Temperature-dependent subsurface growth during atomic layer deposition on polypropylene and cellulose fibers.

Nucleation and subsequent growth of aluminum oxide by atomic layer deposition (ALD) on polypropylene fiber substrates is strongly dependent on processing temperature and polymer backbone structure. Deposition on cellulose cotton, which contains ample hydroxyl sites for ALD nucleation and growth on the polymer backbone, readily produces a uniform and conformal coating. However, similar ALD processing on polypropylene, which contains no readily available active sites for growth initiation, results in a graded and intermixed polymer/inorganic interface layer. The structure of the polymer/inorganic layer depends strongly on the process temperature, where lower temperature (60 degrees C) produced a more abrupt transition. Cross-sectional transmission electron microscopy images of polypropylene fibers coated at higher temperature (90 degrees C) show that non-coalesced particles form in the near-surface region of the polymer, and the particles grow in size and coalesce into a film as the number of ALD cycles increases. Quartz crystal microbalance analysis on polypropylene films confirms enhanced mass uptake at higher processing temperatures, and X-ray photoelectron spectroscopy data also confirm heterogeneous mixing between the aluminum oxide and the polypropylene during deposition at higher temperatures. The strong temperature dependence of film nucleation and subsurface growth is ascribed to a relatively large increase in bulk species diffusivity that occurs upon the temperature-driven free volume expansion of the polypropylene. These results provide helpful insight into mechanisms for controlled organic/inorganic thin film and fiber materials integration.