journal article·2021-01Open access

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

Min Tu, Benzheng Xia, Dmitry E. Kravchenko, Max Lutz Tietze, Alexander John Cruz, Ivo Stassen, Tom Hauffman, Joan Teyssandier, Steven De Feyter, Zheng Wang, Roland A. Fischer, Benedetta Marmiroli, Heinz Amenitsch, Ana Torvisco, Miriam de J. Velásquez-Hernández, Paolo Falcaro, Rob Ameloot

Nature Materials· Volume 20· Issue 1

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.
Source: europepmc · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Metal-Organic Frameworks: Synthesis and Applications · Copper Interconnects and Reliability · Corrosion Behavior and Inhibition

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (67)

Show source-provided references
1. Aizenberg, J., Black, A. J. & Whitesides, G. M. Control of crystal nucleation by patterned self-assembled monolayers. Nature 398, 495–498 (1999).10.1038/19047 ↗
2. Liddle, J. A. & Gallatin, G. M. Nanomanufacturing: a perspective. ACS Nano 10, 2995–3014 (2016).10.1021/acsnano.5b03299 ↗
3. Isaacoff, B. P. & Brown, K. A. Progress in top-down control of bottom-up assembly. Nano Lett. 17, 6508–6510 (2017).10.1021/acs.nanolett.7b04479 ↗
4. Smith, K. H., Tejeda-Montes, E., Poch, M. & Mata, A. Integrating top-down and self-assembly in the fabrication of peptide and protein-based biomedical materials. Chem. Soc. Rev. 40, 4563–4577 (2011).10.1039/c1cs15064b ↗
5. Liu, C.-C. et al. Directed self-assembly of block copolymers for 7 nanometre FinFET technology and beyond. Nat. Electron. 1, 562–569 (2018).10.1038/s41928-018-0147-4 ↗
6. Batten, S. R. et al. Terminology of metal–organic frameworks and coordination polymers (IUPAC Recommendations 2013). Pure Appl. Chem. 85, 1715–1724 (2013).10.1351/PAC-REC-12-11-20 ↗
7. Bennett, T. D. & Horike, S. Liquid, glass and amorphous solid states of coordination polymers and metal–organic frameworks. Nat. Rev. Mater. 3, 431–440 (2018).10.1038/s41578-018-0054-3 ↗
8. Usman, M., Mendiratta, S. & Lu, K.-L. Semiconductor metal–organic frameworks: future low-bandgap materials. Adv. Mater. 29, 1605071 (2017).10.1002/adma.201605071 ↗
9. Krishtab, M. et al. Vapor-deposited zeolitic imidazolate frameworks as gap-filling ultra-low-k dielectrics. Nat. Commun. 10, 3729 (2019).10.1038/s41467-019-11703-x ↗
10. Ryder, M. R. et al. Dielectric properties of zeolitic imidazolate frameworks in the broad-band infrared regime. J. Phys. Chem. Lett. 9, 2678–2684 (2018).10.1021/acs.jpclett.8b00799 ↗
11. Lustig, W. P. et al. Metal–organic frameworks: functional luminescent and photonic materials for sensing applications. Chem. Soc. Rev. 46, 3242–3285 (2017).10.1039/C6CS00930A ↗
12. Stassen, I. et al. An updated roadmap for the integration of metal–organic frameworks with electronic devices and chemical sensors. Chem. Soc. Rev. 46, 3185–3241 (2017).10.1039/C7CS00122C ↗
13. Falcaro, P. et al. MOF positioning technology and device fabrication. Chem. Soc. Rev. 43, 5513–5560 (2014).10.1039/C4CS00089G ↗
14. Ito, T. & Okazaki, S. Pushing the limits of lithography. Nature 406, 1027–1031 (2000).10.1038/35023233 ↗
15. Lu, G., Farha, O. K., Zhang, W., Huo, F. & Hupp, J. T. Engineering ZIF-8 thin films for hybrid MOF-based devices. Adv. Mater. 24, 3970–3974 (2012).10.1002/adma.201202116 ↗
16. Stassen, I. et al. Chemical vapour deposition of zeolitic imidazolate framework thin films. Nat. Mater. 15, 304–310 (2016).10.1038/nmat4509 ↗
17. Okada, K. et al. Copper conversion into Cu(OH)2 nanotubes for positioning Cu3(BTC)2 MOF crystals: controlling the growth on flat plates, 3D architectures, and as patterns. Adv. Funct. Mater. 24, 1969–1977 (2014).10.1002/adfm.201303303 ↗
