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  1. Free, publicly-accessible full text available July 11, 2024
  2. Free, publicly-accessible full text available July 1, 2024
  3. Size-controlled polymer nanodomes (PNDs) benefit a broad cross-section of existing and emerging technologies. Condensed droplet polymerization (CDP) is a vacuum-based synthesis technology that produces PNDs from monomer precursors in a single step. However, the effect of synthesis and processing conditions on the PND size distribution remains elusive. Towards size distribution control, we report the effect of substrate temperature, on which monomer droplets condense, on the size distribution of PNDs. We take a reductionist approach and operate the CDP under batch mode to match the conditions commonly used in condensation research. Notably, despite the rich knowledge base in dropwise condensation, the behavior of nonpolar liquids like a common monomer, i.e., 2-hydroxyethyl methacrylate (HEMA), is not well understood. We bridge that gap by demonstrating that dropwise condensation of HEMA follows a two-stage growth process. Early-stage growth is dominated by drop nucleation and growth, giving rise to relatively uniform sizes with a lognormal distribution, whereas late-stage growth is dominated by the combined effect of drop coalescence and renucleation, leading to a bimodal size distribution. This new framework for understanding the PND size distribution enables an unprecedented population of PNDs. Their controlled size distribution has the potential to enable programmable properties for emergent materials.

     
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  4. Conformal coating of nanopores with functional polymer nanolayers is the key to many emerging technologies such as miniature sensors and membranes for advanced molecular separations. While the polymer coatings are often used to introduce functional moieties, their controlled growth under nanoconfinement could serve as a new approach to manipulate the size and shape of coated nanopores, hence, enabling novel functions like molecular separation. However, precise control of coating thickness in the longitudinal direction of a nanopore is limited by the lack of a characterization method to profile coating thickness within the nanoconfined space. Here, we report an experimental approach that combines ion milling (IM) and high-resolution field emission scanning electron microscopy (FESEM) for acquiring an accurate depth profile of ultrathin (∼20 nm or less) coatings synthesized inside nanopores via initiated chemical vapor deposition (iCVD). The enhanced capability of this approach stems from the excellent x–y resolution achieved by FESEM (i.e., 4.9 nm/pixel), robust depth ( z) control enabled by IM (step size as small as 100 nm with R2 = 0.992), and the statistical power afforded by high-throughput sampling (i.e., ∼2000 individual pores). With that capability, we were able to determine with unparalleled accuracy and precision the depth profile of coating thickness and iCVD kinetics along 110-nm-diameter nanopores. That allowed us to uncover an unexpected coating depth profile featuring a maximum rate of polymerization at ∼250 nm underneath the top surface, i.e., down the pores, which we termed “necking.” The necking phenomenon deviates considerably from the conventionally assumed monotonous decrease in thickness along the longitudinal direction into a nanopore, as predicted by the diffusion-limited kinetics model of free radical polymerization. An initiator-centric collision model was then developed, which suggests that under the experimental conditions, the confinement imposed by the nanopores may lead to local amplification of the effective free radical concentration at z ≤ 100 nm and attenuation at z ≥ 500 nm, thus contributing to the observed necking phenomenon. The ion-milling-enabled depth profiling of ultrathin coatings inside nanopores, along with the initiator-mediated coating thickness control in the z-direction, may serve to enhance the performance of size-exclusion filtration membranes and even provide more flexible control of nanopore shape in the z dimension.

     
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