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.

Mode properties of circularly symmetric waveguides with one special type of bianisotropy are studied using finite element approach. We find that the polarization degeneracy in circularly symmetric waveguides can be eliminated, by introducing intrinsic crossing coupling between electric and magnetic moments in the constituent units of the waveguide media. Breaking the polarization degeneracy in high order mode groups is also confirmed numerically. With the bianisotropic parameters chosen in this work, the x and y-polarized modes remain decoupled. Typically, the y-polarized modes remain completely unchanged, while the x-polarized modes are turned into leaky modes that are lossy along propagation direction. A perturbation model from coupled mode theory is developed to explain the results and shows excellent agreement. Such asymmetric behavior between different polarizations might be feasible and useful for developing compact polarizers in terahertz or mid-infrared regime.

Using an advanced functional photoresist we introduce direct-laser-written (DLW) 3D microstructures capable of complete degradation on demand. The networks consist exclusively of reversible bonds, formed by irradiation of a phenacyl sulfide linker, giving disulfide bonds in a radical-free step-growth polymerization via a reactive thioaldehyde. The bond formation was verified in solution by ESI-MS. To induce cleavage, dithiothreitol causes a thiol-disulfide exchange, erasing the written structure. The mild cleavage of the disulfide network is highly orthogonal to other, for example, acrylate-based DLW structures. To emphasize this aspect, DLW structures were prepared incorporating reversible structural elements into a non-reversible acrylate-based standard scaffold, confirming subsequent selective cleavage. The high lateral resolution achievable was verified by the preparation of well-defined line gratings with line separations of down to 300 nm.

Three-dimensional microstructures are fabricated employing the direct laser writing process and radical thiol-ene polymerization. The resin system consists of a two-photon photoinitiator and multifunctional thiols and olefins. Woodpile photonic crystals with 22 layers and a rod distance of 2 μm are fabricated. The structures are characterized via scanning electron microscopy and focused ion beam milling. The thiol-ene polymerization during fabrication is verified via infrared spectroscopy. The structures are grafted in a subsequent thiol-Michael addition reaction with different functional maleimides. The success of the grafting reaction is evaluated via laser scanning microscopy and X-ray photoelectron spectroscopy. The grafting density is calculated to be close to 200 molecules μm(-2) .

Recent developments in stimulated-emission depletion (STED) microscopy have led to a step change in the achievable resolution and allowed breaking the diffraction limit by large factors. The core principle is based on a reversible molecular switch, allowing for light-triggered activation and deactivation in combination with a laser focus that incorporates a point or line of zero intensity. In the past years, the concept has been transferred from microscopy to maskless laser lithography, namely direct laser writing (DLW), in order to overcome the diffraction limit for optical lithography. Herein, we propose and experimentally introduce a system that realizes such a molecular switch for lithography. Specifically, the population of intermediate-state photoenol isomers of α-methyl benzaldehydes generated by two-photon absorption at 700 nm fundamental wavelength can be reversibly depleted by simultaneous irradiation at 440 nm, suppressing the subsequent Diels-Alder cycloaddition reaction which constitutes the chemical core of the writing process. We demonstrate the potential of the proposed mechanism for STED-inspired DLW by covalently functionalizing the surface of glass substrates via the photoenol-driven STED-inspired process exploiting reversible photoenol activation with a polymerization initiator. Subsequently, macromolecules are grown from the functionalized areas and the spatially coded glass slides are characterized by atomic-force microscopy. Our approach allows lines with a full-width-at-half-maximum of down to 60 nm and line gratings with a lateral resolution of 100 nm to be written, both surpassing the diffraction limit.

Three-dimensional microstructures are fabricated utilizing direct laser writing combined with a non-radical step polymerization based on multiphoton-induced Diels-Alder chemistry of o -quinodimethanes and maleimides. Woodpile photonic crystals with a total of fi ve axial periods and a rod spacing of down to 500 nm are fabricated. The structures are characterized via scanning electron microscopy and focused ion beam milling. In addition, corresponding photonic stop bands are investigated via light microscopy as well as transmission and refl ection spectroscopy. The Diels-Alder based network formation during direct laser writing is verifi ed via infrared spectroscopy. Spatially resolved surface patterning of covalently bonded functional molecules on fabricated structures is demonstrated by employing the direct laser writing setup and a bromine containing maleimide. The successful surface modifi cation is verifi ed via time-of-fl ight secondary ion mass spectrometry.

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.

A wavelength selective technique for light-induced network formation based on two photo-active moieties, namely ortho-methylbenzaldehyde and tetrazole is introduced. The network forming species are photo-reactive star polymers generated via reversible activation fragmentation chain transfer (RAFT) polymerization, allowing the network to be based on almost any vinylic monomer. Direct laser writing (DLW) allows to form any complex three-dimensional structure based on the photo-reactive star polymers.