DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electronic Structures, Bonding Configurations, and Band-Gap-Opening Properties of Graphene Binding with Low-Concentration Fluorine

Abstract

To better understand the effects of low-level fluorine in graphene-based sensors, first-principles density functional theory (DFT) with van der Waals dispersion interactions has been employed to investigate the structure and impact of fluorine defects on the electrical properties of single-layer graphene films. The results show that both graphite-2H and graphene have zero band gaps. When fluorine bonds to a carbon atom, the carbon atom is pulled slightly above the graphene plane, creating what is referred to as a CF defect. The lowest-binding energy state is found to correspond to two CF defects on nearest neighbor sites, with one fluorine above the carbon plane and the other below the plane. Overall this has the effect of buckling the graphene. The results further show that the addition of fluorine to graphene leads to the formation of an energy band (BF) near the Fermi level, contributed mainly from the 2p orbitals of fluorine with a small contribution from the porbitals of the carbon. Among the 11 binding configurations studied, our results show that only in two cases does the BF serve as a conduction band and open a band gap of 0.37 eV and 0.24 eV respectively. The binding energy decreases with decreasingmore » fluorine concentration due to the interaction between neighboring fluorine atoms. The obtained results are useful for sensor development and nanoelectronics.« less

Authors:
ORCiD logo [1];  [2];  [1]
  1. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
  2. National Energy Technology Lab. (NETL), Morgantown, WV (United States); National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
Publication Date:
Research Org.:
National Energy Technology Lab. (NETL), Pittsburgh, PA, and Morgantown, WV (United States). In-house Research
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1209521
Report Number(s):
NETL-PUB-1162
Journal ID: ISSN 2191-1363
Resource Type:
Accepted Manuscript
Journal Name:
ChemistryOpen
Additional Journal Information:
Journal Volume: 4; Journal Issue: 5; Journal ID: ISSN 2191-1363
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Duan, Yuhua, Stinespring, Charter D., and Chorpening, Benjamin. Electronic Structures, Bonding Configurations, and Band-Gap-Opening Properties of Graphene Binding with Low-Concentration Fluorine. United States: N. p., 2015. Web. doi:10.1002/open.201500074.
Duan, Yuhua, Stinespring, Charter D., & Chorpening, Benjamin. Electronic Structures, Bonding Configurations, and Band-Gap-Opening Properties of Graphene Binding with Low-Concentration Fluorine. United States. https://doi.org/10.1002/open.201500074
Duan, Yuhua, Stinespring, Charter D., and Chorpening, Benjamin. Thu . "Electronic Structures, Bonding Configurations, and Band-Gap-Opening Properties of Graphene Binding with Low-Concentration Fluorine". United States. https://doi.org/10.1002/open.201500074. https://www.osti.gov/servlets/purl/1209521.
@article{osti_1209521,
title = {Electronic Structures, Bonding Configurations, and Band-Gap-Opening Properties of Graphene Binding with Low-Concentration Fluorine},
author = {Duan, Yuhua and Stinespring, Charter D. and Chorpening, Benjamin},
abstractNote = {To better understand the effects of low-level fluorine in graphene-based sensors, first-principles density functional theory (DFT) with van der Waals dispersion interactions has been employed to investigate the structure and impact of fluorine defects on the electrical properties of single-layer graphene films. The results show that both graphite-2H and graphene have zero band gaps. When fluorine bonds to a carbon atom, the carbon atom is pulled slightly above the graphene plane, creating what is referred to as a CF defect. The lowest-binding energy state is found to correspond to two CF defects on nearest neighbor sites, with one fluorine above the carbon plane and the other below the plane. Overall this has the effect of buckling the graphene. The results further show that the addition of fluorine to graphene leads to the formation of an energy band (BF) near the Fermi level, contributed mainly from the 2p orbitals of fluorine with a small contribution from the porbitals of the carbon. Among the 11 binding configurations studied, our results show that only in two cases does the BF serve as a conduction band and open a band gap of 0.37 eV and 0.24 eV respectively. The binding energy decreases with decreasing fluorine concentration due to the interaction between neighboring fluorine atoms. The obtained results are useful for sensor development and nanoelectronics.},
doi = {10.1002/open.201500074},
journal = {ChemistryOpen},
number = 5,
volume = 4,
place = {United States},
year = {Thu Jun 18 00:00:00 EDT 2015},
month = {Thu Jun 18 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Functionalization of Graphene: Covalent and Non-Covalent Approaches, Derivatives and Applications
journal, September 2012

