Stability of Polymer Grafted Nanoparticle Monolayers: Impact of Architecture and Polymer–Substrate Interactions on Dewetting

The stability of polymer thin films is crucial to a broad range of technologies, including sensors, energy storage, filtration, and lithography. Recently, the demonstration of rapid deposition on solid substrates of ordered monolayers of polymer grafted nanoparticles (PGN) has increased potential for inks to additively manufacture such components. Herein, enhanced stability against dewetting of these self-assembled PGN films (gold nanoparticle functionalized with polystyrene (AuNP-PS)) is discussed in context to linear polystyrene (PS) analogues using high throughput surface gradients: surface energy (20–45 mN/m) and temperature (90–160 °C). PGNs exhibit a lower surface (γ<sub>p</sub>) and interfacial (γ<sub>sp</sub>) energy relative to linear polymers, which results in increased thermal and energetic stability by 10–25 °C and 5–15 mN/m, respectively. This enhanced wetting–dewetting transition is qualitatively consistent with the behavior of star macromolecules and depends on the architecture of the polymer canopy. Increased film stability through canopy architecture expands the manufacturability of thin film hybrids and refines postprocessing conditions to maximize local PGN order.