Ultrahigh-printing-speed photoresists for additive manufacturing

Printing technology for precise additive manufacturing at the nanoscale currently relies on two-photon lithography. Although this methodology can overcome the Rayleigh limit to achieve nanoscale structures, it still operates at too slow of a speed for large-scale practical applications. Here we show an extremely sensitive zirconium oxide hybrid-(2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine) (ZrO₂-BTMST) photoresist system that can achieve a printing speed of 7.77 m s^-1, which is between three and five orders of magnitude faster than conventional polymer-based photoresists. We build a polygon laser scanner-based two-photon lithography machine with a linear stepping speed approaching 10 m s^-1. Using the ZrO₂-BTMST photoresist, we fabricate a square raster with an area of 1 cm² in ~33 min. Furthermore, the extremely small chemical components of the ZrO₂-BTMST photoresist enable high-precision patterning, leading to a line width as small as 38 nm. Calculations assisted by characterizations reveal that the unusual sensitivity arises from an efficient light-induced polarity change of the ZrO₂ hybrid. We envisage that the exceptional sensitivity of our organic-inorganic hybrid photoresist may lead to a viable large-scale additive manufacturing nanofabrication technology.