Two Distinct Stages of Structural Modification of ZIF-L MOF under Electron-Beam Irradiation

Supriya Ghosh, Hwanhui Yun, Prashant Kumar, Sabrina Conrad, Michael Tsapatsis, K. Andre Mkhoyan

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Metal-organic frameworks (MOFs) are gaining more prominence as low-dielectric materials for applications in electronic devices and sensors using top-down electron-beam patterning. Using a combination of electron diffraction and electron energy-loss spectroscopy (EELS) in a transmission electron microscope, the details of structural modification of ZIF-L MOF under electron-beam irradiation were identified. It was found that the modification of ZIF-L under the electron beam happens in two distinct stages. In addition to the collapse of the original ZIF-L porous framework and loss of crystallinity occurring at the initial low-dose stage, it was observed that the disordered ZIF-L then undergoes a second stage of changes, where the molecular structure of the linker starts to breakdown. Further, it was observed that the degradation of the linker molecules in the second stage of the ZIF-L modification has a considerable impact on its dielectric function, shifting energies of the electronic transitions.

Original languageEnglish (US)
Pages (from-to)5681-5689
Number of pages9
JournalChemistry of Materials
Issue number14
StatePublished - Jun 8 2021

Bibliographical note

Funding Information:
This work was supported primarily by the National Science Foundation through the University of Minnesota MRSEC under award numbers DMR-1420013 and DMR-2011401. Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from the NSF through the MRSEC and the NNCI (award number ECCS-2025124) programs. The authors thank Dr. Jason C. Myers for help with probe current measurements and TEM assistance.

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