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Covalent functionalization of graphene offers opportunities for tailoring its properties and is an unavoidable consequence of some graphene synthesis techniques. However, the changes induced by the functionalization are not well understood. By using atomic sources to control the extent of the oxygen and nitrogen functionalization, we studied the evolution in the structure and properties at the atomic scale. Atomic oxygen reversibly introduces epoxide groups whilst, under similar conditions, atomic nitrogen irreversibly creates diverse functionalities including substitutional, pyridinic, and pyrrolic nitrogen. Atomic oxygen leaves the Fermi energy at the Dirac point (i.e., undoped), whilst atomic nitrogen results in a net n-doping; however, the experimental results are consistent with the dominant electronic effect for both being a transition from delocalized to localized states, and hence the loss of the signature electronic structure of graphene.
Dreyer, D. R.; Park, S.; Bielawski, C. W.; Ruoff, R. S. The chemistry of graphene oxide. Chem. Soc. Rev. 2010, 39, 228-240.
Liu, N.; Luo, F.; Wu, H. X.; Liu, Y. H.; Zhang, C.; Chen, J. One-step ionic-liquid-assisted electrochemical synthesis of ionic-liquid-functionalized graphene sheets directly from graphite. Adv. Funct. Mater. 2008, 18, 1518-1525.
Dreyer, D. R.; Todd, A. D.; Bielawski, C. W. Harnessing the chemistry of graphene oxide. Chem. Soc. Rev. 2014, 43, 5288-5301.
Wang, Y.; Shao, Y. Y.; Matson, D. W.; Li, J. H.; Lin, Y. H. Nitrogen-doped graphene and its application in electrochemical biosensing. ACS Nano 2010, 4, 1790-1798.
Mo, Z. Y.; Zheng, R. P.; Peng, H. L.; Liang, H. G.; Liao, S. J. Nitrogen-doped graphene prepared by a transfer doping approach for the oxygen reduction reaction application. J. Power Sources 2014, 245, 801-807.
Wood, K. N.; O'Hayre, R.; Pylypenko, S. Recent progress on nitrogen/carbon structures designed for use in energy and sustainability applications. Energy Environ. Sci. 2014, 7, 1212-1249.
Wang, H. B.; Maiyalagan, T.; Wang, X. Review on recent progress in nitrogen-doped graphene: Synthesis, characterization, and its potential applications. ACS Catal. 2012, 2, 781-794.
Qu, L. T.; Liu, Y.; Baek, J. B.; Dai, L. M. Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 2010, 4, 1321-1326.
Wei, D. C.; Liu, Y. Q.; Wang, Y.; Zhang, H. L.; Huang, L. P.; Yu, G. Synthesis of N-doped graphene by chemical vapor deposition and its electrical properties. Nano Lett. 2009, 9, 1752-1758.
Zabet-Khosousi, A.; Zhao, L. Y.; Pálová, L.; Hybertsen, M. S.; Reichman, D. R.; Pasupathy, A. N.; Flynn, G. W. Segregation of sublattice domains in nitrogen-doped graphene. J. Am. Chem. Soc. 2014, 136, 1391-1397.
Yuan, J. T.; Ma, L. P.; Pei, S. F.; Du, J. H.; Su, Y.; Ren, W. C.; Cheng, H. M. Tuning the electrical and optical properties of graphene by ozone treatment for patterning monolithic transparent electrodes. ACS Nano 2013, 7, 4233-4241.
Leconte, N.; Moser, J.; Ordejón, P.; Tao, H. H.; Lherbier, A.; Bachtold, A.; Alsina, F.; Sotomayor Torres, C. M.; Charlier, J. C.; Roche, S. Damaging graphene with ozone treatment: A chemically tunable metal-insulator transition. ACS Nano 2010, 4, 4033-4038.
Peltekis, N.; Kumar, S.; McEvoy, N.; Lee, K.; Weidlich, A.; Duesberg, G. S. The effect of downstream plasma treatments on graphene surfaces. Carbon 2012, 50, 395-403.
Hossain, M. Z.; Johns, J. E.; Bevan, K. H.; Karmel, H. J.; Liang, Y. T.; Yoshimoto, S.; Mukai, K.; Koitaya, T.; Yoshinobu, J.; Kawai, M. et al. Chemically homogeneous and thermally reversible oxidation of epitaxial graphene. Nat. Chem. 2012, 4, 305-309.
