From Single to Multi‐Glass/Ceramic Microarchitectures via Two‐Photon Lithography

Two‐photon lithography (TPL), as an additive manufacturing (AM) technique, facilitates the low‐temperature fabrication of microarchitectures, yet the integration of spatially varying inorganic compositions within a microarchitecture footprint remains largely unexplored. This work examines the transition from single to multi‐material manufacture and, study the optical properties of SiO 2 glass and its combination with inorganic loadings. The latter approach, i.e., multi‐composition printing, is evaluated using a fluidic cell for photoresin exchange, enabling spatially varied patterning. Using thermal annealing at 650 °C, single‐ and multi‐inorganic printed replicas are produced with tailored chemical components. Yet, even though state‐of‐the‐art photoresins are well‐optimized for single‐material printing (e.g., SiO 2 , TiO 2 , and ZrO 2 ), the necessity of adjusting photoresins is highlighted for multi‐material printing. Annealed multi‐printed replicas rely on composition‐specific photoresins, such as the inorganic mass fraction, which can significantly influence the fidelity of the post‐annealed microarchitecture. Additionally, insights into these microarchitectures' chemical, morphological, and optical behavior are provided through characterization methods, including scanning electron microscopy (SEM), energy‐dispersive X‐ray spectroscopy (EDX), confocal fluorescence microscopy, and cathodoluminescence (CL). The results highlight the importance of formulation and processing conditions for achieving inorganic multi‐printing.