18. Dalstein, O. et al. Nanoimprinted, submicrometric, MOF-based 2D photonic structures: toward easy selective vapors sensing by a smartphone camera. Adv. Funct. Mater. 26, 81–90 (2016).10.1002/adfm.201503016 ↗
19. Razmjou, A. et al. Preparation of iridescent 2D photonic crystals by using a mussel-inspired spatial patterning of ZIF-8 with potential applications in optical switch and chemical sensor. ACS Appl. Mater. Interfaces 9, 38076–38080 (2017).10.1021/acsami.7b13618 ↗
20. Wang, Y., Fedin, I., Zhang, H. & Talapin, D. V. Direct optical lithography of functional inorganic nanomaterials. Science 357, 385–388 (2017).10.1126/science.aan2958 ↗
21. Garcia, R., Knoll, A. W. & Riedo, E. Advanced scanning probe lithography. Nat. Nanotechnol. 9, 577–587 (2014).10.1038/nnano.2014.157 ↗
22. Nakayama, K. et al. High-mobility organic transistors with wet-etch-patterned top electrodes: a novel patterning method for fine-pitch integration of organic devices. Adv. Mater. Interfaces 1, 1300124 (2014).10.1002/admi.201300124 ↗
23. Kumar, R., Singh, N., Chang, C. K., Dong, L. & Wong, T. K. S. Deep-ultraviolet resist contamination for copper/low-k dual-damascene patterning. J. Vac. Sci. Technol. B 22, 1052 (2004).10.1116/1.1738672 ↗
24. Baklanov, M. R. et al. Plasma processing of low-k dielectrics. J. Appl. Phys. 113, 041101 (2013).10.1063/1.4765297 ↗
25. Maldonado, J. R. & Peckerar, M. X-ray lithography: some history, current status and future prospects. Microelectron. Eng. 161, 87–93 (2016).10.1016/j.mee.2016.03.052 ↗
26. Chen, Y. Nanofabrication by electron beam lithography and its applications: a review. Microelectron. Eng. 135, 57–72 (2015).10.1016/j.mee.2015.02.042 ↗
27. Banerjee, R. et al. High-throughput synthesis of zeolitic imidazolate frameworks and application to CO2 capture. Science 319, 939–943 (2008).10.1126/science.1152516 ↗
28. Widmer, R. N. et al. X-ray radiation-induced amorphization of metal–organic frameworks. Phys. Chem. Chem. Phys. 21, 12389–12395 (2019).10.1039/C9CP01463B ↗
29. Innocenzi, P., Malfatti, L., Marmiroli, B. & Falcaro, P. Hard X-rays and soft-matter: processing of sol–gel films from a top down route. J. Solgel Sci. Technol. 70, 236–244 (2014).10.1007/s10971-013-3227-y ↗
30. Schweinefuß, M. E. et al. Zeolitic imidazolate framework-71 nanocrystals and a novel SOD-type polymorph: solution mediated phase transformations, phase selection via coordination modulation and a density functional theory derived energy landscape. Dalton Trans. 43, 3528–3536 (2014).10.1039/c3dt52992d ↗
31. Shen, K. et al. Ordered macro–microporous metal–organic framework single crystals. Science 359, 206–210 (2018).10.1126/science.aao3403 ↗
32. Luo, Y., Ahmad, M., Schug, A. & Tsotsalas, M. Rising up: hierarchical metal–organic frameworks in experiments and simulations. Adv. Mater. 31, 1901744 (2019).10.1002/adma.201901744 ↗
33. Choi, J. O., Moore, J. A., Corelli, J. C., Silverman, J. P. & Bakhru, H. Degradation of poly(methylmethacrylate) by deep ultraviolet, x‐ray, electron beam, and proton beam irradiations. J. Vac. Sci. Technol. B 6, 2286–2289 (1988).10.1116/1.584071 ↗
34. Ihee, H. et al. Ultrafast X-ray diffraction of transient molecular structures in solution. Science 309, 1223–1227 (2005).10.1126/science.1114782 ↗
35. Yuan, R. et al. Chlorine-radical-mediated photocatalytic activation of C–H bonds with visible light. Angew. Chem. Int. Ed. 52, 1035–1039 (2013).10.1002/anie.201207904 ↗
36. Lewandowski, M. & Ollis, D. F. Halide acid pretreatments of photocatalysts for oxidation of aromatic air contaminants: rate enhancement, rate inhibition, and a thermodynamic rationale. J. Catal. 217, 38–46 (2003).
