274336 Analysis of Defect-Induced Amorphization of Single-Layer Graphene
Defect engineering of graphene has been studied extensively, both experimentally and computationally, aimed at approaches for tuning graphene’s electronic, optical, and mechanical properties. Ion-beam and electron-beam irradiation have been employed to introduce in the honeycomb lattice of graphene defects, such as vacancies, reconstructions with pentagon and heptagon rings, as well as larger-scale defects such as two-dimensional (2D) holes or voids. Recent experimental studies also have reported defect-induced amorphization of graphene after high electron-beam exposure. High-resolution imaging of the resulting amorphized graphene demonstrated that such irradiation-induced amorphized graphene remains a coherent single-layer 2D structure that consists of a random patch of polygons and also contains 2D holes.
In this presentation, we address some fundamental questions on the defect-induced amorphization of graphene, including how the defect-induced structure and morphology depend on the inserted defect concentration, the determination of the onset of defect-induced amorphization, and the effects of the defect density and amorphization transition on the graphene’s electronic structure and properties. Our study was based on isothermal-isobaric molecular-dynamics (MD) simulations according to a reliable bond-order potential for the description of interatomic interactions in graphene and using large supercells that contain thousands of C atoms. Random distributions of single vacancies (or other types of point defects) were introduced into the graphene honeycomb lattice at a given concentration and the response of the defective graphene sheets was explored systematically over a broad range of defect concentration based on a variant of simulated annealing. The analysis of the simulation results for the relaxation of the defective graphene samples included detailed structural and morphological characterization of the relaxed configurations based on calculation of certain metrics, such as the radial distribution function, structural order parameters, and RMS surface roughness; the relaxed configurations consitute computer models of irradiated graphene. Finally, we used density-functional tight-binding calculations to compute the electronic density of states of the structurally relaxed configurations.
We predict that the onset of the amorphization transition occurs at an inserted vacancy concentration between 5 and 10%, with the transition becoming less abrupt with vacancy concentration as temperature increases, and determine the surface roughness as a function of defect concentration. Our predictions for the defect-induced amorphization transition are similar for all the types of point defects examined in our study. We find that the computed amorphized configurations are in good agreement with those observed in recent experiments of high-dose exposure of graphene to 100-keV electron irradiation. We also find that the electronic density of states of vacancy-amorphized graphene is characterized by introduction of localized states near the Fermi level of perfect single-layer graphene, consistent with those arising from random vacancy insertion in graphene at low concentrations. Our findings set the stage for exploratory work on the functionalization of defect-amorphized graphene toward useful band-gap engineering and tuning of electronic transport and optical properties.
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