correlation functions. We have found that the coverage of about 0.3 is optimal for producing a uniform, constant-porosity multilayer in a minimum number of adsorption cycles. The single-layer coverage has also a significant effect on the primary maximum of 2D radial distribution function. In the case of multilayer with the coverage lower than 0.30 the 2D pair-correlation functions of even layers exhibit maxima decreasing with the increase in the layer number. We have verified our theoretical predictions experimentally. We have used fluorescence microscopy to determine the 2D pair-correlation functions for the second, third, and fourth layers of multilayer formed of micron-sized spherical latex particles. We have found a good agreement between our theoretical and experimental results, which confirms the validity of the extended RSA model. (C) 2015 Elsevier B.V. All rights reserved.