37. Sivaguru, P., Wang, Z., Zanoni, G. & Bi, X. Cleavage of carbon–carbon bonds by radical reactions. Chem. Soc. Rev. 48, 2615–2656 (2019).10.1039/C8CS00386F ↗
38. Cruz, A. J. et al. Integrated cleanroom process for the vapor-phase deposition of large-area zeolitic imidazolate framework thin films. Chem. Mater. 31, 9462–9471 (2019).10.1021/acs.chemmater.9b03435 ↗
39. Japip, S., Liao, K.-S., Xiao, Y. & Chung, T.-S. Enhancement of molecular-sieving properties by constructing surface nano-metric layer via vapor cross-linking. J. Membr. Sci. 497, 248–258 (2016).10.1016/j.memsci.2015.09.045 ↗
40. Taylor, A. W., Men, S., Clarke, C. J. & Licence, P. Acidity and basicity of halometallate-based ionic liquids from X-ray photoelectron spectroscopy. RSC Adv. 3, 9436–9445 (2013).10.1039/c3ra40260f ↗
41. Hou, J. et al. Halogenated metal–organic framework glasses and liquids. J. Am. Chem. Soc. 142, 3880–3890 (2020).10.1021/jacs.9b11639 ↗
42. Saitoh, R., Kanazawa, A., Kanaoka, S. & Aoshima, S. Cationic polymerization of p-methylstyrene using various metal chlorides: design rationale of initiating systems for controlled polymerization of styrenes. Polym. J. 48, 933–940 (2016).10.1038/pj.2016.43 ↗
43. Furukawa, S., Reboul, J., Diring, S., Sumida, K. & Kitagawa, S. Structuring of metal–organic frameworks at the mesoscopic/macroscopic scale. Chem. Soc. Rev. 43, 5700–5734 (2014).10.1039/C4CS00106K ↗
44. Gangnaik, A. S., Georgiev, Y. M. & Holmes, J. D. New generation electron beam resists: a review. Chem. Mater. 29, 1898–1917 (2017).10.1021/acs.chemmater.6b03483 ↗
45. Conrad, S. et al. Controlling dissolution and transformation of zeolitic imidazolate frameworks by using electron-beam-induced amorphization. Angew. Chem. Int. Ed. 57, 13592–13597 (2018).10.1002/anie.201809921 ↗
46. Seo, E., Choi, B. K. & Kim, O. Determination of proximity effect parameters and the shape bias parameter in electron beam lithography. Microelectron. Eng. 53, 305–308 (2000).10.1016/S0167-9317(00)00320-8 ↗
47. Nathawat, R., Kumar, A., Acharya, N. K. & Vijay, Y. K. XPS and AFM surface study of PMMA irradiated by electron beam. Surf. Coat. Technol. 203, 2600–2604 (2009).10.1016/j.surfcoat.2009.02.054 ↗
48. Li, K. et al. High speed e-beam writing for large area photonic nanostructures—a choice of parameters. Sci. Rep. 6, 32945 (2016).10.1038/srep32945 ↗
49. Khay, I. et al. Assessment of the energetic performances of various ZIFs with SOD or RHO topology using high pressure water intrusion–extrusion experiments. Dalton Trans. 45, 4392–4400 (2016).10.1039/C5DT03486H ↗
50. Zhang, K. et al. Alcohol and water adsorption in zeolitic imidazolate frameworks. Chem. Commun. 49, 3245–3247 (2013).10.1039/c3cc39116g ↗
51. Dalstein, O. et al. Evaporation-directed crack-patterning of metal–organic framework colloidal films and their application as photonic sensors. Angew. Chem. Int. Ed. 56, 14011–14015 (2017).10.1002/anie.201706745 ↗
