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

Duan, Yuhua; Stinespring, Charter D.; Chorpening, Benjamin

doi:10.1002/open.201500074

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

Journal Article · Thu Jun 18 00:00:00 EDT 2015 · ChemistryOpen

DOI:https://doi.org/10.1002/open.201500074· OSTI ID:1209521

^[1]; Stinespring, Charter D. ^[2]; Chorpening, Benjamin ^[1]

National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
National Energy Technology Lab. (NETL), Morgantown, WV (United States); National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: National Energy Technology Lab. (NETL), Pittsburgh, PA, and Morgantown, WV (United States). In-house Research

Sponsoring Organization:: USDOE Office of Fossil Energy (FE)

OSTI ID:: 1209521

Report Number(s):: NETL-PUB-1162

Journal Information:: ChemistryOpen, Vol. 4, Issue 5; ISSN 2191-1363

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 18 works

Citation information provided by
Web of Science

References (62)

Functionalization of Graphene: Covalent and Non-Covalent Approaches, Derivatives and Applications Georgakilas, Vasilios; Otyepka, Michal; Bourlinos, Athanasios B. Chemical Reviews, Vol. 112, Issue 11 https://doi.org/10.1021/cr3000412	journal	September 2012
Adsorption of $H_{2} O$ , $N H_{3}$ , CO, $N O_{2}$ , and NO on graphene: A first-principles study Leenaerts, O.; Partoens, B.; Peeters, F. M. Physical Review B, Vol. 77, Issue 12 https://doi.org/10.1103/PhysRevB.77.125416	journal	March 2008
High Efficiency Graphene Solar Cells by Chemical Doping Miao, Xiaochang; Tongay, Sefaattin; Petterson, Maureen K. Nano Letters, Vol. 12, Issue 6 https://doi.org/10.1021/nl204414u	journal	May 2012
Graphene-Based Supercapacitor with an Ultrahigh Energy Density Liu, Chenguang; Yu, Zhenning; Neff, David Nano Letters, Vol. 10, Issue 12 https://doi.org/10.1021/nl102661q	journal	December 2010
Large Reversible Li Storage of Graphene Nanosheet Families for Use in Rechargeable Lithium Ion Batteries Yoo, EunJoo; Kim, Jedeok; Hosono, Eiji Nano Letters, Vol. 8, Issue 8, p. 2277-2282 https://doi.org/10.1021/nl800957b	journal	August 2008
Mechanisms of the Oxygen Reduction Reaction on Defective Graphene-Supported Pt Nanoparticles from First-Principles Lim, Dong-Hee; Wilcox, Jennifer The Journal of Physical Chemistry C, Vol. 116, Issue 5 https://doi.org/10.1021/jp210796e	journal	January 2012
Epitaxial Graphene Transistors on SiC Substrates Kedzierski, Jakub; Hsu, Pei-Lan; Healey, Paul IEEE Transactions on Electron Devices, Vol. 55, Issue 8 https://doi.org/10.1109/TED.2008.926593	journal	August 2008
Tunable Quantum Dots in Bilayer Graphene Pereira,, J. Milton; Vasilopoulos, P.; Peeters, F. M. Nano Letters, Vol. 7, Issue 4 https://doi.org/10.1021/nl062967s	journal	April 2007
The electronic properties of graphene Castro Neto, A. H.; Guinea, F.; Peres, N. M. R. Reviews of Modern Physics, Vol. 81, Issue 1, p. 109-162 https://doi.org/10.1103/RevModPhys.81.109	journal	January 2009
Chiral tunnelling and the Klein paradox in graphene Katsnelson, M. I.; Novoselov, K. S.; Geim, A. K. Nature Physics, Vol. 2, Issue 9 https://doi.org/10.1038/nphys384	journal	August 2006
Two-dimensional gas of massless Dirac fermions in graphene Novoselov, K. S.; Geim, A. K.; Morozov, S. V. Nature, Vol. 438, Issue 7065, p. 197-200 https://doi.org/10.1038/nature04233	journal	November 2005
The chemistry of graphene oxide Dreyer, Daniel R.; Park, Sungjin; Bielawski, Christopher W. Chem. Soc. Rev., Vol. 39, Issue 1 https://doi.org/10.1039/B917103G	journal	January 2010
Rational Design of Carboxyl Groups Perpendicularly Attached to a Graphene Sheet: A Platform for Enhanced Biosensing Applications Bonanni, Alessandra; Chua, Chun Kiang; Pumera, Martin Chemistry - A European Journal, Vol. 20, Issue 1 https://doi.org/10.1002/chem.201303582	journal	December 2013
Trapping of Metal Atoms in Vacancies of Carbon Nanotubes and Graphene Rodríguez-Manzo, Julio A.; Cretu, Ovidiu; Banhart, Florian ACS Nano, Vol. 4, Issue 6 https://doi.org/10.1021/nn100356q	journal	May 2010
Control of Graphene's Properties by Reversible Hydrogenation: Evidence for Graphane Elias, D. C.; Nair, R. R.; Mohiuddin, T. M. G. Science, Vol. 323, Issue 5914 https://doi.org/10.1126/science.1167130	journal	January 2009