  • Georgakilas, Vasilios; Otyepka, Michal; Bourlinos, Athanasios B.
  • Chemical Reviews, Vol. 112, Issue 11
  • DOI: 10.1021/cr3000412

Adsorption of H 2 O , N H 3 , CO, N O 2 , and NO on graphene: A first-principles study
journal, March 2008


High Efficiency Graphene Solar Cells by Chemical Doping
journal, May 2012

  • Miao, Xiaochang; Tongay, Sefaattin; Petterson, Maureen K.
  • Nano Letters, Vol. 12, Issue 6
  • DOI: 10.1021/nl204414u

Graphene-Based Supercapacitor with an Ultrahigh Energy Density
journal, December 2010

  • Liu, Chenguang; Yu, Zhenning; Neff, David
  • Nano Letters, Vol. 10, Issue 12
  • DOI: 10.1021/nl102661q

Large Reversible Li Storage of Graphene Nanosheet Families for Use in Rechargeable Lithium Ion Batteries
journal, August 2008

  • Yoo, EunJoo; Kim, Jedeok; Hosono, Eiji
  • Nano Letters, Vol. 8, Issue 8, p. 2277-2282
  • DOI: 10.1021/nl800957b

Mechanisms of the Oxygen Reduction Reaction on Defective Graphene-Supported Pt Nanoparticles from First-Principles
journal, January 2012

  • Lim, Dong-Hee; Wilcox, Jennifer
  • The Journal of Physical Chemistry C, Vol. 116, Issue 5
  • DOI: 10.1021/jp210796e

Epitaxial Graphene Transistors on SiC Substrates
journal, August 2008

  • Kedzierski, Jakub; Hsu, Pei-Lan; Healey, Paul
  • IEEE Transactions on Electron Devices, Vol. 55, Issue 8
  • DOI: 10.1109/TED.2008.926593

Tunable Quantum Dots in Bilayer Graphene
journal, April 2007

  • Pereira,, J. Milton; Vasilopoulos, P.; Peeters, F. M.
  • Nano Letters, Vol. 7, Issue 4
  • DOI: 10.1021/nl062967s

The electronic properties of graphene
journal, January 2009

  • Castro Neto, A. H.; Guinea, F.; Peres, N. M. R.
  • Reviews of Modern Physics, Vol. 81, Issue 1, p. 109-162
  • DOI: 10.1103/RevModPhys.81.109

Chiral tunnelling and the Klein paradox in graphene
journal, August 2006

  • Katsnelson, M. I.; Novoselov, K. S.; Geim, A. K.
  • Nature Physics, Vol. 2, Issue 9
  • DOI: 10.1038/nphys384

Two-dimensional gas of massless Dirac fermions in graphene
journal, November 2005

  • Novoselov, K. S.; Geim, A. K.; Morozov, S. V.
  • Nature, Vol. 438, Issue 7065, p. 197-200
  • DOI: 10.1038/nature04233

The chemistry of graphene oxide
journal, January 2010

  • Dreyer, Daniel R.; Park, Sungjin; Bielawski, Christopher W.
  • Chem. Soc. Rev., Vol. 39, Issue 1
  • DOI: 10.1039/B917103G

Rational Design of Carboxyl Groups Perpendicularly Attached to a Graphene Sheet: A Platform for Enhanced Biosensing Applications
journal, December 2013

  • Bonanni, Alessandra; Chua, Chun Kiang; Pumera, Martin
  • Chemistry - A European Journal, Vol. 20, Issue 1
  • DOI: 10.1002/chem.201303582

Trapping of Metal Atoms in Vacancies of Carbon Nanotubes and Graphene
journal, May 2010

  • Rodríguez-Manzo, Julio A.; Cretu, Ovidiu; Banhart, Florian
  • ACS Nano, Vol. 4, Issue 6
  • DOI: 10.1021/nn100356q

Control of Graphene's Properties by Reversible Hydrogenation: Evidence for Graphane
journal, January 2009


Plasma-chemical bromination of graphitic materials and its use for subsequent functionalization and grafting of organic molecules
journal, November 2010


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

Impact of Chlorine Functionalization on High-Mobility Chemical Vapor Deposition Grown Graphene
journal, July 2013


Transition metal adatom and dimer adsorbed on graphene: Induced magnetization and electronic structures
journal, May 2010


