Initiation of atomic layer deposition of metal oxides on polymer substrates by water plasma pretreatment

The role of surface hydroxyl content in atomic layer deposition (ALD) of aluminum oxide (AO) on polymers is demonstrated by performing an atomic layer deposition of AO onto a variety of polymer types, before and after pretreatment in a plasma struck in water vapor. The treatment and deposition reactions are performed in situ in a high vacuum chamber that is interfaced to an x-ray photoelectron spectrometer to prevent adventitious exposure to atmospheric contaminants. X-ray photoelectron spectroscopy is used to follow the surface chemistries of the polymers, including theformation of surface hydroxyls and subsequent growth of AO by ALD. Using dimethyl aluminum isopropoxide and water as reactants, ALD is obtained for water-plasma-treated poly(styrene) (PS), poly(propylene) (PP), poly(vinyl alcohol) (PVA), and poly(ethylene naphthalate) (PEN). For PS, PP, and PEN, initial growth rates of AO on the native (untreated) polymers are at least an order of magnitude lower than on the same polymer surface following the plasma treatment. By contrast, native PVA is shown to initiate ALD of AO as a result of the presence of intrinsic surface hydroxyls that are derived from the repeat unit of this polymer.