Defect migration and phase transformations in 2D iron chloride inside bilayer graphene

TL;DR

This study investigates atomic-scale defect behaviors and phase transformations in iron chloride intercalated bilayer graphene, revealing defect roles and a novel Fe5Cl18 phase, advancing understanding of 2D material intercalation.

Contribution

It provides new insights into defect dynamics and phase changes in intercalated 2D materials using STEM and first-principles calculations.

Findings

Identification of Fe vacancies, adatoms, and interstitials with distinct behaviors

Observation of a new Fe5Cl18 phase with unusual stoichiometry

Elucidation of defect roles in phase transformations

Abstract

The intercalation of metal chlorides, and particularly iron chlorides, into graphitic carbon structures has recently received lots of attention, as it can not only protect this two-dimensional (2D) magnetic system from the effects of the environment, but also substantially alter the magnetic, electronic, and optical properties of both intercalant and host material. At the same time, the intercalation can result in the formation of structural defects, or defects can appear under external stimuli, which can affect materials performance. These aspects have received so far little attention in the dedicated experiments. In this study, we investigate the behavior of atomic-scale defects in iron chlorides intercalated into bilayer graphene (BLG) by using scanning transmission electron microscopy (STEM) and first-principles calculations. We observe transformations between the FeCl2 and FeCl3 phases and elucidate the role of defects in the transformations. Specifically, three types of defects are identified: Fe vacancies in FeCl2 domains, Fe adatoms and interstitials in FeCl3 domains, each exhibiting distinct dynamic behaviors. We also observed a crystalline phase with an unusual stoichiometry of Fe5Cl18 which has not been reported before. Our findings not only advance the understanding of intercalation mechanism of 2D materials but also highlight the profound impact of atomic-scale defects on their properties and potential technological applications.