Fused silica glass is the material of choice for many high‐performance components in optics due to its high optical transparency combined with its high thermal, chemical, and mechanical stability. Especially, the generation of fused silica microstructures is of high interest for microoptical and biomedical applications. Direct laser writing (DLW) is a suitable technique for generating such devices, as it enables nearly arbitrary structuring down to the sub‐micrometer level. In this work, true 3D structuring of transparent fused silica glass using DLW with tens of micrometer resolution and a surface roughness of Ra ≈ 6 nm is demonstrated. The process uses a two‐photon curable silica nanocomposite resin that can be structured by DLW, with the printout being convertible to transparent fused silica glass via thermal debinding and sintering. This technology will enable a plethora of applications from next‐generation optics and photonics to microfluidic and biomedical applications with resolutions on the scale of tens of micrometers.

3D printing has emerged as an enabling technology for miniaturization. High‐precision printing techniques such as stereolithography are capable of printing microreactors and lab‐on‐a‐chip devices for efficient parallelization of biological and biochemical reactions under reduced uptake of reactants. In the world of chemistry, however, up until now, miniaturization has played a minor role. The chemical and thermal stability of regular 3D printing resins is insufficient for sustaining the harsh conditions of chemical reactions. Novel material formulations that produce highly stable 3D‐printed chips are highly sought for bringing chemistry up‐to‐date on the development of miniaturization. In this work, a brief review of recent developments in highly stable materials for 3D printing is given. This work focuses on three highly stable 3D‐printable material systems: transparent silicate glasses, ceramics, and fluorinated polymers. It is further demonstrated that 3D printing is also a versatile technique for surface structuring of polymers to enhance their wetting performance. Such micro/nanostructuring is key to selectively wetting surface patterns that are versatile for chemical arrays and droplet synthesis.

Polymethylmethacrylate (PMMA) is one of the most important thermoplastic materials and is a widely used material in microfluidics. However, PMMA is usually structured using industrial scale replication processes, such as hot embossing or injection molding, not compatible with rapid prototyping. In this work, we demonstrate that microfluidic chips made from PMMA can be 3D printed using fused deposition modeling (FDM). We demonstrate that using FDM microfluidic chips with a minimum channel cross-section of ~300 µm can be printed and a variety of different channel geometries and mixer structures are shown. The optical transparency of the chips is shown to be significantly enhanced by printing onto commercial PMMA substrates. The use of such commercial PMMA substrates also enables the integration of PMMA microstructures into the printed chips, by first generating a microstructure on the PMMA substrates, and subsequently printing the PMMA chip around the microstructure. We further demonstrate that protein patterns can be generated within previously printed microfluidic chips by employing a method of photobleaching. The FDM printing of microfluidic chips in PMMA allows the use of one of microfluidics’ most used industrial materials on the laboratory scale and thus significantly simplifies the transfer from results gained in the lab to an industrial product.

Fused silica glass is the preferred material for applications which require long-term chemical and mechanical stability as well as excellent optical properties. The manufacturing of complex hollow microstructures within transparent fused silica glass is of particular interest for, among others, the miniaturization of chemical synthesis towards more versatile, configurable and environmentally friendly flow-through chemistry as well as high-quality optical waveguides or capillaries. However, microstructuring of such complex three-dimensional structures in glass has proven evasive due to its high thermal and chemical stability as well as mechanical hardness. Here we present an approach for the generation of hollow microstructures in fused silica glass with high precision and freedom of three-dimensional designs. The process combines the concept of sacrificial template replication with a room-temperature molding process for fused silica glass. The fabricated glass chips are versatile tools for, among other, the advance of miniaturization in chemical synthesis on chip.

Highly fluorinated perfluoropolyether (PFPE) methacrylates are of great interest for transparent and chemically resistant microfluidic chips. However, so far only a few examples of material formulations for three-dimensional (3D) printing of these polymers have been demonstrated. In this paper we show that microfluidic chips can be printed using these highly fluorinated polymers by 3D stereolithography printing. We developed photocurable resin formulations that can be printed in commercial benchtop stereolithography printers. We demonstrate that the developed formulations can be printed with minimal cross-sectional area of 600 µm for monolithic embedded microfluidic channels and 200 µm for open structures. The printed and polymerized PFPE methacrylates show a good transmittance above 70% at wavelengths between 520–900 nm and a high chemical resistance when being exposed to organic solvents. Microfluidic mixers were printed to demonstrate the great variability of different designs that can be printed using stereolithography.