Advanced Morphological Control of Polymeric Surfaces Using Initiated Chemical Vapor Deposition (iCVD)

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.