Layer-by-Layer Assembly of Thin Films Containing Exfoliated Pristine Graphene Nanosheets and Polyethyleneimine

A method for the modification of surface properties through the deposition of stabilized graphene nanosheets is described. Here, the thickness of the film is controlled through the use of the layer-by-layer technique, where the sequential adsorption of the cationic polyethyleneimine (PEI) is followed by the adsorption of anionic graphene sheets modified with layers of polyethylene oxide polypropylene oxide polyethylene oxide (PEO-PPO-PEO) surfactants. The graphene particles were prepared using the surfactant-assisted liquid-phase exfoliation technique, with the low residual negative charge arising from edge defects. The buildup of the multilayer assembly through electrostatic interactions was strongly influenced by the solution conditions, including pH, ionic strength, and ionic species. Thereby, not only could the thickness of the film be tailored through the choice of the number of bilayers deposited but the viscoelastic properties of the film could also be modified by changing solution conditions at which the different species were deposited. The quartz crystal microbalance was used to measure the mass of graphene and polyelectrolyte immobilized at the interface as well as to probe the energy dissipated in the adsorbed layer.