Metal–organic frameworks (MOFs) offer disruptive potential in micro- and optoelectronics because of the unique properties of these microporous materials. Nanoscale patterning is a fundamental step in the implementation of MOFs in miniaturized solid-state devices. Conventional MOF patterning methods suffer from low resolution and poorly defined pattern edges. Here, we demonstrate the resist-free, direct X-ray and electron-beam lithography of MOFs. This process avoids etching damage and contamination and leaves the porosity and crystallinity of the patterned MOFs intact. The resulting high-quality patterns have excellent sub-50-nm resolution, and approach the mesopore regime. The compatibility of X-ray and electron-beam lithography with existing micro- and nanofabrication processes will facilitate the integration of MOFs in miniaturized devices.
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M.T. acknowledges the financial support from a Marie Skłodowska‐Curie Individual Fellowship (no. 708439, VAPOMOF). R.A. acknowledges funding from the European Research Council (no. 716472, VAPORE) and the Research Foundation Flanders (FWO) for funding in the research projects G083016N and 1501618N and the infrastructure project G0H0716N. P.F. acknowledges funding from the European Research Council (no. 771834, POPCRYSTAL) and LP-03. J.T. and S.D.F. acknowledge support by FWO and KU Leuven internal funds. M.L.T. acknowledges the financial support from an FWO senior postdoctoral fellowship (12ZK720N). D.E.K. acknowledges the Marie Skłodowska-Curie Training Network (no. 765378, HYCOAT) for the financial support. This work was additionally supported (Z.W. and R.A.F.) by the DFG Priority Program 1982 COORNETs (www.coornets.tum.de). This research project has received funding from the EU’s H2020 framework programme for research and innovation under grant agreements 801464 FETOPEN-1-2016-2017 and 654360 NFFA-Europe (proposal IDs 399, 462, 589, 596 and 854). T. Stassin and J. Marreiros are acknowledged for the help and discussions regarding the SAXS measurements. We thank E. Hedlund and M. Roeffaers for the assistance with the installation of the diffraction grating sensor setup, B. Raes and J. van de Vondel for the help with the EBL tool and M. Krishtab for the discussion on MOFs for low-k dielectrics.
The authors declare no competing interests.
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a, 3D optical profilometry of a ZIF-71 pattern (dumbbell shape), and the corresponding cross-section SEM images (b). c, 3D optical profilometry of a ZIF-71 patterns (square) and the corresponding top-view SEM images (d). e, 3D optical profilometry of a ZIF-71 patterns (hexagon) and the corresponding top-view SEM images (f).
a, SEM image of pristine ZIF-8_dcIm single crystals. b, SEM image of ZIF-8_dcIm single crystals of which part has been cut away via XRL (red dashed box). c, SEM images of ZIF-8_dcIm single crystals after XRL patterning with a negative hexagonal grid mask. d-g, SEM images of ZIF-8_dcIm single crystals after XRL patterning with different shaped positive masks. All crystals were spread on double-sided Kapton tape on a Si wafer. Because of the weak adhesion between the crystals and the substrate, some patterned crystals were tilted or fell over (for example, the rod-shaped crystals in panel c) after development. The imprint on the substrate occurs because of the X-ray-induced damage of the Kapton tape.
SEM images of EBL-patterned ZIF-71 patterns with different sizes of trenches: a, 70 nm; b, 100 nm; c, 200 nm; d, 500 nm. SEM images of EBL-patterned ZIF-71 patterns with different sizes of square-shaped holes: e, 70 nm; f, 100 nm; g, 200 nm; h, 500 nm.
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Tu, M., Xia, B., Kravchenko, D.E. et al. Direct X-ray and electron-beam lithography of halogenated zeolitic imidazolate frameworks. Nat. Mater. 20, 93–99 (2021). https://doi.org/10.1038/s41563-020-00827-x