Atomically Resolved Elucidation of the Electrochemical Covalent Molecular Grafting Mechanism of Single Layer Graphene
Abstract
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.
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Understanding Charge Separation and Transfer at Interfaces in Energy Materials (CST)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1370041
- Alternate Identifier(s):
- OSTI ID: 1401684
- Grant/Contract Number:
- SC0001091; FG02-06ER46286; AC02-05CH11231; F-1529; F-1631
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Materials Interfaces
- Additional Journal Information:
- Journal Volume: 3; Journal Issue: 16; Related Information: CST partners with University of Texas at Austin (lead); Sandia National Laboratories; Journal ID: ISSN 2196-7350
- Publisher:
- Wiley-VCH
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; angle resolved photoelectron spectroscopy; electronic properties in graphene; graphene covalent functionalization; scanning tunneling microscopy
Citation Formats
Gearba, Raluca I., Kim, Minjung, Mueller, Kory M., Veneman, Peter A., Lee, Kayoung, Holliday, Bradley J., Chan, Calvin K., Chelikowsky, James R., Tutuc, Emanuel, and Stevenson, Keith J. Atomically Resolved Elucidation of the Electrochemical Covalent Molecular Grafting Mechanism of Single Layer Graphene. United States: N. p., 2016.
Web. doi:10.1002/admi.201600196.
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. Atomically Resolved Elucidation of the Electrochemical Covalent Molecular Grafting Mechanism of Single Layer Graphene. United States. https://doi.org/10.1002/admi.201600196
Gearba, Raluca I., Kim, Minjung, Mueller, Kory M., Veneman, Peter A., Lee, Kayoung, Holliday, Bradley J., Chan, Calvin K., Chelikowsky, James R., Tutuc, Emanuel, and Stevenson, Keith J. Mon .
"Atomically Resolved Elucidation of the Electrochemical Covalent Molecular Grafting Mechanism of Single Layer Graphene". United States. https://doi.org/10.1002/admi.201600196. https://www.osti.gov/servlets/purl/1370041.
@article{osti_1370041,
title = {Atomically Resolved Elucidation of the Electrochemical Covalent Molecular Grafting Mechanism of Single Layer Graphene},
author = {Gearba, Raluca I. and Kim, Minjung and Mueller, Kory M. and Veneman, Peter A. and Lee, Kayoung and Holliday, Bradley J. and Chan, Calvin K. and Chelikowsky, James R. and Tutuc, Emanuel and Stevenson, Keith J.},
abstractNote = {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.},
doi = {10.1002/admi.201600196},
journal = {Advanced Materials Interfaces},
number = 16,
volume = 3,
place = {United States},
year = {Mon Jun 20 00:00:00 EDT 2016},
month = {Mon Jun 20 00:00:00 EDT 2016}
}
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