Application of nanometer thick fluoropolymer films onto metal and semiconducting substrates is described. In the first step, nanometer-sized polymer particles are generated by a process of homogeneous nucleation during the rapid expansion of supercritical fluid solutions. These gas-phase particles are then charged as they are being formed by application of a high voltage to the expansion nozzle. In this way the charged nanoparticles can be collected on a solid surface forming uniform coatings with thicknesses from tens of nanometers to several micrometers thick. Supercritical carbon dioxide solutions of three different fluoropolymers were used to generate different types of coatings. This represents a ‘green’ process for film deposition. A further unique aspect of this process is that the small charged nanoparticles can be deposited to electrically conducting microscopic regions with a spatial resolution better than 50 nm.