Tailoring Self‐Organized Growth of Biomimetic Inorganic–Organic Multilayers with a Permeable Microcompartment

Abstract Organisms such as marine glass sponges, molluscan animals, crustaceans, and mammals develop inorganic–organic multilayers in ambient conditions. This structural motif of inorganic–organic multilayers has a central function in reconciling strength and toughness, nacre being a well‐studied example. Although biomimetic multilayers have been successfully processed through particle assembly and multistep deposition, the development of a self‐organized approach to transforming molecular subunits into this macroscopic architecture remains a challenging task. The present study introduces a permeable microcompartment for the self‐organized growth of an inorganic–organic multilayer. In the microcompartment enclosed by a graphene oxide membrane, multiple mineral layers separated by nanometer‐thin organic layers grow via a phase‐separation process that can be described quantitatively through a kinetic model. This model permits the adjustment of boundary conditions to regulate the average thickness of the mineral layers in a predictable manner. The synthetic process can be applied to a wide range of mineral compositions, polymorphs, as well as organic interphase. Particularly, the deliberate introduction of a continuous polymeric interphase provides a means of localizing the damage through crack deflection. This opens the possibility of using self‐organization within a permeable microcompartment to facilitate the growth of biomimetic inorganic–organic multilayers with a range of structural and functional properties.