Electron beam controlled covalent attachment of small organic molecules to graphene

Markevich, Alexander; Kurasch, Simon; Lehtinen, Ossi; Reimer, Oliver; Feng, Xinliang; Müllen, Klaus; Turchanin, Andrey; Khlobystov, Andrei N.; Kaiser, Ute; Besley, Elena

Abstract

The electron beam induced functionalization of graphene through the formation of covalent bonds between free radicals of polyaromatic molecules and CC bonds of pristine graphene surface has been explored using first principles calculations and high-resolution transmission electron microscopy. We show that the energetically strongest attachment of the radicals occurs along the armchair direction in graphene to carbon atoms residing in different graphene sub-lattices. The radicals tend to assume vertical position on graphene substrate irrespective of direction of the bonding and the initial configuration. The "standing up" molecules, covalently anchored to graphene, exhibit two types of oscillatory motion-bending and twisting-caused by the presence of acoustic phonons in graphene and dispersion attraction to the substrate. The theoretically derived mechanisms are confirmed by near atomic resolution imaging of individual perchlorocoronene (C24Cl12) molecules on graphene. Our results facilitate the understanding of controlled functionalization of graphene employing electron irradiation as well as mechanisms of attachment of impurities via the processing of graphene nanoelectronic devices by electron beam lithography.

Citation

Markevich, A., Kurasch, S., Lehtinen, O., Reimer, O., Feng, X., Müllen, K., Turchanin, A., Khlobystov, A. N., Kaiser, U., & Besley, E. (2016). Electron beam controlled covalent attachment of small organic molecules to graphene. Nanoscale, 8(5), 2711-2719. https://doi.org/10.1039/c5nr07539d

• Journal Article Type: Article
• Acceptance Date: Dec 24, 2015
• Online Publication Date: Jan 28, 2016
• Publication Date: Jan 28, 2016
• Deposit Date: Sep 8, 2023
• Publicly Available Date: Sep 19, 2023
• Journal: Nanoscale
• Print ISSN: 2040-3364
• Electronic ISSN: 2040-3372
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 8
• Issue: 5
• Pages: 2711-2719
• DOI: https://doi.org/10.1039/c5nr07539d
• Keywords: General Materials Science
• Public URL: https://nottingham-repository.worktribe.com/output/23521076
• Publisher URL: https://pubs.rsc.org/en/content/articlelanding/2016/NR/C5NR07539D
• Additional Information: : This document is CrossCheck deposited; : Supplementary Information; : The Royal Society of Chemistry has an exclusive publication licence for this journal; OPEN ACCESS: This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0); : Received 28 October 2015; Accepted 24 December 2015; Accepted Manuscript published 4 January 2016; Advance Article published 13 January 2016; Version of Record published 28 January 2016