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Ultrahigh-printing-speed photoresists for additive manufacturing

Nature Nanotechnology volume 19, pages 51–57 (2024)Cite this article

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Abstract

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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Fig. 1: TPL oil-immersion exposure mode schematic and structures of BTMST and the ZrO2 hybrid.
Fig. 2: Patterns exposed by a polygon laser scanner-based TPL machine with a light wavelength of 780 nm using ZrO2-BTMST photoresists.
Fig. 3: SEM images of ZrO2-BTMST photoresists exposed by a galvanometric scanner-based TPL machine with a light wavelength of 532 nm.
Fig. 4: Experimental characterizations and DFT calculations of initiator BTMST.
Fig. 5: DFT-COSMO simulated structures and charge distributions.
Fig. 6: Plausible patterning mechanism of ZrO2-BTMST photoresists.

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Data availability

The data that support the findings of this study are available within the paper and the Supplementary Information. Other relevant data are available from the corresponding authors on reasonable request. Source data are provided with this paper.

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Acknowledgements

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.

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Authors and Affiliations

  1. Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing, P. R. China

    Tianqi Liu, Peipei Tao, Xiaolin Wang, Qianqian Wang, Hao Cui, Jianlong Wang, Yaping Tang, Hong Xu & Xiangming He

  2. Research Center for Intelligent Chips and Devices, Zhejiang Lab, Hangzhou, P. R. China

    Hongqing Wang & Cuifang Kuang

  3. State Key Laboratory of Modern Optical Instrumentation, College of Optical Science and Engineering, Zhejiang University, Hangzhou, P. R. China

    Minfei He & Cuifang Kuang

  4. MOE Key Laboratory of Macromolecular Synthesis and Functionalization, State Key Laboratory of Silicon Materials, International Research Center for X Polymers, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, P. R. China

    Jin Tang & Ning Huang

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Contributions

T.L. and H.X. conceived and designed the experiments. T.L. and P.T. performed structural characterization. T.L., H.W. and M.H. performed TPL performance tests of materials. X.W. and Q.W. performed material synthesis. H.W., M.H. and C.K. constructed the two-photon lithography machines. H.X. and H.C. performed computational calculations. T.L., J.W., Y.T., J.T., N.H., C.K., H.X. and X.H. contributed to the data analysis. T.L., C.K., H.X. and X.H. wrote the paper. All authors participated in the discussion and correction of the paper.

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Correspondence to Cuifang Kuang, Hong Xu or Xiangming He.

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Nature Nanotechnology thanks Shih-Chi Chen and the other, anonymous, reviewer for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary experimental procedures, Supplementary Figs. 1–26, Tables 1–4 and references.

Supplementary Data

Source data for supplementary information.

Source data

Source Data Fig. 2

Source data of the lithographic patterns and structures, and the width and thickness of the line patterns in Fig. 2.

Source Data Fig. 3

Source data of the lithographic patterns and structures in Fig. 3.

Source Data Fig. 4

Source data of the FT-IR and UV–vis spectra, DFT calculated structure of initiator BTMST in Fig. 4.

Source Data Fig. 5

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. 19, 51–57 (2024). https://doi.org/10.1038/s41565-023-01517-w

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