Three-dimensional (3D) laser micro- and nanoprinting based upon multi-photon absorption has made its way from early scientific discovery to industrial manufacturing processes, e.g., for advanced microoptical components. However, so far, most realized 3D architectures are composed of only a single polymeric material. Here, we review 3D printing of multi-materials on the nano- and microscale. We start with material properties that have been realized, using multi-photon photoresists. Printed materials include bulk polymers, conductive polymers, metals, nanoporous polymers, silica glass, chalcogenide glasses, inorganic single crystals, natural polymers, stimuli-responsive materials, and polymer composites. Next, we review manual and automated processes achieving dissimilar material properties in a single 3D structure by sequentially photo-exposing multiple photoresists as 3D analogs of 2D multicolor printing. Instructive examples from biology, optics, mechanics, and electronics are discussed. An emerging approach – without counterpart in 2D graphical printing – prints 3D structures combining dissimilar material properties in one 3D structure by using only a single photoresist. A controlled stimulus applied during the 3D printing process defines and determines material properties on the voxel level. Change of laser power and/or wavelength, or application of quasi-static electric fields allow for the seamless manipulation of desired materials properties.
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