Adatoms in graphene
journal, July 2009

  • Castro Neto, A. H.; Kotov, V. N.; Nilsson, J.
  • Solid State Communications, Vol. 149, Issue 27-28
  • DOI: 10.1016/j.ssc.2009.02.040

Electrical control of the chemical bonding of fluorine on graphene
journal, February 2011


Novel surface chemical synthesis route for large area graphene-on-insulator films
journal, May 2012

  • Raghavan, Srikanth; Denig, Tobias J.; Nelson, Timothy C.
  • Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 30, Issue 3
  • DOI: 10.1116/1.4710997

On the so-called “semi-ionic” C–F bond character in fluorine–GIC
journal, January 2004


Conformational analysis. 130. MM2. A hydrocarbon force field utilizing V1 and V2 torsional terms
journal, December 1977

  • Allinger, Norman L.
  • Journal of the American Chemical Society, Vol. 99, Issue 25
  • DOI: 10.1021/ja00467a001

Chemistry Makes Graphene beyond Graphene
journal, August 2014

  • Liao, Lei; Peng, Hailin; Liu, Zhongfan
  • Journal of the American Chemical Society, Vol. 136, Issue 35
  • DOI: 10.1021/ja5048297

Electron-Electron Interactions in Graphene: Current Status and Perspectives
journal, July 2012


Band gaps and structural properties of graphene halides and their derivates: A hybrid functional study with localized orbital basis sets
journal, July 2012

  • Karlický, František; Zbořil, Radek; Otyepka, Michal
  • The Journal of Chemical Physics, Vol. 137, Issue 3
  • DOI: 10.1063/1.4736998

Structures of fluorinated graphene and their signatures
journal, March 2011


Band Gaps and Optical Spectra of Chlorographene, Fluorographene and Graphane from G 0 W 0 , GW 0 and GW Calculations on Top of PBE and HSE06 Orbitals
journal, August 2013

  • Karlický, František; Otyepka, Michal
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 9
  • DOI: 10.1021/ct400476r

Graphene to fluorographene and fluorographane: a theoretical study
journal, December 2012


Electronic and Magnetic Properties of Fluorinated Graphene with Different Coverage of Fluorine
journal, August 2012

  • Liu, H. Y.; Hou, Z. F.; Hu, C. H.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 34
  • DOI: 10.1021/jp303279r

Structural Models of Fluorine-Graphite Intercalation Compounds from Density Functional Theory
journal, April 2004

  • Bettinger, Holger F.; Kudin, Konstantin N.; Scuseria, Gustavo E.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 15
  • DOI: 10.1021/jp0310854

A Mechanistic Study of Graphene Fluorination
journal, March 2013

  • Lee, Sung-Sik; Jang, Sung-Woo; Park, Kkochorong
  • The Journal of Physical Chemistry C, Vol. 117, Issue 10
  • DOI: 10.1021/jp310826d

Patterning nanoroads and quantum dots on fluorinated graphene
journal, December 2010


Structural and electronic properties of single-side fluorinated graphene C4F under equibiaxial strains
journal, April 2014

  • Qu, Li-Hua; Zhang, Jian-Min; Xu, Ke-Wei
  • Physica E: Low-dimensional Systems and Nanostructures, Vol. 58
  • DOI: 10.1016/j.physe.2013.11.004

Magnetization of graphane by dehydrogenation
journal, November 2009

  • Şahin, H.; Ataca, C.; Ciraci, S.
  • Applied Physics Letters, Vol. 95, Issue 22
  • DOI: 10.1063/1.3268792

Electronic and optical properties of fluorinated graphene: A many-body perturbation theory study
journal, March 2013


Theoretical study of the electronic properties of fluorographene
journal, December 2010

  • Contreras, Cristina Nava; Cocoletzi, Heriberto Hernandez; Anota, Ernesto Chigo
  • Journal of Molecular Modeling, Vol. 17, Issue 8
  • DOI: 10.1007/s00894-010-0914-2

Structure of graphite by neutron diffraction
journal, November 1975


Structure and dynamics of microcrystalline graphite, graphon, by neutron scattering
journal, January 1976

  • Gamlen, P. H.; White, J. W.
  • Journal of the Chemical Society, Faraday Transactions 2, Vol. 72
  • DOI: 10.1039/f29767200446

Electronic structure of graphite: Effect of hydrostatic pressure
journal, February 1995


Density functional study of graphite bulk and surface properties
journal, February 2006


From graphene to graphite: Electronic structure around the K point
journal, August 2006


