Atomically Resolved Elucidation of the Electrochemical Covalent Molecular Grafting Mechanism of Single Layer Graphene

Gearba, Raluca I.; Kim, Minjung; Mueller, Kory M.; Veneman, Peter A.; Lee, Kayoung; Holliday, Bradley J.; Chan, Calvin K.; Chelikowsky, James R.; Tutuc, Emanuel; Stevenson, Keith J.

doi:10.1002/admi.201600196

Title: Atomically Resolved Elucidation of the Electrochemical Covalent Molecular Grafting Mechanism of Single Layer Graphene

Journal Article · Mon Jun 20 00:00:00 EDT 2016 · Advanced Materials Interfaces

DOI:https://doi.org/10.1002/admi.201600196· OSTI ID:1370041

Gearba, Raluca I. ^[1]; Kim, Minjung ^[2]; Mueller, Kory M. ^[3]; Veneman, Peter A. ^[3]; Lee, Kayoung ^[4]; Holliday, Bradley J. ^[3]; Chan, Calvin K. ^[5]; Chelikowsky, James R. ^[6]; Tutuc, Emanuel ^[4]; Stevenson, Keith J. ^[7]

Univ. of Texas, Austin, TX (United States). Center for Nano- and Molecular Science and Technology
Univ. of Texas, Austin, TX (United States). Dept. of Chemical Engineering; Yale Univ., New Haven, CT (United States). Dept. of Applied Physics
Univ. of Texas, Austin, TX (United States). Dept. of Chemistry
Univ. of Texas, Austin, TX (United States). Microelectronics Research Center
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Univ. of Texas, Austin, TX (United States). Dept. of Chemical Engineering, and Dept. of Physics; Univ. of Texas, Austin, TX (United States). Center for Computational Materials; Univ. of Texas, Austin, TX (United States). Inst. for Computational Engineering and Sciences
Univ. of Texas, Austin, TX (United States). Center for Nano- and Molecular Science and Technology; Skolkovo Inst. of Science and Technology Center for Electrochemical Energy Storage, Moscow (Russia)

Engineering graphene at the atomic level via chemical doping, substrate interactions or lateral confinement opens up avenues for precise tuning of its electronic and magnetic properties. Chemical doping by covalent modification routes using electrochemical tools offers rich opportunities that are yet to be fully explored. The key to controlling graphene's physicochemical properties requires a detailed atomistic understanding of the geometry and mechanism of the covalent attachment process. By employing diaryliodonium salts instead of the commonly used diazonium salts, precise molecular grafting onto epitaxial graphene is achieved. Using atomically resolved imaging via scanning tunneling microscopy it is shown that for single layer, high quality, low defect graphene, the functionalization process is controlled by kinetics rather than thermodynamics in accord with Marcus–Gerisher theory. The predominance of the preferential pairwise attachment of molecular grafts specifically on the same graphene sublattice gives rise to ferromagnetic properties previously observed in nitrophenyl modified graphene. Furthermore, p-type doping has been quantified by electrical measurements and angle resolved photoelectron spectroscopy. Overall this electrochemical route for precise covalent functionalization of single layer graphene is general and can be straightforwardly extended to other 2D few-layer confined materials such as transition metal chalcogenides.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Understanding Charge Separation and Transfer at Interfaces in Energy Materials (CST)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: SC0001091; FG02-06ER46286; AC02-05CH11231; F-1529; F-1631

OSTI ID:: 1370041

Alternate ID(s):: OSTI ID: 1401684

Journal Information:: Advanced Materials Interfaces, Vol. 3, Issue 16; Related Information: CST partners with University of Texas at Austin (lead); Sandia National Laboratories; ISSN 2196-7350

Publisher:: Wiley-VCHCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 9 works

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Title: Atomically Resolved Elucidation of the Electrochemical Covalent Molecular Grafting Mechanism of Single Layer Graphene

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