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Xolography for linear volumetric 3D printing

Abstract

The range of applications for additive manufacturing is expanding quickly, including mass production of athletic footwear parts1, dental ceramics2 and aerospace components3 as well as fabrication of microfluidics4, medical devices5, and artificial organs6. The light-induced additive manufacturing techniques7 used are particularly successful owing to their high spatial and temporal control, but such techniques still share the common motifs of pointwise or layered generation, as do stereolithography8, laser powder bed fusion9, and continuous liquid interface production10 and its successors11,12. Volumetric 3D printing13,14,15,16,17,18,19,20 is the next step onward from sequential additive manufacturing methods. Here we introduce xolography, a dual colour technique using photoswitchable photoinitiators to induce local polymerization inside a confined monomer volume upon linear excitation by intersecting light beams of different wavelengths. We demonstrate this concept with a volumetric printer designed to generate three-dimensional objects with complex structural features as well as mechanical and optical functions. Compared to state-of-the-art volumetric printing methods, our technique has a resolution about ten times higher than computed axial lithography without feedback optimization, and a volume generation rate four to five orders of magnitude higher than two-photon photopolymerization. We expect this technology to transform rapid volumetric production for objects at the nanoscopic to macroscopic length scales.

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Fig. 1: Xolography 3D printing technology.
Fig. 2: Volumetric digital manufacturing.
Fig. 3: Characterization of high-resolution object features.

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Data availability

The data that support the findings of this study are available within the paper and Supplementary Information. Additional supporting data generated during the present study are available from the corresponding authors upon reasonable request.

References

  1. Zastrow, M. 3D printing gets bigger, faster and stronger. Nature 578, 20–23 (2020).

    Article  ADS  CAS  Google Scholar 

  2. Galante, R., Figueiredo-Pina, C. G. & Serro, A. P. Additive manufacturing of ceramics for dental applications: a review. Dent. Mater. J. 35, 825–846 (2019).

    Article  CAS  Google Scholar 

  3. Najmon, J. C., Raeisi, S. & Tovar, A. Review of additive manufacturing technologies and applications in the aerospace industry. In Additive Manufacturing for the Aerospace Industry (eds Froes, F. & Boyer, R.) (Elsevier, 2019).

  4. Ahmadi, A. et al. Additive manufacturing of laminar flow cells for single-molecule experiments. Sci. Rep. 9, 16784 (2019).

    Article  ADS  Google Scholar 

  5. Douroumis, D. 3D printing of pharmaceutical and medical applications: a new era. Pharm. Res. 36, 42 (2019).

    Article  Google Scholar 

  6. Lee, A. et al. 3D bioprinting of collagen to rebuild components of the human heart. Science 365, 482–487 (2019).

    Article  ADS  CAS  Google Scholar 

  7. Jung, K. et al. Designing with light: advanced 2D, 3D, and 4D materials. Adv. Mater. 32, 1903850 (2020).

    Article  CAS  Google Scholar 

  8. Hull, C. W. Apparatus for production of three-dimensional objects by stereolithography. US Patent 4,575,330 (1986).

  9. Zhang, D. et al. Additive manufacturing of ultrafine-grained high-strength titanium alloys. Nature 576, 91–95 (2019).

    Article  ADS  CAS  Google Scholar 

  10. Tumbleston, J. et al. Additive manufacturing. Continuous liquid interface production of 3D objects. Science 347, 1349–1352 (2015).

    Article  ADS  CAS  Google Scholar 

  11. Walker, D. A., Hedrick, J. L. & Mirkin, C. A. Rapid, large-volume, thermally controlled 3D printing using a mobile liquid interface. Science 366, 360–364 (2019).

    Article  ADS  CAS  Google Scholar 

  12. de Beer, M. P. et al. Rapid, continuous additive manufacturing by volumetric polymerisation inhibition patterning. Sci. Adv. 5, eaau8723 (2019).

    Article  ADS  Google Scholar 

  13. Shusteff, M. et al. One-step volumetric additive manufacturing of complex polymer structures. Sci. Adv. 3, eaao5496 (2017).

    Article  Google Scholar 

  14. Kelly, B. E. et al. Volumetric additive manufacturing via tomographic reconstruction. Science 363, 1075–1079 (2019).

    Article  ADS  CAS  Google Scholar 

  15. Loterie, D., Delrot, P. & Moser, C. High-resolution volumetric additive manufacturing. Nat. Commun. 11, 852 (2020).

    Article  ADS  CAS  Google Scholar 

  16. Baldachini, T. Three-Dimensional Microfabrication Using Two-Photon Polymerisation: Fundamentals, Technology and Applications (Elsevier, 2019).

