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Title: 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:
 [1];  [2];  [3];  [3];  [4];  [3];  [5];  [6];  [4];  [7]
  1. Univ. of Texas, Austin, TX (United States). Center for Nano- and Molecular Science and Technology
  2. Univ. of Texas, Austin, TX (United States). Dept. of Chemical Engineering; Yale Univ., New Haven, CT (United States). Dept. of Applied Physics
  3. Univ. of Texas, Austin, TX (United States). Dept. of Chemistry
  4. Univ. of Texas, Austin, TX (United States). Microelectronics Research Center
  5. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  6. 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
  7. 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. 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, and Stevenson, Keith J. Mon . "Atomically Resolved Elucidation of the Electrochemical Covalent Molecular Grafting Mechanism of Single Layer Graphene". United States. doi: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 = {2016},
month = {6}
}

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Works referenced in this record:

Anthraquinonedisulfonate adsorption, electron-transfer kinetics, and capacitance on ordered graphite electrodes: the important role of surface defects
journal, April 1992

  • McDermott, Mark T.; Kneten, Kristin; McCreery, Richard L.
  • The Journal of Physical Chemistry, Vol. 96, Issue 7
  • DOI: 10.1021/j100186a063

Electrochemically Driven Covalent Functionalization of Graphene from Fluorinated Aryl Iodonium Salts
journal, May 2013

  • Chan, Calvin K.; Beechem, Thomas E.; Ohta, Taisuke
  • The Journal of Physical Chemistry C, Vol. 117, Issue 23
  • DOI: 10.1021/jp311519j

Defect-induced magnetism in graphene
journal, March 2007


Exceptional ballistic transport in epitaxial graphene nanoribbons
journal, February 2014

  • Baringhaus, Jens; Ruan, Ming; Edler, Frederik
  • Nature, Vol. 506, Issue 7488
  • DOI: 10.1038/nature12952

Progress, Challenges, and Opportunities in Two-Dimensional Materials Beyond Graphene
journal, March 2013

  • Butler, Sheneve Z.; Hollen, Shawna M.; Cao, Linyou
  • ACS Nano, Vol. 7, Issue 4, p. 2898-2926
  • DOI: 10.1021/nn400280c

Inductively heated synthesized graphene with record transistor mobility on oxidized silicon substrates at room temperature
journal, October 2013

  • Tao, Li; Lee, Jongho; Li, Huifeng
  • Applied Physics Letters, Vol. 103, Issue 18
  • DOI: 10.1063/1.4828501

Role of carbon surface diffusion on the growth of epitaxial graphene on SiC
journal, March 2010


Potential-Directed Assembly of Aryl Iodonium Salts onto Silicon {100} Hydride Terminated and Platinum Surfaces
journal, November 2005

  • Dirk, Shawn M.; Pylypenko, Svitlana; Howell, Stephen W.
  • Langmuir, Vol. 21, Issue 24
  • DOI: 10.1021/la052311z

Atom-scale covalent electrochemical modification of single-layer graphene on SiC substrates by diaryliodonium salts
journal, September 2015


Finite-difference-pseudopotential method: Electronic structure calculations without a basis
journal, February 1994


Microstructure evolution of diazonium functionalized graphene: A potential approach to change graphene electronic structure
journal, January 2012

  • Zhu, Huarui; Huang, Ping; Jing, Long
  • J. Mater. Chem., Vol. 22, Issue 5
  • DOI: 10.1039/C1JM14862A

Chemical approach to the realization of electronic devices in epitaxial graphene
journal, September 2009

  • Bekyarova, Elena; Itkis, Mikhail E.; Ramesh, Palanisamy
  • physica status solidi (RRL) - Rapid Research Letters, Vol. 3, Issue 6
  • DOI: 10.1002/pssr.200903110

Covalent Electron Transfer Chemistry of Graphene with Diazonium Salts
journal, September 2012

  • Paulus, Geraldine L. C.; Wang, Qing Hua; Strano, Michael S.
  • Accounts of Chemical Research, Vol. 46, Issue 1, p. 160-170
  • DOI: 10.1021/ar300119z

