Bridging the Synthesis Gap: Ionic Liquids Enable Solvent-Mediated Reaction in Vapor-Phase Deposition.

Molecular layer deposition (MLD) is an attractive, vapor-phase deposition method for applications requiring ultrathin organic materials, such as photolithography, lithium batteries, and microelectronics. By using sequential self-limiting surface reactions, MLD offers excellent control over thickness and conformality, but there are also challenges such as a limited range of possible film compositions and long deposition times. In this study, we introduce a modified technique, termed ionic liquid assisted MLD (IL-MLD), that can overcome these barriers. By performing the surface reactions inside of an ultrathin layer of a compatible ionic liquid (IL), solvent effects are replicated inside a vacuum system, broadening the possible reactions to a much wider suite of chemistries. Using this strategy, the MLD of polyetherketoneketone, an industrially and research-relevant, high-performance thermoplastic, is reported. With this proof-of-concept, we demonstrate that IL-MLD can enable the synthesis of polymers via solvent- or catalyst-mediated reactions and establish an approach that may allow solution chemistries to be accessed in other vapor deposition techniques as well.