Abstract
Three-dimensional (3D) printing1,2,3,4,5,6,7,8,9 has revolutionized manufacturing processes for electronics10,11,12, optics13,14,15, energy16,17, robotics18, bioengineering19,20,21 and sensing22. Downscaling 3D printing23 will enable applications that take advantage of the properties of micro- and nanostructures24,25. However, existing techniques for 3D nanoprinting of metals require a polymer–metal mixture, metallic salts or rheological inks, limiting the choice of material and the purity of the resulting structures. Aerosol lithography has previously been used to assemble arrays of high-purity 3D metal nanostructures on a prepatterned substrate26,27, but in limited geometries26,27,28,29,30. Here we introduce a technique for direct 3D printing of arrays of metal nanostructures with flexible geometry and feature sizes down to hundreds of nanometres, using various materials. The printing process occurs in a dry atmosphere, without the need for polymers or inks. Instead, ions and charged aerosol particles are directed onto a dielectric mask containing an array of holes that floats over a biased silicon substrate. The ions accumulate around each hole, generating electrostatic lenses that focus the charged aerosol particles into nanoscale jets. These jets are guided by converged electric-field lines that form under the hole-containing mask, which acts similarly to the nozzle of a conventional 3D printer, enabling 3D printing of aerosol particles onto the silicon substrate. By moving the substrate during printing, we successfully print various 3D structures, including helices, overhanging nanopillars, rings and letters. In addition, to demonstrate the potential applications of our technique, we printed an array of vertical split-ring resonator structures. In combination with other 3D-printing methods, we expect our 3D-nanoprinting technique to enable substantial advances in nanofabrication.
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Data availability
Source data for phenomenological model results and reflection spectra are provided. Source data are provided with this paper.
Code availability
The procedure used to obtain the phenomenological model prediction (using MathCAD) is provided in Supplementary Information.
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Acknowledgements
This work was supported by the Global Frontier R&D program of the Center for Multiscale Energy System (2012M3A6A7054855) and Mid-Career Research program (2020R1A2C2101132) by the National Research Foundation (NRF) under the Ministry of Science and ICT (MSIT), Korea. J.R. acknowledges the Global Frontier R&D program of the Center for Advanced Meta-Materials (2019M3A6B3030637), the Mid-Career Researcher program (2019R1A2C3003129) and the Regional Leading Research Center program (2019R1A5A8080290) funded by the NRF-MSIT, Korea. Y.Y. acknowledges a fellowship from the Hyundai Motor Chung Mong-Koo foundation. M.K. acknowledges the NRF Global PhD fellowship (2017H1A2A1043204) funded by the Ministry of Education, Korea. We thank K. Bang for atomic force microscopy (AFM) measurement.
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Contributions
M.C. conceived the idea, and W.J., Y.-H.J. and M.C. designed the experiments. W.J. and Y.-H.J. implemented the experimental set-up and conducted experiments. P.V.P. suggested the Faraday line concept and built the phenomenological models. W.J., Y.-H.J., J.F., P.V.P. and M.C. analysed data and participated in discussions, together with J.S. and K.-Y.K. J.R. and Y.Y. designed the vSRR devices and optical measurements. Y.Y., M.K. and J.R. performed optical calculations and related analysis. Y.Y., J.R., H.-Y.T. and T.T. performed optical measurements. H.C. did initial experiments using a mask. W.J., Y.-H.J., P.V.P., J.F., Y.Y., J.R. and M.C. wrote the paper. J.R. directed optical studies. M.C. led the work.
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Extended data figures and tables
Extended Data Fig. 1 Experimental setup for 3D nanoprinting and surface potential distribution of the SiNx mask measured after printing helices.
a, The setup consists of a particle source, an SMPS and a 3D-nanoprinting system, with a piezoelectric nanostage controlled by a computer. Charged aerosols are generated by a spark discharge generator and flow into the 3D-nanoprinting system via N2 carrier gas (details in Methods section ‘Generation of charged aerosols’). We measured the size distribution of the nanoparticles by using the SMPS before printing structures (Methods section ‘Size distribution measurement of metal nanoparticles’; size distribution data in Extended Data Fig. 3a–d). b, 3D surface potential distribution (colour scale) of the SiNx mask in the 3D-nanoprinting system. c, Kelvin force microscopy data of the surface potential distribution along the white dashed arrow in b, confirming the presence of ions on the surface of the SiNx mask. The black line is the raw data and the red line represents the average of these data (658 μV).
Extended Data Fig. 2 SEM images of printed wall-like 3D structures.
The process for printing wall-like structures is similar to tip-directed growth because the tip apexes can spread along the line of the wall. a, b, Top-view (a) and tilt-view (b) images of the letters ‘SNU’ (abbreviation for Seoul National University; width, 600 nm; height, 3.5 μm). c, d, Top-view (c) and tilt-view (d) images of fallen-over tables (width, 700 nm; height, 3.1 μm). e, f, Top-view (e) and tilt-view (f) images of castle-like structures (height, 3.2 μm). The fabricated shapes of the structures follow the shapes designed on the mask, as shown in Supplementary Table 1. However, the growth of each structure is not perfectly uniform along the slit because the converging prefocusing electric field is not uniform along the slit, owing to edge effects. The design of mask patterns should be optimized to produce the exact desired structure.
