Mechanisms and reactions during atomic layer deposition on polymers

There is significant growing interest in atomic layer deposition onto polymers for barrier coatings, nanoscale templates, surface modification layers and other applications. The ability to control the reaction between ALD precursors and polymers opens new opportunities in ALD materials processing. It is well recognized that ALD on many polymers involves subsurface precursor diffusion and reaction which are not encountered during ALD on solid surfaces. This article reviews recent insights into chemical reactions that proceed during ALD on polymers, with particular focus on the common Al2O3 reaction sequence using trimethyl aluminum (TMA) and water. We highlight the role of different polymer reactive groups in film growth, and how the balance between precursor diffusion and reaction can change as deposition proceeds. As a strong Lewis acid, TMA forms adducts with Lewis base sites within the polymer, and the reactions that proceed are determined by the neighboring bond structure. Moreover, the Lewis base sites can be saturated by TMA, producing a self-limiting half-reaction within a three-dimensional polymer, analogous to a self-limiting half-reaction commonly observed during ALD on a solid planar surface.