Plasma-chemical bromination of graphitic materials and its use for subsequent functionalization and grafting of organic molecules Friedrich, J. F.; Wettmarshausen, S.; Hanelt, S. Carbon, Vol. 48, Issue 13 https://doi.org/10.1016/j.carbon.2010.06.054	journal	November 2010
Properties of Fluorinated Graphene Films Robinson, Jeremy T.; Burgess, James S.; Junkermeier, Chad E. Nano Letters, Vol. 10, Issue 8 https://doi.org/10.1021/nl101437p	journal	August 2010
Impact of Chlorine Functionalization on High-Mobility Chemical Vapor Deposition Grown Graphene Zhang, Xu; Hsu, Allen; Wang, Han ACS Nano, Vol. 7, Issue 8 https://doi.org/10.1021/nn4026756	journal	July 2013
Transition metal adatom and dimer adsorbed on graphene: Induced magnetization and electronic structures Cao, Chao; Wu, Min; Jiang, Jianzhong Physical Review B, Vol. 81, Issue 20 https://doi.org/10.1103/PhysRevB.81.205424	journal	May 2010
Adatoms in graphene Castro Neto, A. H.; Kotov, V. N.; Nilsson, J. Solid State Communications, Vol. 149, Issue 27-28 https://doi.org/10.1016/j.ssc.2009.02.040	journal	July 2009
Electrical control of the chemical bonding of fluorine on graphene Sofo, J. O.; Suarez, A. M.; Usaj, Gonzalo Physical Review B, Vol. 83, Issue 8 https://doi.org/10.1103/PhysRevB.83.081411	journal	February 2011
Novel surface chemical synthesis route for large area graphene-on-insulator films 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 https://doi.org/10.1116/1.4710997	journal	May 2012
On the so-called “semi-ionic” C–F bond character in fluorine–GIC Sato, Yuta; Itoh, Keiji; Hagiwara, Rika Carbon, Vol. 42, Issue 15 https://doi.org/10.1016/j.carbon.2004.08.012	journal	January 2004
Conformational analysis. 130. MM2. A hydrocarbon force field utilizing V1 and V2 torsional terms Allinger, Norman L. Journal of the American Chemical Society, Vol. 99, Issue 25 https://doi.org/10.1021/ja00467a001	journal	December 1977
Chemistry Makes Graphene beyond Graphene Liao, Lei; Peng, Hailin; Liu, Zhongfan Journal of the American Chemical Society, Vol. 136, Issue 35 https://doi.org/10.1021/ja5048297	journal	August 2014
Electron-Electron Interactions in Graphene: Current Status and Perspectives Kotov, Valeri N.; Uchoa, Bruno; Pereira, Vitor M. Reviews of Modern Physics, Vol. 84, Issue 3 https://doi.org/10.1103/RevModPhys.84.1067	journal	July 2012
Band gaps and structural properties of graphene halides and their derivates: A hybrid functional study with localized orbital basis sets Karlický, František; Zbořil, Radek; Otyepka, Michal The Journal of Chemical Physics, Vol. 137, Issue 3 https://doi.org/10.1063/1.4736998	journal	July 2012
Structures of fluorinated graphene and their signatures Şahin, H.; Topsakal, M.; Ciraci, S. Physical Review B, Vol. 83, Issue 11 https://doi.org/10.1103/PhysRevB.83.115432	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 Karlický, František; Otyepka, Michal Journal of Chemical Theory and Computation, Vol. 9, Issue 9 https://doi.org/10.1021/ct400476r	journal	August 2013
Graphene to fluorographene and fluorographane: a theoretical study Paupitz, R.; Autreto, P. A. S.; Legoas, S. B. Nanotechnology, Vol. 24, Issue 3 https://doi.org/10.1088/0957-4484/24/3/035706	journal	December 2012
Electronic and Magnetic Properties of Fluorinated Graphene with Different Coverage of Fluorine Liu, H. Y.; Hou, Z. F.; Hu, C. H. The Journal of Physical Chemistry C, Vol. 116, Issue 34 https://doi.org/10.1021/jp303279r	journal	August 2012
Structural Models of Fluorine-Graphite Intercalation Compounds from Density Functional Theory ^† Bettinger, Holger F.; Kudin, Konstantin N.; Scuseria, Gustavo E. The Journal of Physical Chemistry A, Vol. 108, Issue 15 https://doi.org/10.1021/jp0310854	journal	April 2004
A Mechanistic Study of Graphene Fluorination Lee, Sung-Sik; Jang, Sung-Woo; Park, Kkochorong The Journal of Physical Chemistry C, Vol. 117, Issue 10 https://doi.org/10.1021/jp310826d	journal	March 2013
Patterning nanoroads and quantum dots on fluorinated graphene Ribas, Morgana A.; Singh, Abhishek K.; Sorokin, Pavel B. Nano Research, Vol. 4, Issue 1 https://doi.org/10.1007/s12274-010-0084-7	journal	December 2010
Structural and electronic properties of single-side fluorinated graphene C4F under equibiaxial strains Qu, Li-Hua; Zhang, Jian-Min; Xu, Ke-Wei Physica E: Low-dimensional Systems and Nanostructures, Vol. 58 https://doi.org/10.1016/j.physe.2013.11.004	journal	April 2014