  17. Zheng, L. et al. Nanofabrication of high-resolution periodic structures with a gap size below 100 nm by two-photon polymerisation. Nanoscale Res. Lett. 14, 134 (2019).

    Article  ADS  Google Scholar 

  18. Geng, Q., Wang, D. & Chen, P. Ultrafast multi-focus 3-D nano-fabrication based on two-photon polymerisation. Nat. Commun. 10, 2179 (2019).

    Article  ADS  Google Scholar 

  19. Saha, S. et al. Scalable submicrometer additive manufacturing. Science 366, 105–109 (2019).

    Article  ADS  CAS  Google Scholar 

  20. Bernal, P. N. et al. Volumetric bioprinting of complex living-tissue constructs within seconds. Adv. Mater. 31, 1970302 (2019).

    Article  Google Scholar 

  21. Swainson, W. K. Method, medium and apparatus for producing three-dimensional figure product. US patent US4041476A (1977).

  22. Scott, T., Kowalski, B., Sullivan, A., Bowman, C. & Mcleod, R. Two-color single-photon photoinitiation and photoinhibition for subdiffraction photolithography. Science 324, 913–917 (2009).

    Article  ADS  CAS  Google Scholar 

  23. Liaros, N. & Fourkas, J. T. Ten years of two-color photolithography. Opt. Mater. Express 9, 3006–3020 (2019).

    Article  ADS  CAS  Google Scholar 

  24. van der Laan, H. L., Burns, M. A. & Scott, T. F. Volumetric photopolymerisation confinement through dual-wavelength photoinitiation and photoinhibition. ACS Macro Lett. 8, 899–904 (2019).

    Article  Google Scholar 

  25. Goulet-Hanssens, A., Eisenreich, F. & Hecht, S. Enlightening materials with photoswitches. Adv. Mater. 32, 1905966 (2020).

    Article  CAS  Google Scholar 

  26. Patel, S., Cao, J. & Lippert, A. A volumetric three-dimensional digital light photoactivatable dye display. Nat. Commun. 8, 15239 (2017).

    Article  ADS  CAS  Google Scholar 

  27. Jeudy, M. J. & Robillard, J. J. Spectral photosensitisation of a variable index material for recording phase holograms with high efficiency. Opt. Commun. 13, 25–28 (1975).

    Article  ADS  CAS  Google Scholar 

  28. Ichimura, K. & Sakuragi, M. A. Spiropyran-iodonium salt system as a two photon radical photoinitiator. J. Polym. Sci. C 26, 185–189 (1988).

    CAS  Google Scholar 

  29. Lee, S.-K. & Neckers, D. Two-photon radical-photoinitiator system based on iodinated benzospiropyrans. Chem. Mater. 3, 858–864 (1991).

    Article  CAS  Google Scholar 

  30. Born, M. & Wolf, E. Principles of Optics: Electromagnetic Theory of Propagation, Interference and Diffraction of Light (Cambridge Univ. Press, 1999).

  31. OSIRIX DICOM Image Library http://www.osirix-viewer.com/resources/dicom-image-library (accessed 2 April 2020).

  32. Kikinis, R., Pieper, S. D. & Vosburgh, K. G. 3D Slicer: a platform for subject-specific image analysis, visualisation, and clinical support. In Intraoperative Imaging and Image-Guided Therapy (ed. Jolesz, F.) (Springer, 2014).

  33. Aloui, F. et al. Refractive index evolution of various commercial acrylic resins during photopolymerisation. Express Polym. Lett. 12, 966–971 (2018).

    Article  CAS  Google Scholar 

  34. Liu, Y. et al. Improvement of the diffraction properties in holographic polymer dispersed liquid crystal Bragg gratings. Opt. Commun. 218, 27–32 (2003).

    Article  ADS  CAS  Google Scholar 

  35. Saleh, B. E. A. et al. Fundamentals of Photonics (John Wiley & Sons, 2019).

  36. Zhou, X. et al. Rayleigh scattering of linear alkylbenzene in large liquid scintillator detectors. Rev. Sci. Instrum. 86, 073310 (2015).

    Article  ADS  Google Scholar 

  37. Coumou, D. J., Mackor, E. L. & Hijmans, J. Isotropic light-scattering in pure liquids. Trans. Faraday Soc. 60, 1539 (1964).

    Article  CAS  Google Scholar 

  38. Fandiño, O., Comuñas, M. J. P., Lugo, L., López, E. R. & Fernández, J. Density measurements under pressure for mixtures of pentaerythritol ester lubricants. Analysis of a density−viscosity relationship. J. Chem. Eng. Data 52, 1429–1436 (2007).

    Article  Google Scholar 

  39. Fandiño, O., Pensado, A. S., Lugo, L., Comuñas, M. J. P. & Fernández, J. Compressed liquid densities of squalane and pentaerythritol tetra(2-ethylhexanoate). J. Chem. Eng. Data 50, 939–946 (2005).

