Tunable Properties of MAPLE-Deposited Thin Films in the Presence of Suppressed Segmental Dynamics

Processing polymer thin films by physical vapor deposition has been a major challenge due to material degradation. This challenge has limited our understanding of morphological control by top-down approaches that can be crucial for many applications. Recently, matrix-assisted pulsed laser evaporation (MAPLE) has emerged as an alternative route to fabricate polymer thin films from near-gas phase growth conditions. In this Letter, we investigate how this approach can result in a stable two-phase film structure of semicrystalline polymers via a unique combination of MAPLE and flash calorimetry. In the case of MAPLE-deposited poly­(ethylene oxide) (PEO) thin films, we find a 35 °C enhancement in the glass transition temperature relative to melt-crystallized films, which is associated with irreversible chain adsorption in the amorphous region of the film. Remarkably, by varying substrate temperature during deposition, we reveal the ability to significantly tune the crystal orientation, extent of crystallinity, and lamellar thickness of MAPLE-deposited PEO thin films.