Generation of Tailored Multi‐Material Microstructures Through One‐Step Direct Laser Writing

Direct laser writing has gained remarkable popularity by offering architectural control of 3D objects at submicron scales. However, it faces limitations when the fabrication of microstructures comprising multiple materials is desired. The generation processes of multi-material microstructures are often very complex, requiring meticulous alignment, as well as a series of step-and-repeat writing and development of the materials. Here, a novel material system based on multilayers of chemically tailored polymers containing anthraquinone crosslinker units is demonstrated. Upon two-photon excitation, the crosslinkers only require nearby aliphatic C,H units as reaction partners to form a crosslinked network. The desired structure can be written into a solid multi-layered material system, wherein the properties of each material can be designed at the molecular level. In this way, C,H insertion crosslinking (CHic) of the polymers within each layer, along with simultaneous reaction at their interfaces, is performed, leading to the one-step fabrication of multi-material microstructures. A multi-material 3D scaffold with a sixfold symmetry is produced to precisely control the adhesion of cells both concerning surface chemistry and topology. The demonstrated material system shows great promise for the fabrication of 3D microstructures with high precision, intricate geometries and customized functionalities.