title: Covalent modification of graphene and graphite using diazonium chemistry: tunable grafting and nanomanipulation.
abstract: We shine light on the covalent modification of graphite and graphene substrates using diazonium chemistry under ambient conditions. We report on the nature of the chemical modification of these graphitic substrates, the relation between molecular structure and film morphology, and the impact of the covalent modification on the properties of the substrates, as revealed by local microscopy and spectroscopy techniques and electrochemistry. By careful selection of the reagents and optimizing reaction conditions, a high density of covalently grafted molecules is obtained, a result that is demonstrated in an unprecedented way by scanning tunneling microscopy (STM) under ambient conditions. With nanomanipulation, i.e., nanoshaving using STM, surface structuring and functionalization at the nanoscale is achieved. This manipulation leads to the removal of the covalently anchored molecules, regenerating pristine sp(2) hybridized graphene or graphite patches, as proven by space-resolved Raman microscopy and molecular self-assembly studies.
authors.affiliation: †Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
authors.forename: John
authors.initials: J
authors.lastname: Greenwood
authors.affiliation: †Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
authors.forename: Thanh Hai
authors.initials: TH
authors.lastname: Phan
authors.affiliation: †Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
authors.forename: Yasuhiko
authors.initials: Y
authors.lastname: Fujita
authors.affiliation: †Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
authors.forename: Zhi
authors.initials: Z
authors.lastname: Li
authors.affiliation: †Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
authors.forename: Oleksandr
authors.initials: O
authors.lastname: Ivasenko
authors.affiliation: †Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
authors.forename: Willem
authors.initials: W
authors.lastname: Vanderlinden
authors.affiliation: †Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
authors.forename: Hans
authors.initials: H
authors.lastname: Van Gorp
authors.affiliation: †Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
authors.forename: Wout
authors.initials: W
authors.lastname: Frederickx
authors.affiliation: †Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
authors.forename: Gang
authors.initials: G
authors.lastname: Lu
authors.affiliation: §Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.
authors.forename: Kazukuni
authors.initials: K
authors.lastname: Tahara
authors.affiliation: §Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.
authors.forename: Yoshito
authors.initials: Y
authors.lastname: Tobe
authors.affiliation: †Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Uji-I
authors.affiliation: †Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.|‡Institute of Applied Physics, Vienna University of Technology, Wiedner Hauptstraße 8-10/E134, A-1040 Vienna, Austria.
authors.forename: Stijn F L
authors.initials: SF
authors.lastname: Mertens
authors.affiliation: †Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
authors.forename: Steven
authors.initials: S
authors.lastname: De Feyter
keywords: AFM; Raman spectroscopy; STM; diazonium; grafting; graphene; self-assembly