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Abstract The systems for multiphoton 3D nanoprinting are rapidly increasing in print speed for larger throughput and scale, unfortunately without also improvement in resolution. Separately, the process of photoinhibition lithography has been demonstrated to enhance the resolution of multiphoton printing through the introduction of a secondary laser source. The photo-chemical dynamics and interactions for achieving photoinhibition in the various multiphoton photoinitiator systems are complex and still not well understood. Here, we examine the photoinhibition process of the common photoinitiator 7-diethylamino 3-thenoylcoumarin (DETC) with inhibition lasers near or at the multiphoton printing laser wavelength in typical low peak intensity, high repetition rate 3D nanoprinting processes. We demonstrate the clear inhibition of the polymerization process consistent with a triplet absorption deactivation mechanism for a DETC photoresist as well as show inhibition for several other photoresist systems. Additionally, we explore options to recover the photoinhibition process when printing with high intensity, low repetition rate lasers. Finally, we demonstrate photoinhibition in a projection multiphoton printing system. This investigation of photoinhibition lithography with common photoinitiators elucidates the possibility for photoinhibition occurring in many resist systems with typical high repetition rate multiphoton printing lasers as well as for high-speed projection multiphoton printing. 

Abstract There is demand for scaling up 3D printing throughput, especially for the multi-photon 3D printing process that provides sub-micrometer structuring capabilities required in diverse fields. In this work, high-speed projection multi-photon printing is combined with spatiotemporal focusing for fabrication of 3D structures in a rapid, layer-by-layer, and continuous manner. Spatiotemporal focusing confines printing to thin layers, thereby achieving print thicknesses on the micron and sub-micron scale. Through projection of dynamically varying patterns with no pause between patterns, a continuous fabrication process is established. A numerical model for computing spatiotemporal focusing and imaging is also presented which is verified by optical imaging and printing results. Complex 3D structures with smooth features are fabricated, with millimeter scale printing realized at a rate above 10 −3 mm 3 s −1 . This method is further scalable, indicating its potential to make fabrications of 3D structures with micro/nanoscale features in a practical time scale a reality. 

Abstract Radical chemistries have attracted burgeoning attention due to their intriguing technological applications in organic electronics, optoelectronics, and magneto‐responsive systems. However, the potential of these magnetically active glassy polymers to transport spin‐selective currents has not been demonstrated. Here, the spin‐transport characteristics of the radical polymer poly(4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl) (PTEO) allow for sustained spin‐selective currents when incorporated into typical device geometries with magnetically polarized electrodes. Annealing thin films of PTEO above its glass transition temperature results in a giant magnetoresistance effect (i.e., an MR of ≈80%) at 4 K. Additionally, ferromagnetic resonance spin‐pumping results in a relatively large effective spin‐mixing conductance of 1.18 × 10¹⁹m⁻²at the NiFe/PTEO interface. Due to the large spin‐density and radical‐radical exchange interactions, there is effective propagation of pure spin currents through PTEO in the NiFe/PTEO/Pd multilayer devices. This results in the transport of spin current over long distances with a spin diffusion length of 90.4 nm. The spin diffusion length and spin mixing conductance values surpass those reported in inorganic and metallic systems and are comparable to conventional doped conjugated polymers. This is the first example of spin transport in a nonconjugated radical polymer, and these findings underscore the promising spin‐transporting potential of radical polymers.