| Since their first introduction in the early 90's, transparent barriers against oxygen and/or water vapor permeation through polymers, such as SiO 2, are the object of increasing interest in the food and pharmaceutical packaging industries, and more recently for the encapsulation of organic-based displays.; It is now well known that these thin layers possess barrier properties only if they are thicker than a certain critical thickness, dc. For example, dc is around 12 nm in the case of SiO2 on Kapton® PI; below this value, the measured “Oxygen Transmission Rate” (OTR, in standard cm3/m2/day/bar) is roughly the same as that of the uncoated polymer. Until now, no detailed research has been carried out to explain this observation, but a hypothesis was proposed in the literature, based on island-like growth structure of the coating for d ≤ dc. According to this hypothesis, the surface energy of the polymeric substrates is so low that the Volmer-Weber (island-coalescence) growth mode occurs.; We have aimed to verify this explanation, that is, to study the initial phase of silicon-compound (SiO2 and SiN) growth on four different polymeric substrates, namely polyimide (Kapton® PI), polycarbonate (Lexan® PC), polypropylene (PP), and polyethyleneterephthalate (Mylar® PET).; Three different deposition methods were used, namely reactive evaporation of SiO, radio-frequency (RF) Plasma Enhanced Chemical Vapor Deposition (RF PECVD), and Distributed Electron Cyclotron Resonance (DECR) PECVD. In this latter case, the substrates were placed in three different positions: (i) in the active glow zone, (ii) downstream, and (iii) downstream, but shielded from photon emission (e.g. VUV) from the plasma.; Angle-Resolved X-Ray Photoelectron Spectroscopy (ARXPS), Rutherford Backscattering Spectroscopy (RBS), and Scanning Electron Microscopy (SEM), the latter performed after Reactive Ion Etching (RIE) by oxygen plasma, revealed that growth indeed occurs in a Volmer-Weber mode in the case of evaporated films. The island coalescence was observed to occur at d = 1.2 nm, at which point the sticking coefficient of precursor species changes drastically.; Finally, we have investigated the presence of an “interphase” between deposited coatings and the polymeric substrate. (Abstract shortened by UMI.)... |
