Centimeter-Scale Curing Depths in Laser-Assisted 3D Printing of Photopolymers Enabled by Er³⁺ Upconversion and Green Light-Absorbing Photosensitizer

Photopolymer resins used in stereolithographic 3D printing are limited to penetration depths of less than 1 mm. Our approach explores the use of near-infrared (NIR) to visible upconversion (UC) emissions from lanthanide-based phosphors to initiate photopolymer crosslinking at a much higher depth. This concept relies on the use of invisibility windows and non-linear optical effects to achieve selective crosslinking in photopolymers. SLA resin formulation capable of absorbing light in the visible region (420-550 nm) was developed, in order to take advantage of efficient green-UC of Er3+/Yb3+ doped phosphor. NIR-green light UC shows versatility in enhancing curing depths in laser patterning. For instance, a structure with a curing depth of 11 +/- 0.2 mm, cured width of 496 +/- 5 mu m and aspect ratios of over 22.2:1 in a single pass via NIR-green light UC. The penetration depth of the reported formulation approached 39 mm. Therefore, this technique would allow curing depths of up to 4 cm. Moreover, it was also demonstrated that this technique can initiate cross-linking directly at the focal point. This shows the potential of NIR-assisted UC as a low-cost method for direct laser writing in volume and 3D printing.