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Direct X-ray and electron-beam lithography of halogenated zeolitic imidazolate frameworks

Nature Materials volume 20, pages 93–99 (2021)Cite this article

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Abstract

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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Fig. 1: Direct patterning of MOF films by XRL and EBL.
Fig. 2: Halogenated ZIF films and single crystals after XRL patterning.
Fig. 3: Mechanistic investigation of the X-ray dose on ZIF-71.
Fig. 4: High-resolution EBL patterning of 100 nm thick ZIF-71 films.
Fig. 5: Porosity characterization and sensing application of patterned ZIF-71 films.

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Data availability

The data represented in Figs. 2a,b, 3 and 5c,d,h are provided with the paper as Source data. The image datasets are available from figshare (https://doi.org/10.6084/m9.figshare.12946922).

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Acknowledgements

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.

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Authors and Affiliations

  1. Centre for Membrane Separations, Adsorption, Catalysis, and Spectroscopy for Sustainable Solutions (cMACS), KU Leuven, Leuven, Belgium

    Min Tu, Benzheng Xia, Dmitry E. Kravchenko, Max Lutz Tietze, Alexander John Cruz, Ivo Stassen & Rob Ameloot

  2. Research Group of Electrochemical and Surface Engineering, Department of Materials and Chemistry, Vrije Universiteit Brussel, Brussels, Belgium

    Alexander John Cruz & Tom Hauffman

  3. Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven, Leuven, Belgium

    Joan Teyssandier & Steven De Feyter

  4. Catalysis Research Centre, Technical University of Munich, Garching, Germany

    Zheng Wang & Roland A. Fischer

  5. Institute of Inorganic Chemistry, Graz University of Technology, Graz, Austria

    Benedetta Marmiroli, Heinz Amenitsch & Ana Torvisco

  6. Institute of Physical and Theoretical Chemistry, Graz University of Technology, Graz, Austria

    Miriam de J. Velásquez-Hernández & Paolo Falcaro

  7. School of Physical Sciences, Faculty of Sciences, University of Adelaide, Adelaide, South Australia, Australia

    Paolo Falcaro

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Contributions

M.T. and R.A. conceived and designed the experiments. M.T. carried out and analysed film deposition, patterning and characterization experiments. M.T., B.X., D.E.K., M.J.V.H., A.T. and P.F. carried out bulk MOF synthesis and characterization. M.T., B.X., D.E.K., I.S. and B.M. carried out the XRL patterning. M.T., B.X., D.E.K. and H.A. carried out SAXS measurements. A.J.C and T.H. conducted the XPS measurements. M.T., J.T. and S.D.F contributed to the AFM measurements. M.T. and M.L.T. designed and conducted the diffraction grating sensing. Z.W. and R.A.F. conducted QCM measurements. The manuscript was written by M.T. and R.A., with the input of all authors.

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Correspondence to Rob Ameloot.

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Extended data

Extended Data Fig. 1 XRL-patterned 300 nm thick ZIF-71 films.

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).

Extended Data Fig. 2 XRL-patterned ZIF-8_Cl single crystals.

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.

Extended Data Fig. 3 EBL-patterned 100 nm thick ZIF-71 film.

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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Supplementary Information Sections 1–8, Figures 1–71, Tables 1–6 and references 1–37.

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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

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