Nanoparticle induced wetting of polymer films and self-assembled multilayers of nanocomponents.

摘要

The control of dewetting for thin polymer films is a technical challenge and of significant academic interest. Although studies have been published on the wetting of polymer films in the presence of nanoparticles, the underlying physics is still a matter of debate. In this work, we report a systematic study of improved wetting behavior of thin polymer films containing nanoparticles, as a function of nanoparticle size and concentration. An enthalpy matched system consisting of polystyrene nanoparticles in linear polystyrene is used to show that nanoparticles are uniformly distributed in the film after spin coating and drying, however on annealing the film above its bulk glass transition temperature the nanoparticles segregate strongly to the solid substrate. We find that for a wide range of film thicknesses and nanoparticle sizes, approximately monolayer substrate coverage of nanoparticles is required for strong dewetting inhibition. We also show that cadmium selenide quantum dots inhibit dewetting of both polystyrene and PMMA thin films. Moreover, TEM microscopy images indicate that CdSe quantum dots segregate primarily to the air surface. Gain of configuration entropy of the melt linear chains promotes segregation of nanoparticles to the substrate, as occurs for polystyrene nanoparticles. However, for CdSe nanoparticles this is offset by surface energy terms which promote segregation of the nanoparticles to the air surface. We argue that this is due to the inert low-energy Oleic acid brush introduced to promote organic compatibility of the quantum dot surfaces.; Finally, we use the nanoparticle induced wetting of a polymer film due to the self-assembly of nanoparticles at the interface to construct the layered assembly of polymer-nanoparticle sandwich films. We report an alternative route to multilayer nanostructures where the layered self-assembly of the constituents is driven by the interplay between entropy, due to architectural differences, and surface energy. The approach is simple, thin film deposition is followed by an aging step to allow segregation of the components, and after stabilization of this layer, the process is repeated. We show that this enables fabrication of multilayers using a wide range of nanoparticles and non-polar polymers. We call this the Self Assembled Multilayers of Nanocomponents or SAMON process.