The electronic structure of graphite: A chemist's introduction to band theory
journal, October 1991

  • Pisanty, Alejandro
  • Journal of Chemical Education, Vol. 68, Issue 10
  • DOI: 10.1021/ed068p804

Band Structure of Graphite
journal, January 1958


Photoemission studies of graphite high-energy conduction-band and valence-band states using soft-x-ray synchrotron radiation excitation
journal, December 1977


Experimental demonstration of complete photonic band gap in graphite structure
journal, September 1997

  • Gadot, F.; Chelnokov, A.; De Lustrac, A.
  • Applied Physics Letters, Vol. 71, Issue 13
  • DOI: 10.1063/1.119396

Band structure and optical properties of graphite
journal, December 1996


A roadmap for graphene
journal, October 2012

  • Novoselov, K. S.; Fal′ko, V. I.; Colombo, L.
  • Nature, Vol. 490, Issue 7419
  • DOI: 10.1038/nature11458

Electric Field Effect in Atomically Thin Carbon Films
journal, October 2004


Electronic and vibrational signatures of Stone-Wales defects in graphene: First-principles analysis
journal, October 2012


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Ab initiomolecular dynamics for liquid metals
journal, January 1993


Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

  • Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
  • Journal of Computational Chemistry, Vol. 32, Issue 7
  • DOI: 10.1002/jcc.21759

A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006


Rational Design of Carboxyl Groups Perpendicularly Attached to a Graphene Sheet: A Platform for Enhanced Biosensing Applications
journal, December 2013

  • Bonanni, Alessandra; Chua, Chun Kiang; Pumera, Martin
  • Chemistry - A European Journal, Vol. 20, Issue 1
  • DOI: 10.1002/chem.201303582

Theoretical study of the electronic properties of fluorographene
journal, December 2010

  • Contreras, Cristina Nava; Cocoletzi, Heriberto Hernandez; Anota, Ernesto Chigo
  • Journal of Molecular Modeling, Vol. 17, Issue 8
  • DOI: 10.1007/s00894-010-0914-2

Functionalization of Graphene: Covalent and Non-Covalent Approaches, Derivatives and Applications
journal, September 2012

  • Georgakilas, Vasilios; Otyepka, Michal; Bourlinos, Athanasios B.
  • Chemical Reviews, Vol. 112, Issue 11
  • DOI: 10.1021/cr3000412

Chemistry Makes Graphene beyond Graphene
journal, August 2014

  • Liao, Lei; Peng, Hailin; Liu, Zhongfan
  • Journal of the American Chemical Society, Vol. 136, Issue 35
  • DOI: 10.1021/ja5048297

Graphene-Based Supercapacitor with an Ultrahigh Energy Density
journal, December 2010

  • Liu, Chenguang; Yu, Zhenning; Neff, David
  • Nano Letters, Vol. 10, Issue 12
  • DOI: 10.1021/nl102661q

Large Reversible Li Storage of Graphene Nanosheet Families for Use in Rechargeable Lithium Ion Batteries
journal, August 2008

  • Yoo, EunJoo; Kim, Jedeok; Hosono, Eiji
  • Nano Letters, Vol. 8, Issue 8, p. 2277-2282
  • DOI: 10.1021/nl800957b

Trapping of Metal Atoms in Vacancies of Carbon Nanotubes and Graphene
journal, May 2010

  • Rodríguez-Manzo, Julio A.; Cretu, Ovidiu; Banhart, Florian
  • ACS Nano, Vol. 4, Issue 6
  • DOI: 10.1021/nn100356q

A roadmap for graphene
journal, October 2012

  • Novoselov, K. S.; Fal′ko, V. I.; Colombo, L.
  • Nature, Vol. 490, Issue 7419
  • DOI: 10.1038/nature11458

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Graphene to fluorographene and fluorographane: a theoretical study
journal, December 2012


Doping Graphene with Metal Contacts
journal, July 2008


Hallmark of Perfect Graphene
journal, June 2004

  • Duplock, Elizabeth J.; Scheffler, Matthias; Lindan, Philip J. D.
  • Physical Review Letters, Vol. 92, Issue 22, Article No. 225502
  • DOI: 10.1103/physrevlett.92.225502

Electric Field Effect in Atomically Thin Carbon Films
journal, October 2004


High Efficiency Graphene Solar Cells by Chemical Doping
text, January 2012


Works referencing / citing this record:

Graphene-Based Smart Platforms for Combined Cancer Therapy
journal, July 2018