We took advantage of pseudopartial wetting to promote the spreading of precursor films whose surface density smoothly decays to zero away from a sessile droplet. By following the spreading dynamics of semidilute precursor films of polybutadiene melts on silicon wafers, we measure molecular diffusion coefficients for different molar masses and temperatures. For homopolymers, chains follow a thermally activated 2D Rouse diffusion mechanism, with an activation energy revealing polymer segment interactions with the surface. This Rouse model is generalized to chains with specific terminal groups.

Nanometer-thick supported films of polymer melts spontaneously form and spread around sessile droplets that are deposited on oxidized silicon wafers. At steady state, the films become dense and adopt a uniform thickness, which is equal to twice the gyration radius of the free polymer. Remarkably, this law applies to a wide variety of melts and does not depend on the polymer chemistry nor on the surface state (oxide layer thickness, temperature, presence of water adsorbed, etc.). We show that existing theoretical descriptions cannot reproduce this experimental result. Conversely, the evolution toward this equilibrium state witnesses the specificity of the interactions at stake in these confined polymer films. The chain spreading dynamics can be modeled by taking into account both the polymer/surface friction and the polymer/polymer friction.

We investigate the evolution over time of the space profiles of precursor films spreading away from a droplet of polymer, in the poorly explored pseudo-partial wetting case. We use polystyrene melt droplets on oxidized silicon wafers. Interestingly, the film thicknesses measured by ellispometric microscopy are found in a 0.01 to 1 nm range. These thicknesses were validated by atomic force microscopy (AFM) measurements performed on the textured film obtained after a quench in temperature. From this, an effective thickness is obtained and compares well to the thicknesses measured by ellipsometry, validating the use of an optical method in this range of thickness. Ellipsometric microscopy provides a height resolution below the ångström with lateral resolution, image size and framerate well adapted to spreading precursor films. From 1 this, we demonstrate that precursor films of polystyrene consist of polymer chains with a surface density decreasing to 0 away from the droplet. We further find that the polymer chains follow a simple diffusive law with diffusion coefficient independent of density. This demonstrate that polystyrene chains spread independently in precursor films in pseudo partial wetting condition. This behavior differs significantly from the case of chains spreading in total wetting, for which the diffusion coefficient was found in the literature to depend on surface density or thickness.