Magnetization of graphane by dehydrogenation Şahin, H.; Ataca, C.; Ciraci, S. Applied Physics Letters, Vol. 95, Issue 22 https://doi.org/10.1063/1.3268792	journal	November 2009
Electronic and optical properties of fluorinated graphene: A many-body perturbation theory study Wei, Wei; Jacob, Timo Physical Review B, Vol. 87, Issue 11 https://doi.org/10.1103/PhysRevB.87.115431	journal	March 2013
Theoretical study of the electronic properties of fluorographene Contreras, Cristina Nava; Cocoletzi, Heriberto Hernandez; Anota, Ernesto Chigo Journal of Molecular Modeling, Vol. 17, Issue 8 https://doi.org/10.1007/s00894-010-0914-2	journal	December 2010
Structure of graphite by neutron diffraction Trucano, Peter; Chen, Ruey Nature, Vol. 258, Issue 5531 https://doi.org/10.1038/258136a0	journal	November 1975
Structure and dynamics of microcrystalline graphite, graphon, by neutron scattering Gamlen, P. H.; White, J. W. Journal of the Chemical Society, Faraday Transactions 2, Vol. 72 https://doi.org/10.1039/f29767200446	journal	January 1976
Electronic structure of graphite: Effect of hydrostatic pressure Ahuja, R.; Auluck, S.; Trygg, J. Physical Review B, Vol. 51, Issue 8 https://doi.org/10.1103/PhysRevB.51.4813	journal	February 1995
All-electron full-potential calculation of the electronic band structure, elastic constants, and equation of state for graphite Boettger, J. C. Physical Review B, Vol. 55, Issue 17 https://doi.org/10.1103/PhysRevB.55.11202	journal	May 1997
Density functional study of graphite bulk and surface properties Ooi, Newton; Rairkar, Asit; Adams, James B. Carbon, Vol. 44, Issue 2 https://doi.org/10.1016/j.carbon.2005.07.036	journal	February 2006
From graphene to graphite: Electronic structure around the $K$ point Partoens, B.; Peeters, F. M. Physical Review B, Vol. 74, Issue 7 https://doi.org/10.1103/PhysRevB.74.075404	journal	August 2006
The electronic structure of graphite: A chemist's introduction to band theory Pisanty, Alejandro Journal of Chemical Education, Vol. 68, Issue 10 https://doi.org/10.1021/ed068p804	journal	October 1991
Band Structure of Graphite Slonczewski, J. C.; Weiss, P. R. Physical Review, Vol. 109, Issue 2 https://doi.org/10.1103/PhysRev.109.272	journal	January 1958
Photoemission studies of graphite high-energy conduction-band and valence-band states using soft-x-ray synchrotron radiation excitation Bianconi, A.; Hagström, S. B. M.; Bachrach, R. Z. Physical Review B, Vol. 16, Issue 12 https://doi.org/10.1103/PhysRevB.16.5543	journal	December 1977
Experimental demonstration of complete photonic band gap in graphite structure Gadot, F.; Chelnokov, A.; De Lustrac, A. Applied Physics Letters, Vol. 71, Issue 13 https://doi.org/10.1063/1.119396	journal	September 1997
Band structure and optical properties of graphite Solanki, A. K.; Kashyap, Arti; Nautiyal, T. Solid State Communications, Vol. 100, Issue 9 https://doi.org/10.1016/0038-1098(96)00471-1	journal	December 1996
A roadmap for graphene Novoselov, K. S.; Fal′ko, V. I.; Colombo, L. Nature, Vol. 490, Issue 7419 https://doi.org/10.1038/nature11458	journal	October 2012
Electric Field Effect in Atomically Thin Carbon Films Novoselov, K. S. Science, Vol. 306, Issue 5696, p. 666-669 https://doi.org/10.1126/science.1102896	journal	October 2004
Electronic and vibrational signatures of Stone-Wales defects in graphene: First-principles analysis Shirodkar, Sharmila N.; Waghmare, Umesh V. Physical Review B, Vol. 86, Issue 16 https://doi.org/10.1103/PhysRevB.86.165401	journal	October 2012
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
A fast and robust algorithm for Bader decomposition of charge density Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes Computational Materials Science, Vol. 36, Issue 3 https://doi.org/10.1016/j.commatsci.2005.04.010	journal	June 2006
Doping Graphene with Metal Contacts Giovannetti, G.; Khomyakov, P. A.; Brocks, G. Physical Review Letters, Vol. 101, Issue 2 https://doi.org/10.1103/physrevlett.101.026803	journal	July 2008
Hallmark of Perfect Graphene Duplock, Elizabeth J.; Scheffler, Matthias; Lindan, Philip J. D. Physical Review Letters, Vol. 92, Issue 22, Article No. 225502 https://doi.org/10.1103/physrevlett.92.225502	journal	June 2004
High Efficiency Graphene Solar Cells by Chemical Doping Miao, Xiaochang; Tongay, Sefaattin; Petterson, Maureen K. arXiv https://doi.org/10.48550/arxiv.1209.0432	text	January 2012

