Two-Photon-Induced Direct 3D Printing of Freeform High-Index Phase-Change Sb2S3 Nanostructures
Chalcogenides have recently emerged as an important class of phase-change materials (PCMs) for nanophotonics, owing to their very high refractive index (RI) and low optical loss in the visible to near-infrared range. They exhibit an ultralarge RI change (> 0.7) upon phase transition, which can be triggered by multiple stimuli such as electrical bias, laser illumination or thermal heating. These properties make them highly appealing materials for flat optics and metasurface applications. Current nanophotonic implementations of chalcogenide PCMs mostly rely on two-dimensional (2D) or quasi three-dimensional (3D) thin film patterning based on the coating of chalcogenide materials from a solid-state target. This limits fast prototyping of 3D freeform micro- and nanostructures, thus restricting geometric design freedom and device functionality. Here, we demonstrate a solution-phase direct printing of chalcogenide PCMs into functional structures. The method is based on dip in two photon-induced solidification (DITPS) of a specially synthesized antimony trisulfide (Sb2S3) precursor solution. Direct printing with DITPS is simple, maskless, fast and cost effective, enabling true freeform 3D printing of photonic devices with sub micron resolution. We show direct writing of Sb2S3 helices with different wire cross section profiles on gold and ITO substrates, as well as functional planar Fresnel zone plates (FZPs) and computer generated hologram metasurfaces (CGHMs) in a single printing step. This freeform DITPS approach thus enables rapid 3D prototyping of high index metasurfaces and opens a route to integrating high-index PCMs into existing photonic architectures and device platforms.