Peptide-based materials are emerging as smart building blocks for nanobiodevices due to the programmability of their properties via the molecular constituents or arrangements. Many clever molecular self-assembly approaches have been devised to produce peptide crystalline structures. However, their freeform shaping remains a challenge due to the intrinsic self-assembly nature. Here, we report the fabrication of freeform, crystalline diphenylalanine (FF) peptide structures by combining meniscus-guided 3D printing with molecular self-assembly. Self-assembly in 3D-printed FF arises from mild thermal activation under precise temperature control of the build platform. After thorough characterizations, we demonstrate layer-by-layer, crystalline 3D printing with a high spatial resolution of 2 μm laterally and 200 nm vertically. The 3D-printed FF exhibits piezoelectricity originating from its crystalline character, showing the potential to become a key constituent for bioelectronic devices. We expect this technique to open up the possibility to create functional devices based on self-assembled organic materials without design restrictions.
Keywords: 3D printing; dipeptides; diphenylalanine; piezoelectricity; self-assembly.