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Light-sheet 3D microprinting via two-colour two-step absorption

Nature Photonics volume 16, pages 784–791 (2022)Cite this article

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Abstract

High-speed high-resolution 3D printing of polymers is highly desirable for many applications, yet still technologically challenging. Today, optics-based printing is in the lead. Projection-based linear optical approaches have achieved high printing rates of around 106 voxels s–1, although at voxel volumes of >100 μm3. Scanning-based nonlinear optical approaches have achieved voxel volumes of <1 μm3, but suffer from low printing speed or high cost because of the required femtosecond lasers. Here we present an approach that we refer to as light-sheet 3D laser microprinting. It combines image projection with an AND-type optical nonlinearity based on two-colour two-step absorption. The underlying photoresin is composed of 2,3-butanedione as the photoinitiator, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl as the scavenger and dipentaerythritol hexaacrylate as the multifunctional monomer. Using continuous-wave laser diodes at 440 nm wavelength for projection and a continuous-wave laser at 660 nm for the light-sheet, we achieve a peak printing rate of 7 × 106 voxels s–1 at a voxel volume of 0.55 μm3.

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Fig. 1: Light-sheet 3D printing via non-degenerate two-step absorption photoinitiation.
Fig. 2: Two-colour point-scanning polymerization threshold experiments on biacetyl-containing photoresins.
Fig. 3: Light-sheet 3D printing setup.
Fig. 4: Suspended lines as 3D printing voxel-size benchmark.
Fig. 5: Oblique-view SEM images of light-sheet 3D printed micro-objects.

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Data availability

The data underlying the plots in this paper and its Supplementary Information and the related 3D printing files are available via the open-access data repository of the Karlsruhe Institute of Technology (https://doi.org/10.5445/IR/1000150926).

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Acknowledgements

We acknowledge fruitful discussions with P. Jöckle and A. Neil-Unterreiner (both from the Institute of Physical Chemistry, KIT). We thank R. Batchelor and M. Nardi (both formerly at the ITCP, KIT) for synthesizing, purifying and analysing the chemicals related to the project. We thank M. A. Seiberlich (Light Technology Institute, KIT) for a measurement using a white-light interferometer. V.H. was partially funded by the Max Planck School of Photonics. This research has additionally been funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy via the Excellence Cluster ‘3D Matter Made to Order’ (EXC-2082/1-390761711), which has also been supported by the Carl Zeiss Foundation through the ‘Carl-Zeiss-Foundation-Focus@HEiKA’, by the State of Baden-Württemberg and by KIT. We further acknowledge support by the Helmholtz program ‘Materials Systems Engineering’ (MSE), the Karlsruhe School of Optics & Photonics (KSOP), and the Ministry of Science, Research and Arts of Baden-Württemberg as part of the sustainability financing of the projects of the Excellence Initiative II. C.B.-K. acknowledges funding via an Australian Research Council (ARC) Laureate Fellowship enabling his photochemical research program (FL170100014).

Author information

Authors and Affiliations

  1. Institute of Applied Physics, Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany

    Vincent Hahn, Pascal Rietz, Frank Hermann & Martin Wegener

  2. Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany

    Vincent Hahn, Pascal Rietz, Patrick Müller, Christopher Barner-Kowollik, Tobias Schlöder, Wolfgang Wenzel & Martin Wegener

  3. Nanoscribe GmbH & Co. KG, Eggenstein-Leopoldshafen, Germany

    Patrick Müller

  4. Centre for Materials Science, School of Chemistry and Physics, Queensland University of Technology (QUT), Brisbane, Queensland, Australia

    Christopher Barner-Kowollik

  5. Institute for Molecular Systems Engineering and Advanced Materials, Ruprecht-Karls-Universität Heidelberg, Heidelberg, Germany

    Eva Blasco

  6. Institute of Organic Chemistry, Ruprecht-Karls-Universität Heidelberg, Heidelberg, Germany

    Eva Blasco

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Contributions

V.H. proposed the idea for light-sheet 3D printing using two-colour two-step absorption to M.W. V.H. and E.B. searched the literature for suitable photoinitiator candidates, including suggestions from C.B.-K. V.H. and P.M. experimentally screened the photoinitiator candidates. V.H. searched the literature for quenchers and scavengers and characterized the photoresins. P.R. characterized the photoresins in argon and oxygen atmospheres. T.S. and W.W. calculated the molecular electronic transitions of biacetyl. V.H. designed the light-sheet 3D printing setup. F.H. set up and programmed the control unit for the LCD and the stages. M.W. supervised the project. All the authors participated in the discussions on the project. V.H. and M.W. drafted an initial version of the manuscript. All the authors contributed to the interpretation of the results and to the writing of the manuscript.

Corresponding author

Correspondence to Vincent Hahn.

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Competing interests

V.H., P.M., E.B. and M.W. are inventors on a patent application filed in Germany on light-sheet 3D printing (DE102018009916A1). The other authors declare no competing interests.

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Peer review information

Nature Photonics thanks Paul Braun and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–20, Tables 1–5, Notes 1–3, Videos 1–5, Methods and references.

Supplementary Video 1

SEM flyby of the quarter-cut roton structure (Fig. 5c).

Supplementary Video 2

Video recording of the printing process of the roton metamaterial structure (Fig. 5c). This view is coaxially aligned to the light-sheet propagation direction. Light from the light-sheet beam and projection beam is removed by chromatic filters. During printing, luminescence can be observed. The video is in real time.

Supplementary Video 3

Video recording of the printing process of the #3DBenchy fleet. The perspective is the same as that in Supplementary Video 2. The video is in real time. In this video, several boats are stitched using a precision stage.

Supplementary Video 4

Low-magnification video recording of the printing process of the #3DBenchy fleet. The light-sheet beam is impinging from the right into the photoresin-filled cuvette. A glass rod serves as the printing substrate and is actuated by a set of high-precision stages. Laser light is filtered out. However, luminescence within the glass-rod can be observed. The video is in real time.

Supplementary Video 5

Video recording of the printing process of the chiral metamaterial (Fig. 5e). The perspective is the same as that in Supplementary Video 2. The video is in real time.

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Hahn, V., Rietz, P., Hermann, F. et al. Light-sheet 3D microprinting via two-colour two-step absorption. Nat. Photon. 16, 784–791 (2022). https://doi.org/10.1038/s41566-022-01081-0

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