Definitive Evidence for Fast Electron Transfer at Pristine Basal Plane Graphite from High-Resolution Electrochemical Imaging
journal, April 2012

  • Lai, Stanley C. S.; Patel, Anisha N.; McKelvey, Kim
  • Angewandte Chemie International Edition, Vol. 51, Issue 22
  • DOI: 10.1002/anie.201200564

Micrometer-Scale Ballistic Transport in Encapsulated Graphene at Room Temperature
journal, June 2011

  • Mayorov, Alexander S.; Gorbachev, Roman V.; Morozov, Sergey V.
  • Nano Letters, Vol. 11, Issue 6
  • DOI: 10.1021/nl200758b

The cyclic voltammetric response of electrochemically heterogeneous surfaces
journal, December 2004


Raman spectroscopy as a versatile tool for studying the properties of graphene
journal, April 2013


Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils
journal, May 2009


Ultrathin Epitaxial Graphite:  2D Electron Gas Properties and a Route toward Graphene-based Nanoelectronics
journal, December 2004

  • Berger, Claire; Song, Zhimin; Li, Tianbo
  • The Journal of Physical Chemistry B, Vol. 108, Issue 52, p. 19912-19916
  • DOI: 10.1021/jp040650f

Hydrogen on graphene: Electronic structure, total energy, structural distortions and magnetism from first-principles calculations
journal, January 2008


Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene
journal, July 2008


Advances in the chemical modification of epitaxial graphene
journal, March 2012


A New View of Electrochemistry at Highly Oriented Pyrolytic Graphite
journal, December 2012

  • Patel, Anisha N.; Collignon, Manon Guille; O’Connell, Michael A.
  • Journal of the American Chemical Society, Vol. 134, Issue 49
  • DOI: 10.1021/ja308615h

Soluble graphene through edge-selective functionalization
journal, February 2010


Quasi-Free-Standing Epitaxial Graphene on SiC Obtained by Hydrogen Intercalation
journal, December 2009


Electrochemical Modification of Indium Tin Oxide Using Di(4-nitrophenyl) Iodonium Tetrafluoroborate
journal, January 2015

  • Charlton, Matthew R.; Suhr, Kristin J.; Holliday, Bradley J.
  • Langmuir, Vol. 31, Issue 2
  • DOI: 10.1021/la503522c

Achieving High-Quality Single-Atom Nitrogen Doping of Graphene/SiC(0001) by Ion Implantation and Subsequent Thermal Stabilization
journal, June 2014

  • Telychko, Mykola; Mutombo, Pingo; Ondráček, Martin
  • ACS Nano, Vol. 8, Issue 7
  • DOI: 10.1021/nn502438k

Properties of Fluorinated Graphene Films
journal, August 2010

  • Robinson, Jeremy T.; Burgess, James S.; Junkermeier, Chad E.
  • Nano Letters, Vol. 10, Issue 8
  • DOI: 10.1021/nl101437p

Self-consistent-field calculations using Chebyshev-filtered subspace iteration
journal, November 2006

  • Zhou, Yunkai; Saad, Yousef; Tiago, Murilo L.
  • Journal of Computational Physics, Vol. 219, Issue 1
  • DOI: 10.1016/j.jcp.2006.03.017

Multi-terminal transport measurements of MoS2 using a van der Waals heterostructure device platform
journal, April 2015

  • Cui, Xu; Lee, Gwan-Hyoung; Kim, Young Duck
  • Nature Nanotechnology, Vol. 10, Issue 6
  • DOI: 10.1038/nnano.2015.70

Nanoscale imaging of chemical interactions: Fluorine on graphite
journal, August 2000

  • Kelly, K. F.; Mickelson, E. T.; Hauge, R. H.
  • Proceedings of the National Academy of Sciences, Vol. 97, Issue 19
  • DOI: 10.1073/pnas.190325397

Regiospecific One-Pot Synthesis of Diaryliodonium Tetrafluoroborates from Arylboronic Acids and Aryl Iodides
journal, June 2008

