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We elucidate a previously unknown synthesis pathway that leads to polymeric nanospheres, orientation-controlled microgels, or microspheroids via single-step polymerization of divinylbenzene (DVB) using initiated chemical vapor deposition (iCVD) in liquid crystals (LC). iCVD supplies vapor-phase reactants continuously, avoiding the critical limitation of reactant-induced disruption of LC structure that has plagued past LC-templated polymerization processes. LC is leveraged as a real-time display of the polymerization conditions and particle emergence, captured using an in situ long–focal range microscope. Detailed image analysis unravels key LC-guided mechanisms during polymerization. pDVB forms nanospheres due to poor solubilization by nematic LC. The nanospheres partition to the LC-solid interface and further assemble into microgel clusters whose orientation is guided by the LC molecular alignment. On further polymerization, microgel clusters transition to microspheroids that resemble liquid drops. We identify key energetic factors that guide trajectories along the synthesis pathway, providing the fundamental basis of a framework for engineering particle synthesis with shape control. 

Ion-conducting polymers (ICPs) are gaining interest in various scientific and technological fields. This review highlights advancements in ICP thin films using chemical vapor deposition (CVD) and addresses challenges of traditional methods. 

Abstract Initiated Chemical Vapor Deposition (iCVD) is a versatile and powerful technique for controlling the morphology of polymeric and hybrid thin films, with applications spanning from electronics to biomedical devices. This review highlights recent advancements in iCVD technology that enable precise morphological control from creating ultrasmooth films to self‐assembled nanostructures. Advances in reactor design now allow for in situ monitoring of key parameters, such as film thickness and surface imaging, providing real‐time insights into material morphology. Surface morphology is influenced by both the substrate and coating layer. For the former, iCVD offers significant advantages in creating defect‐free, conformal coatings over complex substrates, making it particularly well‐suited for flexible electronics, optical devices, and antifouling/antimicrobial biointerfaces. For the latter, iCVD has been leveraged for the fabrication of microstructured coatings that improve energy storage, gas sensing, and pathogen detection, superhydrophobic or anti‐icing surfaces. Its all‐dry processing and compatibility with temperature‐sensitive substrates further emphasize its potential for sustainable manufacturing. The ability to fine‐tune film chemistry and morphology, combined with the scalability, positions iCVD as a promising tool for addressing future technological challenges in advanced materials design. 

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.