Barinov, A.; Malcioğlu, B. O.; Fabris, S.; Sun, T.; Gregoratti, L.; Dalmiglio, M.; Kiskinova, M. Initial stages of oxidation on graphitic surfaces: Photoemission study and density functional theory calculations. J. Phys. Chem. C 2009, 113, 9009-9013.
Marsden, A. J.; Phillips, M.; Wilson, N. R. Friction force microscopy: A simple technique for identifying graphene on rough substrates and mapping the orientation of graphene grains on copper. Nanotechnology 2013, 24, 255704.
Wilson, N. R.; Marsden, A. J.; Saghir, M.; Bromley, C. J.; Schaub, R.; Costantini, G.; White, T. W.; Partridge, C.; Barinov, A.; Dudin, P. et al. Weak mismatch epitaxy and structural feedback in graphene growth on copper foil. Nano Res. 2013, 6, 99-112.
Marsden, A. J.; Asensio, M. C.; Avila, J.; Dudin, P.; Barinov, A.; Moras, P.; Sheverdyaeva, P. M.; White, T. W.; Maskery, I.; Costantini, G. et al. Is graphene on copper doped? Phys. Status Solidi-Rapid Res. Lett. 2013, 7, 643-646.
Blume, R.; Kidambi, P. R.; Bayer, B. C.; Weatherup, R. S.; Wang, Z. J.; Weinberg, G.; Willinger, M. G.; Greiner, M.; Hofmann, S.; Knop-Gericke, A. et al. The influence of intercalated oxygen on the properties of graphene on polycrystalline Cu under various environmental conditions. Phys. Chem. Chem. Phys. 2014, 16, 25989-26003.
Sheng, Z. H.; Shao, L.; Chen, J. J.; Bao, W. J.; Wang, F. B.; Xia, X. H. Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis. ACS Nano 2011, 5, 4350-4358.
Usachov, D.; Vilkov, O.; Grüneis, A.; Haberer, D.; Fedorov, A.; Adamchuk, V. K.; Preobrajenski, A. B.; Dudin, P.; Barinov, A.; Oehzelt, M. et al. Nitrogen-doped graphene: Efficient growth, structure, and electronic properties. Nano Lett. 2011, 11, 5401-5407.
Zhang, L.; Ye, Y. F.; Cheng, D. D.; Zhang, W. H.; Pan, H. B.; Zhu, J. F. Simultaneous reduction and N-doping of graphene oxides by low-energy N2+ ion sputtering. Carbon 2013, 62, 365-373.
Scardamaglia, M.; Aleman, B.; Amati, M.; Ewels, C.; Pochet, P.; Reckinger, N.; Colomer, J. F.; Skaltsas, T.; Tagmatarchis, N.; Snyders, R. et al. Nitrogen implantation of suspended graphene flakes: Annealing effects and selectivity of sp2 nitrogen species. Carbon 2014, 73, 371-381.
Banhart, F.; Kotakoski, J.; Krasheninnikov, A. V. Structural defects in graphene. ACS Nano 2011, 5, 26-41.
Terrones, H.; Lv, R. T.; Terrones, M.; Dresselhaus, M. S. The role of defects and doping in 2D graphene sheets and 1D nanoribbons. Rep. Prog. Phys. 2012, 75, 062501.
Gómez-Navarro, C.; Meyer, J. C.; Sundaram, R. S.; Chuvilin, A.; Kurasch, S.; Burghard, M.; Kern, K.; Kaiser, U. Atomic structure of reduced graphene oxide. Nano Lett. 2010, 10, 1144-1148.
Cretu, O.; Krasheninnikov, A. V.; Rodríguez-Manzo, J. A.; Sun, L. T.; Nieminen, R. M.; Banhart, F. Migration and localization of metal atoms on strained graphene. Phys. Rev. Lett. 2010, 105, 196102.
Lee, G. D.; Wang, C. Z.; Yoon, E.; Hwang, N. M.; Kim, D. Y.; Ho, K. M. Diffusion, coalescence, and reconstruction of vacancy defects in graphene layers. Phys. Rev. Lett. 2005, 95, 205501.
Fujimoto, Y.; Saito, S. Formation, stabilities, and electronic properties of nitrogen defects in graphene. Phys. Rev. B 2011, 84, 245446.
Hou, Z. F.; Wang, X. L.; Ikeda, T.; Terakura, K.; Oshima, M.; Kakimoto, M.; Miyata, S. Interplay between nitrogen dopants and native point defects in graphene. Phys. Rev. B 2012, 85, 165439.
