In this article, the growth of polymer nanoparticles formed at the liquid–vapor interface via vapor phase polymerization is studied. The particles grow by polymer aggregation, which is driven by the surface tension interaction between the liquid and polymer. It is demonstrated that the mechanism of particle growth is determined by whether polymer particles remain at the liquid–vapor interface or submerge into the liquid. The position of the particles depends on the interaction between the polymer and the liquid. For example, the deposition of poly(n‐butyl acrylate) onto poly(dimethyl siloxane) and Krytox liquids leads to the formation of nanoparticles that remain at the liquid–vapor interface. The size of these particles increases as a function of deposition time. The deposition of poly(4‐vinylpyridine) onto poly(dimethyl siloxane) and Krytox leads to the formation of nanoparticles that submerge into the liquid. The size of these particles does not significantly change with deposition time. Our study offers a new rapid, one‐step synthetic approach for fabricating functional polymer nanoparticles for applications in catalysis, photonics, and drug delivery.
