A combined theoretical and experimental study is presented to investigate the interplay of forces in the spin-dewetting process in order to achieve enhanced control over droplet generation. In this regard, toluene–polystyrene (PS) film is spin dewetted on a solid substrate to generate an array of droplets. The underlying mechanisms of the spin dewetting of the films into the droplets are explained with the help of a theoretical model followed by a long-wave linear stability analysis (LWLSA). Stabilizing forces like solution viscosity and surface tension play essential roles. The study uncovers that the centripetal force stretches the film radially outward, before it becomes ultrathin and undergoes dewetting under the influence of van der Waals forces, while the surface tension force acts as a stabilizing influence. On the other hand, the viscous force kinetically stabilizes the system to expedite or delay drop formation on the substrate. An imbalance of these factors ultimately decides the droplet spacing, which leads to interesting morphologies such as singlet, doublet, triplet, and clusters of droplets at specific PS concentrations in the range 0.0001–0.0005%, with a ~10–14 nm average droplet height. The experimental data revealed that, at ~3000 rpm, PS (0.01–0.1%) results in critical droplet spacings of λ_max~98–172 μm, leading to immediate dewetting and uniform droplet formation. Our theoretical predictions are in close agreement with the experimental results, validating the present model. The insights gained in this work provide a foundation by presenting a robust framework for controlled droplet generation by optimizing process parameters to achieve the desired droplet size, distribution, and uniformity. The findings have broad applications in material science, biomedical engineering, and related disciplines.

Pathways to fabricate self-organized nanostructures have been identified exploiting the instabilities of ultrathin (<100 nm) polystyrene (PS) film on the polydimethylsiloxane (PDMS) substrates loaded with discrete and closely packed gold nanoparticles (AuNPs). The AuNPs were deposited on the PDMS substrates by chemical treatment, and the size and periodicity of the AuNPs were varied before coating the PS films. The study unveils that the physicochemical heterogeneity created by the AuNPs on the PDMS surface could guide the hole-formation, influence the average spacing between the holes formed at the initial dewetting stage, and affects the spacing and periodicity of the droplets formed at the end of the dewetting phase. The size and spacing of the holes and the droplets could be tuned by varying the nanoparticle loading on the PDMS substrate. Interestingly, as compared to the dewetting of PS films on the homogeneous PDMS surfaces, the AuNP guided dewetted patterns show ten-fold miniaturization, leading to the formation of the micro-holes and nanodroplets. The spacing between the droplets could also see a ten-fold reduction resulting in high-density random patterns on the PDMS substrate. Further, the use of a physicochemical substrate with varying density of physicochemical heterogeneities could impose a long-range order to the dewetted patterns to develop a gradient surface. The reported results can be of significance in the fabrication of high-density nanostructures exploiting the self-organized instabilities of thin polymers films.