El-Barbary, A. A.; Telling, R. H.; Ewels, C. P.; Heggie, M. I.; Briddon, P. R. Structure and energetics of the vacancy in graphite. Phys. Rev. B 2003, 68, 144107.
Robertson, A. W.; Allen, C. S.; Wu, Y. M. A.; He, K.; Olivier, J.; Neethling, J.; Kirkland, A. I.; Warner, J. H. Spatial control of defect creation in graphene at the nanoscale. Nat. Commun. 2012, 3, 1144.
Bostwick, A.; McChesney, J.; Emtsev, K.; Seyller, T.; Horn, K.; Kevan, S.; Rotenberg, E. Quasiparticle transformation during a metal-insulator transition in graphene. Phys. Rev. Lett. 2009, 103, 056404.
Castro Neto, A. H.; Guinea, F.; Peres, N. M. R.; Novoselov, K. S.; Geim, A. K. The electronic properties of graphene. Rev. Mod. Phys. 2009, 81, 109-162.
Gómez-Navarro, C.; Weitz, R. T.; Bittner, A. M.; Scolari, M.; Mews, A.; Burghard, M.; Kern, K. Electronic transport properties of individual chemically reduced graphene oxide sheets. Nano Lett. 2007, 7, 3499-3503.
Hou, Z. F.; Wang, X. L.; Ikeda, T.; Terakura, K.; Oshima, M.; Kakimoto, M. Electronic structure of N-doped graphene with native point defects. Phys. Rev. B 2013, 87, 165401.
Usachov, D.; Fedorov, A.; Vilkov, O.; Senkovskiy, B.; Adamchuk, V. K.; Yashina, L. V.; Volykhov, A. A.; Farjam, M.; Verbitskiy, N. I.; Grüneis, A. et al. The chemistry of imperfections in N-graphene. Nano Lett. 2014, 14, 4892-4988.
Nair, R. R.; Ren, W. C.; Jalil, R.; Riaz, I.; Kravets, V. G.; Britnell, L.; Blake, P.; Schedin, F.; Mayorov, A. S.; Yuan, S. J. et al. Fluorographene: A two-dimensional counterpart of Teflon. Small 2010, 6, 2877-2884.
Elias, D. C.; Nair, R. R.; Mohiuddin, T. M. G.; Morozov, S. V.; Blake, P.; Halsall, M. P.; Ferrari, A. C.; Boukhvalov, D. W.; Katsnelson, M. I.; Geim, A. K. et al. Control of graphene's properties by reversible hydrogenation: Evidence for graphane. Science 2009, 323, 610-613.
Avila, J.; Razado-Colambo, I.; Lorcy, S.; Lagarde, B.; Giorgetta, J. L.; Polack, F.; Asensio, M. C. ANTARES, a scanning photoemission microscopy beamline at SOLEIL. J. Phys. Conf. Ser. 2013, 425, 192023.
Meyer, R. R.; Kirkland, A. I.; Saxton, W. O. A new method for the determination of the wave aberration function for high resolution TEM: 1. Measurement of the symmetric aberrations. Ultramicroscopy 2002, 92, 89-109.
Clark, S. J.; Segall, M. D.; Pickard, C. J.; Hasnip, P. J.; Probert, M. I. J.; Refson, K.; Payne, M. C. First principles methods using CASTEP. Z. Kristall. 2005, 220, 567-570.
Perdew, J. P.; Wang, Y. Accurate and simple analytic representation of the electron-gas correlation energy. Phys. Rev. B 1992, 45, 13244-13249.
Vanderbilt, D. Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Phys. Rev. B 1990, 41, 7892-7895.
Monkhorst, H. J.; Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 1976, 13, 5188-5192.
Byrd, R. H.; Nocedal, J.; Schnabel, R. B. Representations of quasi-Newton matrices and their use in limited memory methods. Math. Program. 1994, 63, 129-156.
Popescu, V.; Zunger, A. Effective band structure of random alloys. Phys. Rev. Lett. 2010, 104, 236403.
Popescu, V.; Zunger, A. Extracting E versus $\overrightarrow{\boldsymbol{k}}$ effective band structure from supercell calculations on alloys and impurities. Phys. Rev. B 2012, 85, 085201.
Brommer, P.; Quigley, D. Automated effective band structures for defective and mismatched supercells. J. Phys. Condens. Matter 2014, 26, 485501.
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