Extended Data Fig. 3 Size distribution of nanoparticles measured by the SMPS and TEM images of the nanoparticles.
a–d, Size distributions of Pd (a), Cu (b), Ag (c) and Au (d) nanoparticles, showing a geometric mean diameter of dg = 9.6 nm (Pd), dg = 9.7 nm (Cu), dg = 6.3 nm (Ag) and dg = 8.4 nm (Au) and a geometric standard deviation of σg = 1.52 (Pd), σg = 1.57 (Cu), σg = 1.45 (Ag) and σg = 1.45 (Au). N is the particle number concentration and dp is the particle diameter. e–h, TEM images of Pd (e), Cu (f), Ag (g) and Au (h) nanoparticles. We deposited nanoparticles on TEM grids before they entered the 3D-nanoprinting system (Extended Data Fig. 1a). These images show the crystalline structures of the nanoparticles.
Extended Data Fig. 4 EDS analysis of nanopillars.
a–i, EDS analysis of single Pd (a–c), Au (d–f) and Ag (g–i) nanopillars. Data show EDS maps (a, d, g) and point (b, e, h) and area (c, f, i) spectra for each material. j, k, The nanopillars consist of almost pure Pd (more than 97 wt%), Au (more than 99 wt%) and Ag (more than 98 wt%) because O and C are always present owing to the exposure of the sample to the environment. White circles (j) indicate individual measured values (n = 10). Data are mean ± s.d.
Extended Data Fig. 5 SEM images of various structures printed by 2D and 3D nanostage motion.
a, 3D zigzag-shaped structures. After initial deposition for 600 s (with this position defined as the origin of the coordinates of the nanostage movement), the piezoelectric nanostage was moved to the left by 1 μm along the x axis at 4.2 nm s−1. Then, it was moved past the origin and further to the right by 1 μm along the x axis at 4.2 nm s−1. Finally, it was moved back to the origin at 4.2 nm s−1. The initial distance between the mask and the substrate was 7 μm. After stationary deposition (600 s), the nanostage was moved down 2 μm at 2.1 nm s−1. b, 3D stair-like structures. After initial deposition for 600 s, the nanostage was jumped to 1 μm from the initial point for 7.5 min of deposition. These two steps were then repeated a second time. The initial distance between the mask and the substrate was 6 μm. After stationary deposition (600 s), the nanostage was moved down 1.5 μm at 1.3 nm s−1. c, d, Top-view (c) and tilt-view (d) SEM images of 3D helices rotated 180° (Rs = 1 μm, ω = 4π h−1, Lp = 1.12 μm). The initial distance between the mask and the substrate was 6 μm. The nanostage was then moved down 1.5 μm at 1.7 nm s−1. e, f, Top-view (e) and tilt-view (f) SEM images of 3D helices rotated 720°. After initial deposition for 180 s, the nanostage was rotated 720° (Rs = 250 nm, ω = 8π h−1, Lp = 430 nm). The initial distance between the mask and the substrate was 2 μm. The nanostage was then moved down 6.3 μm at 3.5 nm s−1. g, h, Top-view (g) and tilt-view (h) SEM images of 3D helices rotated 360° anticlockwise and then 360° clockwise, after initial deposition for 240 s (Rs = 250 nm, ω = 8π h−1, Lp = 320 nm). The initial distance between the mask and the substrate was 2 μm. The nanostage was then moved down 6.3 μm at 3.5 nm s−1.
Extended Data Fig. 6 Reproducibility of 45° overhanging Au structures and 3D helices.
a–c, Tilt-view SEM images of three different 45° overhanging Au structures. d, e, Statistical data for a–c (n = 12). f–h, Tilt-view SEM images of three different 3D helices. i, j, Statistical data for f–h (n = 10). Panels a and f correspond to Fig. 2c and Fig. 3a, respectively. White circles in d and i indicate individual measured values. Data (d, e, i, j) are mean ± s.d.
Extended Data Fig. 8 Manufacturing process of Au vertical SRRs.
We fabricated vertical SRRs using a mask with round-hole patterns with a spacing of 13 μm and diameter of 4 μm. The distance between the mask and substrate was consistently 5 μm during the fabrication process. a, SEM image of a magnified single vertical SRR. The numbers in boxes represent the manufacturing sequence. First, we first achieved a 1.8-μm-long bottom parallel line in surface-writing mode, using a horizontal translation speed of 66.7 nm s−1 over a total nanostage translation distance of 2 μm. After four repeated printing steps in writing mode, the bottom parallel line grew to a thickness of 500 nm. Second, we grew a 1.2-μm-tall vertical pillar at the left-hand end of the bottom line structure. Third, the nanostage was moved to the right-hand end of the bottom line, and this positioning was maintained for 170 s to grow a pillar with a height of 3.2 μm. Fourth, the nanostage was jumped to a horizontal distance of 550 nm from the top of the vertical pillar printed in the third step and translated 1.6 μm at a continuous speed of 17.8 nm s−1 to print the top line, which is parallel to the bottom line. More details of the structural dimensions are provided in Supplementary Table 2. b, Top-view SEM image of fabricated vertical SRRs, showing the first (red dashed boxes) and second (blue dashed boxes) arrays of vertical SRRs. To increase the structure density and thus magnetic-field intensity, the nanostage was moved 6.5 μm along the x and y axes to overlay the second vertical SRR array at the centre of the first. The manufacturing of the second array followed process outlined in a. This resulted in vertical SRRs spaced at a constant distance of 9.2 μm in the magnetic-field propagation direction.
Supplementary information
Supplementary Information
This file contains Supplementary Methods, Supplementary Results, Supplementary Tables 1-6, Supplementary Figures 1-7 and the procedure for obtaining phenomenological model prediction.
Video 1
The 30 degree slanted overhanging structure.
Video 2
The 45 degree slanted overhanging structure.
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Jung, W., Jung, YH., Pikhitsa, P.V. et al. Three-dimensional nanoprinting via charged aerosol jets. Nature 592, 54–59 (2021). https://doi.org/10.1038/s41586-021-03353-1
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DOI: https://doi.org/10.1038/s41586-021-03353-1
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