Lehnert Tibor, Kretschmer Silvan, Bräuer Fredrik, Krasheninnikov Arkady V, Kaiser Ute
Electron Microscopy Group of Materials Science, Ulm University, 89081 Ulm, Germany.
Institute for Quantum Optics, Ulm University, 89081 Ulm, Germany.
Nanoscale. 2021 Dec 2;13(46):19626-19633. doi: 10.1039/d1nr04792b.
Quasi-two-dimensional (2D) sodium chloride (NaCl) crystals of various lateral sizes between graphene sheets were manufactured supersaturation from a saline solution. Aberration-corrected transmission electron microscopy was used for systematic investigations of the crystals and their decomposition under an 80 kV electron beam. Counterintuitively, bigger clusters were found to disintegrate faster under electron irradiation, but in general no correlation between crystal sizes and electron doses at which the crystals decompose was found. As for the destruction process, an abrupt decomposition of the crystals was observed, which can be described by a logistic decay function. Density-functional theory molecular dynamics simulations provide insights into the destruction mechanism, and indicate that even without account for ionization and electron excitations, free-standing NaCl crystals must quickly disintegrate due to the ballistic displacement of atoms from their surface and edges during imaging. However, graphene sheets mitigate damage development by stopping the displaced atoms and enable the immediate recombination of defects at the surface of the crystal. At the same time, once a hole in graphene appears, the displaced atoms escape, giving rise to the quick destruction of the crystal. Our results provide quantitative data on the stability of encapsulated quasi 2D NaCl crystals under electron irradiation and allow the conclusion that only high-quality graphene is suitable for protecting ionic crystals from beam damage in electron microscopy studies.
通过使盐溶液达到过饱和状态,制备出了石墨烯片层间具有不同横向尺寸的准二维(2D)氯化钠(NaCl)晶体。利用像差校正透射电子显微镜对这些晶体及其在80 kV电子束下的分解情况进行了系统研究。与直觉相反,发现较大的团簇在电子辐照下分解得更快,但总体上未发现晶体尺寸与晶体分解时的电子剂量之间存在关联。至于破坏过程,观察到晶体的突然分解,这可以用逻辑衰减函数来描述。密度泛函理论分子动力学模拟为破坏机制提供了深入见解,并表明即使不考虑电离和电子激发,在成像过程中,独立的NaCl晶体也会因原子从其表面和边缘的弹道位移而迅速分解。然而,石墨烯片层通过阻止被位移的原子来减轻损伤的发展,并使晶体表面的缺陷立即复合。同时,一旦石墨烯中出现一个洞,被位移的原子就会逸出,导致晶体迅速破坏。我们的结果提供了关于电子辐照下封装的准二维NaCl晶体稳定性的定量数据,并得出结论:在电子显微镜研究中,只有高质量的石墨烯才适合保护离子晶体免受束流损伤。