52. Michalak, D. J. et al. Porosity scaling strategies for low-k films. J. Mater. Res. 30, 3363–3385 (2015).10.1557/jmr.2015.313 ↗
53. Pérennès, F., De Bona, F. & Pantenburg, F. J. Deep X-ray lithography beamline at Elettra. Nucl. Instrum. Meth. A 467–468, 1274–1278 (2001).10.1016/S0168-9002(01)00632-5 ↗
54. Amenitsch, H. et al. First performance assessment of the small-angle X-ray scattering beamline at Elettra. J. Synchrotron Rad. 5, 506–508 (1998).10.1107/S090904959800137X ↗
55. Hammersley, A. P., Svensson, S. O., Hanfland, M., Fitch, A. N. & Hausermann, D. Two-dimensional detector software: from real detector to idealised image or two-theta scan. High. Press. Res. 14, 235–248 (1996).10.1080/08957959608201408 ↗
56. Blessing, R. H. An empirical correction for absorption anisotropy. Acta Cryst. A 51, 33–38 (1995).10.1107/S0108767394005726 ↗
57. Sheldrick, G. M. A short history of SHELX. Acta Cryst. A 64, 112–122 (2008).10.1107/S0108767307043930 ↗
58. Spek, A. L. Single-crystal structure validation with the program PLATON. J. Appl Cryst. 36, 7–13 (2003).10.1107/S0021889802022112 ↗
59. Spek, A. L. PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to the calculated structure factors. Acta Cryst. C. 71, 9–18 (2015).10.1107/S2053229614024929 ↗
60. Nečas, D. & Klapetek, P. Gwyddion: an open-source software for SPM data analysis. Open Phys. 10, 181–188 (2011).10.2478/s11534-011-0096-2 ↗
61. Horcas, I. et al. WSXM: A software for scanning probe microscopy and a tool for nanotechnology. Rev. Sci. Instrum. 78, 013705 (2007).10.1063/1.2432410 ↗
62. Tu, M., Wannapaiboon, S., Khaletskaya, K. & Fischer, R. A. Engineering zeolitic imidazolate framework (ZIF) thin film devices for selective detection of volatile organic compounds. Adv. Funct. Mater. 25, 4470–4479 (2015).10.1002/adfm.201500760 ↗
63. Le Ouay, B. et al. Nanostructuration of PEDOT in porous coordination polymers for tunable porosity and conductivity. J. Am. Chem. Soc. 138, 10088–10091 (2016).10.1021/jacs.6b05552 ↗
64. Herzinger, C. M., Johs, B., McGahan, W. A., Woollam, J. A. & Paulson, W. Ellipsometric determination of optical constants for silicon and thermally grown silicon dioxide via a multi-sample, multi-wavelength, multi-angle investigation. J. Appl. Phys. 83, 3323–3336 (1998).10.1063/1.367101 ↗
65. Eslava, S. et al. Characterization of a molecular sieve coating using ellipsometric porosimetry. Langmuir 23, 12811–12816 (2007).10.1021/la7028388 ↗
66. Grzybowski, B. A., Qin, D. & Whitesides, G. M. Beam redirection and frequency filtering with transparent elastomeric diffractive elements. Appl. Opt. 38, 2997–3002 (1999).10.1364/AO.38.002997 ↗
67. Tanuma, S., Powell, C. J. & Penn, D. R. Calculation of electron inelastic mean free paths (IMFPs) VII. Reliability of the TPP-2M IMFP predictive equation. Surf. Interface Anal. 35, 268–275 (2003).10.1002/sia.1526 ↗