  • Bielawski, Marcin; Aili, David; Olofsson, Berit
  • The Journal of Organic Chemistry, Vol. 73, Issue 12
  • DOI: 10.1021/jo8004974

Covalent functionalization of monolayered transition metal dichalcogenides by phase engineering
journal, November 2014

  • Voiry, Damien; Goswami, Anandarup; Kappera, Rajesh
  • Nature Chemistry, Vol. 7, Issue 1
  • DOI: 10.1038/nchem.2108

Parallel self-consistent-field calculations via Chebyshev-filtered subspace acceleration
journal, December 2006


Determination of α and β site defects on graphite using C60-adsorbed STM tips
journal, October 1998


Activation of highly ordered pyrolytic graphite for heterogeneous electron transfer: relationship between electrochemical performance and carbon microstructure
journal, February 1989

  • Bowling, Robert J.; Packard, Richard T.; McCreery, Richard L.
  • Journal of the American Chemical Society, Vol. 111, Issue 4
  • DOI: 10.1021/ja00186a008

Direct Measurement of the Fermi Energy in Graphene Using a Double-Layer Heterostructure
journal, March 2012


Ground State of the Electron Gas by a Stochastic Method
journal, August 1980


Long-Range Electronic Perturbations Caused by Defects Using Scanning Tunneling Microscopy
journal, May 1989


The rise of graphene
journal, March 2007

  • Geim, A. K.; Novoselov, K. S.
  • Nature Materials, Vol. 6, Issue 3, p. 183-191
  • DOI: 10.1038/nmat1849

Emergence of magnetism in graphene materials and nanostructures
journal, April 2010


Synthesis and structure of two-dimensional transition-metal dichalcogenides
journal, July 2015


Two-dimensional layered transition-metal dichalcogenides for versatile properties and applications
journal, July 2015


The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets
journal, April 2013

  • Chhowalla, Manish; Shin, Hyeon Suk; Eda, Goki
  • Nature Chemistry, Vol. 5, Issue 4, p. 263-275
  • DOI: 10.1038/nchem.1589

Large Scale Growth and Characterization of Atomic Hexagonal Boron Nitride Layers
journal, August 2010

  • Song, Li; Ci, Lijie; Lu, Hao
  • Nano Letters, Vol. 10, Issue 8, p. 3209-3215
  • DOI: 10.1021/nl1022139

Raman Spectrum of Graphene and Graphene Layers
journal, October 2006


Covalent Modification of Graphene and Graphite Using Diazonium Chemistry: Tunable Grafting and Nanomanipulation
journal, April 2015


Silicene: Compelling Experimental Evidence for Graphenelike Two-Dimensional Silicon
journal, April 2012


Spectroscopy of Covalently Functionalized Graphene
journal, October 2010

  • Niyogi, Sandip; Bekyarova, Elena; Itkis, Mikhail E.
  • Nano Letters, Vol. 10, Issue 10
  • DOI: 10.1021/nl1021128

Black phosphorus field-effect transistors
journal, March 2014


Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide
journal, February 2009

  • Emtsev, Konstantin V.; Bostwick, Aaron; Horn, Karsten
  • Nature Materials, Vol. 8, Issue 3
  • DOI: 10.1038/nmat2382

Layer-Resolved Graphene Transfer via Engineered Strain Layers
journal, October 2013


Air Stable p-Doping of WSe 2 by Covalent Functionalization
journal, September 2014

  • Zhao, Peida; Kiriya, Daisuke; Azcatl, Angelica
  • ACS Nano, Vol. 8, Issue 10
  • DOI: 10.1021/nn5047844

High-Performance Single Layered WSe2 p-FETs with Chemically Doped Contacts
journal, June 2012

  • Fang, Hui; Chuang, Steven; Chang, Ting Chia
  • Nano Letters, Vol. 12, Issue 7, p. 3788-3792
  • DOI: 10.1021/nl301702r

Covalent Chemistry for Graphene Electronics
journal, September 2011

  • Niyogi, Sandip; Bekyarova, Elena; Hong, Jeongmin
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 19
  • DOI: 10.1021/jz200426d

Fine Structure Constant Defines Visual Transparency of Graphene
journal, June 2008