Deposition of Super-Hydrophobic and Oleophobic Fluorocarbon Films in Radio Frequency Glow Discharges L. Laguardia, * 1 D. Ricci, 1 E. Vassallo, 1 A. Cremona, 1 E. Mesto, 2 F. Grezzi, 1 F. Dellera 1 Fluorocarbon films using a monomer, 1H, 1H, 2H-perfluoro–1-dodecene were depos- ited in a continuous radio frequency (RF) glow discharge, the process was carried out in a parallel-plate RF discharge onto stainless steel reactor in order to produce coating with a water-and oil–repellent surface. Fourier-Transform Infrared spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS) revealed that the films obtained contain mainly perfluoromethylene (CF 2 ) species. Film wettability was tested using water and hydrocarbon liquids for contact angle measurements, furthermore surface energy was also calculated. Oil-repellency was found to increase as the amount of CF 2 species increases in the film structure. Film morphology was studied by Atomic Force Microscopy (AFM), films showing an usual morphology from that typical of Plasma Polymerised Fluorocarbon (PPFC) films. The combination of the low surface energy coating and the surface morphology produces materials which are both water and oil repellency. Keywords: fluoropolymer; glow-discharge; oil-repellency; surface energy; water-repellency Introduction Fluorocarbon films (CFx) obtained by plasma enhanced chemical vapour deposi- tion (PECVD) in continuous process are attractive materials applied in various fields for their outstanding properties: good adhesion to organic and inorganic sub- strates, [1] the presence of low intermolecu- lar forces, which give rise to relatively inert surfaces with extremely low free energy, [2] biocompatibility, [3] a low friction coeffi- cient. [4] Thin films with a tuneable F/C ratio can be deposited in glow discharge with many different fluorinated monomers, such as fluoroalkyls, fluorohydroalkyls, cyclo- fluoroalkyls, fluorobenzene, as pure feed or in mixture with various additives. [5] The feed supplies the plasma phase with CF x radicals, F atoms, and with charged particles. CF x radicals are the building blocks for the polymeric deposits. The relative abundance of these active species are affected not only by monomer feed but also by input power, pressure, feed addi- tives, etc. [6] Films derived from many fluoromono- mers show excellent hydrophobicity, [7] but few studies have specifically examined oleophobicity. Conventionally, plasma polymerization of fluorocarbon films has been accom- plished using a low molecular mass mono- mer, such as C 2 F 6 , [8] C 4 F 8 . [9] A few research groups have investigated higher molecular mass monomers to produce a film domi- nated by CF 2 species. In our work, continuous R.F. glow dis- charge fed with 1H, 1H, 2H-perfluoro-1- dodecene monomer was used to deposit CF x films on silicon substrate to produce water and oil- repellent surfaces. Macromol. Symp. 2007, 247, 295–302 DOI: 10.1002/masy.200750133 295 1 Istituto di Fisica del Plasma ENEA-CNR- EURATOM, Milano, Italy E-mail: Laguardia@ifp.cnr.it 2 Universita ` degli Studi di Bari, Dipartimento Geomi- neralogico, Italy Copyright ß 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim