Deterministic integration of arbitrary semiconductor heterostructures opens a new class of modern electronics and optoelectronics. However, the realization of such heterostructures continues to suffer from impracticality, requiring energy-and labor-intensive, time-consuming fabrication processes. Here a 3D printing approach to fabricate freestanding metal halide perovskite nanowire heterostructures with a high degree of control over shape and composition is demonstrated. These features arise from freeform guiding of evaporationdriven perovskite crystallization by a femtoliter precursor meniscus formed on a printing nozzle. By using a double-barreled nanopipette as a printing nozzle, "all-at-once" heterostructure fabrication is achieved within seconds. The 3D-printed perovskite nanowire heterojunctions with multiple emission colors provide exciting optical functionalities such as programmable color mixing and encryption at the single nanopixel level. This "lithography-free" additive approach opens up the possibility to freely design and realize heterostructurebased devices without the constraints of traditional manufacturing processes.
The functionalities of peptide microstructures and nanostructures can be enhanced by controlling their crystallinity. Gaining control over the crystallinity within the desired structure, however, remains a challenge. We have developed a three-dimensional (3D) printing method that enables spatioselective programming of the crystallinity of diphenylalanine (FF) dipeptide microarchitectures. A femtoliter ink meniscus is used to spatially control reprecipitation self-assembly, enabling the printing of a freestanding FF microstructure with programmed shape and crystallinity. The self-assembly crystallization of FF can be switched on and off at will by controlling the evaporation of the binary solvent. The evaporation-dependent crystallization was theoretically studied by the numerical simulation of supersaturation fields in the meniscus. We found that a 3D-printed FF microarchitecture with spatially programmed crystallinity can carry a 3D digital optical anisotropy pattern, applicable to generating polarizationencoded anticounterfeiting labels. This crystallinity-controlled additive manufacturing will pave the new way for facilitating the creation of peptide-based devices.
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