AbstractInnovative materials enable two‐photon polymerization for precise additive fabrication of intricate optical components. Existing polymeric inks suffer from poor optical performance due to their high organic content. Silica‐rich sol‐gel ink (75 wt%, under ambient conditions) is presented for high‐precision three‐dimensional (3D) printing of microscale structures and optical devices. A photoinitiator with high‐efficiency nonlinear absorption is introduced to initiate two‐photon polymerization. Utilizing a commercial direct laser writing system, 3D‐printing is demonstrated including the optimization of printing parameters and ink characterization. The optical performance of the printed microscale elements using the new sol‐gel ink surpasses commercially available polymeric inks on key metrics: Printed elements exhibit extremely low surface roughness, 3nm; visible and near‐IR light transmission is greater than 90%; Printed elements present enhanced mechanical and chemical resistance to common organic solvents; Structures exhibit low isotropic shrinkage, <10%; Elements withstand continuous‐wave laser intensities exceeding 7 × 105 W cm−2. Direct writing onto an optical fiber tip with no need for surface functionalization is presented, with the demonstration of a tall waveguide taper (≈1:5 aspect ratio) with low losses and modal crosstalk, and a freestanding photonic lantern mode multiplexer. The new ink can be utilized in a variety of applications and across many materials, requiring compact, durable, and complex optical elements.
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