Cited By (3)

Graphene-Based Smart Platforms for Combined Cancer Therapy Gu, Zhanjun; Zhu, Shuang; Yan, Liang Advanced Materials, Vol. 31, Issue 9 https://doi.org/10.1002/adma.201800662	journal	July 2018
Pressure induced phase transition and band gap controlling in defective graphene mono-sheet: Density functional theory Talla, Jamal A. Materials Research Express, Vol. 6, Issue 11 https://doi.org/10.1088/2053-1591/ab4408	journal	September 2019
Facile Synthesis of Heterojunctioned ZnO/Bi2S3 Nanocomposites for Enhanced Photocatalytic Reduction of Aqueous Cr(VI) under Visible-Light Irradiation Yuan, Xiaoya; Wu, Xue; Feng, Zijuan Catalysts, Vol. 9, Issue 7 https://doi.org/10.3390/catal9070624	journal	July 2019

Similar Records

Hydrogen and fluorine co-decorated silicene: A first principles study of piezoelectric properties

Journal Article · Sun Jun 14 00:00:00 EDT 2015 · Journal of Applied Physics · OSTI ID:1209521

Noor-A-Alam, Mohammad; Kim, Hye Jung; Shin, Young-Han

Atomic mechanisms of fracture in silicon: Ab initio quantum molecular dynamics calculations

Miscellaneous · Fri Jan 01 00:00:00 EST 1993 · OSTI ID:1209521

Huang, Yin Min

Core Level Shifts of Hydrogenated Pyridinic and Pyrrolic Nitrogen in the Nitrogen-Containing Graphene-Based Electrocatalysts: In-Plane vs Edge Defects

Journal Article · Wed Dec 07 00:00:00 EST 2016 · Journal of Physical Chemistry. C · OSTI ID:1209521

Matanovic, Ivana; Artyushkova, Kateryna; Strand, Matthew B.; +3 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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

Citation Formats

References (62)

Cited By (3)

Similar Records

Related Subjects