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.
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H.X. gratefully acknowledges funding support from the National Natural Science Foundation of China (grant no. 52073161), the Tsinghua University Initiative Scientific Research Program (grant no. 2021Z11GHX010), the Beijing Municipal Science & Technology Commission, Administrative Commission of Zhongguancun Science Park (grant no. Z211100004821008) and the Major Scientific Project of Zhejiang Lab (grant no. 2020MC0AE01). T.L. gratefully acknowledges funding support from the China Postdoctoral Science Foundation (grant no. 2021M701826). C.K. gratefully acknowledges funding support from the Major Scientific Project of Zhejiang Lab (grant no. 2020MC0AE01). We thank Y. Wang for his help in experimental measurements of mechanism studies.
The authors declare no competing interests.
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Source data of the lithographic patterns and structures, and the width and thickness of the line patterns in Fig. 2.
Source data of the lithographic patterns and structures in Fig. 3.
Source data of the FT-IR and UV–vis spectra, DFT calculated structure of initiator BTMST in Fig. 4.
Source data of the DFT calculated structures of the components of the photoresist in Fig. 5.
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Liu, T., Tao, P., Wang, X. et al. Ultrahigh-printing-speed photoresists for additive manufacturing. Nat. Nanotechnol. (2023). https://doi.org/10.1038/s41565-023-01517-w