    Article  Google Scholar 

  40. Fandiño, O., Pensado, A. S., Lugo, L., Comuñas, M. J. P. & Fernández, J. Volumetric behaviour of the environmentally compatible lubricants pentaerythritol tetraheptanoate and pentaerythritol tetranonanoate at high pressures. Green Chem. 7, 775–783 (2005).

    Article  Google Scholar 

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Acknowledgements

We thank D. Radzinski for continuous support, F. Pinno and N. Wandel for SEM measurements, P. Fengler and A. F. Thünemann as well as J. Müller and A. Gurlo for help with material property measurements, S. Schneider and M. Dinter for 3D visualization of the printing zone, A. Steinbach for CAD modelling of the optical setup, and M. Vollmer for proofreading the manuscript.

Author information

Authors and Affiliations

Authors

Contributions

M. Regehly and S.H. designed the research and wrote the paper. Y.G. designed the spiropyran photoinitiator. Synthesis and characterization was performed by Y.G. and M. Reuter. Theoretical work and simulations by M. Regehly. Volumetric printer development was done by M. Regehly, M. Reuter, D.P.K. and C.-Y.C. 3D data processing was done by M. Reuter, E.I. and M. Regehly. Development of resin formulations, characterization and post-processing were performed by N.F.K., E.I. and Y.G. Software development was done by K.K. and B.A.

Corresponding authors

Correspondence to Martin Regehly or Stefan Hecht.

Ethics declarations

Competing interests

Two patents (DE 10 2019 115 336 and DE 10 2019 129 868) have been filed related to the topic covered in this publication.

Additional information

Peer review information Nature thanks Cyrille Boyer, Robert McLeod and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Peer reviewer reports are available.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data figures and tables

Extended Data Fig. 1 Synthesis of DCPI.

MeI, methyl iodide (CH3I).

Extended Data Fig. 2 1H NMR (500 MHz, CDCl3) of DCPI

.

Extended Data Fig. 3 13C NMR (126 MHz, CDCl3) of DCPI

.

Extended Data Fig. 4 19F NMR (471 MHz, CDCl3) of DCPI

.

Extended Data Fig. 5 Optical design and characterization of the light sheet generator.

a, Schematic representation of the optical setup. L1, Powell lens. L2, L3, cylindrical lenses. S, beamsplitter. M, mirrors. A, linear axis. C, cuvette. b, Partial image of the light sheet in one arm at waist position. c, Horizontal lineout of the light sheet intensity distribution.

Extended Data Fig. 6 Results of the calibration procedure.

a, Diagram showing an array of tested irradiance/velocity combinations, which are used to identify the parameter space for xolography 3D printing. b, Photograph of the automated testing procedure in a 1-cm cuvette containing resin 1.

Extended Data Fig. 7 Optimal light sheet waist widths.

The plot shows the FWHM waist sizes dFWHM of the light sheet against volume depth D for different values of the homogeneity factor β. The simulation has been performed for the design wavelength of λ = 375 nm and assumed refractive index of the resin of n = 1.56 (375 nm).

Extended Data Fig. 8 Simulation of light sheet intensity distributions.

a, Exponential intensity decrease along the 1-cm volume depth for single-side illumination. b, Double-sided illumination leads to a nearly homogenous distribution for 1-cm depth. c, Maximum deviation from the average intensity in percentage for volume depths of up to 10 cm.

Extended Data Fig. 9 Mechanical characterization of printed and post-processed test specimen.

a, Stress–strain curve obtained at a nominal strain rate of 4 × 10−2 s−1. The inset shows the sample mounted to the holder of the tensile testing machine. b, Modulus-temperature behaviour acquired using a 1 K min−1 heating ramp rate and an amplitude of 30 µm at an oscillation frequency of 1 Hz. The inset shows the sample mounted to the stage of the dynamic mechanical analyser.

Supplementary information

Peer Review File

Video 1

: Xolography volumetric 3D printing. Video of the printing process in 1, 3 and 5 cm volume depth. Solidified objects are highly transparent and only visible via diffuse light scattering.

Video 2

: Function test of the printed flowcell. A simple example of multicomponent systems with mechanical functionalities made by volumetric 3D printing in one step without the need for subsequent assembly.

Video 3

| Stability demonstration of the anatomical model. If required, xolography creates objects with similar mechanical stability compared to conventional point-by-point or layer-by-layer production processes.

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Regehly, M., Garmshausen, Y., Reuter, M. et al. Xolography for linear volumetric 3D printing. Nature 588, 620–624 (2020). https://doi.org/10.1038/s41586-020-3029-7

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