Mechanism of Electron-Beam-Induced Structural Degradation in ZIF-8 and its Electron Dose Tolerance

Abstract

Zeolitic-imidazolate frameworks (ZIFs) are crystalline microporous materials with promising potential for gas adsorption and catalysis application. Further research advances include studies on integrating ZIFs into nanodevice concepts. In detail for the application, e.g., electron-beam-assisted structural modifications or patterning, there is a need to understand potential structural degradation processes caused by such electron beams. Advanced transmission electron microscopy (TEM) has demonstrated its ability to study structures at the nanoscale. Here, we systematically investigated electron-beam-induced loss in crystallinity in ZIF-8 under various experimental conditions, using as measure the attenuation of the relative intensity and the relative displacement of electron diffraction Bragg planes with increasing cumulative electron dose. The {110} Bragg planes reflect the overall stability of the ZIF-8 unit-cell structure, while the {431} Bragg planes assess the stability of its micropore structure. We considered a relative loss of Bragg plane intensity of 37% as the threshold for determining the critical electron dose, which varied for different Bragg planes, with 35.6 ± 8.4 e^–Å^–2 for {110} and 11.4 ± 3.0 e^–Å^–2 for {431}. However, the critical dose per breakage of N–Zn bonds in a ZnN₄ tetrahedra per different Bragg plane was found to be ∼3 e^–Å^–2, which indicates continuous, simultaneous breakage of N–Zn bonds throughout the crystal, confirming radiolysis as the dominant damage mechanism. In addition, we investigated the effects of TEM experiment parameters, including acceleration voltage, electron dose rate, cryogenic sample temperature, in situ sample drying, and change in conductivity of the sample substrate (e.g., graphene). Our results unravel the degradation mechanisms in ZIF-8 and provide threshold parameters for maximizing resolution in electron-beam-assisted experiments and processes.