Atomically resolved imaging of highly ordered alternating fluorinated graphene

One of the most desirable goals of graphene research is to produce ordered two-dimensional (2D) chemical derivatives of suitable quality for monolayer device fabrication. Here we reveal, by focal series exit wave reconstruction (EWR), that C2F chair is a stable graphene derivative and demonstrates pristine long-range order limited only by the size of a functionalized domain. Focal series of images of graphene and C2F chair formed by reaction with XeF2 were obtained at 80 kV in an aberration-corrected transmission electron microscope. EWR images reveal that single carbon atoms and carbon-fluorine pairs in C2F chair alternate strictly over domain sizes of at least 150 nm(2) with electron diffraction indicating ordered domains ≥ 0.16 μm(2). Our results also indicate that, within an ordered domain, functionalization occurs on one side only as theory predicts. In addition, we show that electron diffraction provides a quick and easy method for distinguishing between graphene, C2F chair and fully fluorinated stoichiometric CF 2D phases.

[1]  W. O. Saxton,et al.  A new method for the determination of the wave aberration function for high-resolution TEM.; 2. Measurement of the antisymmetric aberrations. , 2004, Ultramicroscopy.

[2]  J. Robinson,et al.  Properties of fluorinated graphene films. , 2010, Nano letters.

[3]  Wei Zhang,et al.  Comparative Study of SWCNT Fluorination by Atomic and Molecular Fluorine , 2012 .

[4]  Ruitao Lv,et al.  The role of defects and doping in 2D graphene sheets and 1D nanoribbons , 2012, Reports on progress in physics. Physical Society.

[5]  S. Banerjee,et al.  Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils , 2009, Science.

[6]  Arthur P. Ramirez,et al.  Strongly Geometrically Frustrated Magnets , 1994 .

[7]  Fu-Rong Chen,et al.  Resolution extension and exit wave reconstruction in complex HREM. , 2004, Ultramicroscopy.

[8]  Steven G. Louie,et al.  Graphene at the Edge: Stability and Dynamics , 2009, Science.

[9]  K. Zou,et al.  Reversible fluorination of graphene: Evidence of a two-dimensional wide bandgap semiconductor , 2010, 1005.0113.

[10]  A. Thust,et al.  Maximum-likelihood method for focus-variation image reconstruction in high resolution transmission electron microscopy , 1996 .

[11]  Richard Beanland,et al.  Graphene oxide: structural analysis and application as a highly transparent support for electron microscopy. , 2009, ACS nano.

[12]  W. O. Saxton,et al.  A new method for the determination of the wave aberration function for high resolution TEM 1. Measurement of the symmetric aberrations. , 2002, Ultramicroscopy.

[13]  M. I. Katsnelson,et al.  On the roughness of single- and bi-layer graphene membranes , 2007, cond-mat/0703033.

[14]  S. Ciraci,et al.  Structures of fluorinated graphene and their signatures , 2011, 1103.3291.

[15]  Graphene reknits its holes. , 2012, Nano letters.

[16]  Ye Xu,et al.  One-pot sonochemical preparation of fluorographene and selective tuning of its fluorine coverage , 2012 .

[17]  R. Nair,et al.  Structure of hydrogen-dosed graphene deduced from low electron energy loss characteristics and density functional calculations , 2010 .

[18]  K. Novoselov,et al.  Control of Graphene's Properties by Reversible Hydrogenation: Evidence for Graphane , 2008, Science.

[19]  V. Kravets,et al.  Fluorographene: a two-dimensional counterpart of Teflon. , 2010, Small.

[20]  Interaction of NH3 with the reduced surface of graphite fluoride C2F , 2010 .

[21]  H. Dai,et al.  Chemically Derived, Ultrasmooth Graphene Nanoribbon Semiconductors , 2008, Science.

[22]  M. Hersam,et al.  Chemically homogeneous and thermally reversible oxidation of epitaxial graphene. , 2012, Nature chemistry.

[23]  Fu-Rong Chen,et al.  ‘Big Bang’ tomography as a new route to atomic-resolution electron tomography , 2012, Nature.

[24]  K. Novoselov,et al.  Graphene reknits its holes. , 2012, Nano letters.

[25]  Angus I. Kirkland,et al.  A new method for the determination of the wave aberration function for high resolution TEM , 2002 .

[26]  J. Warner,et al.  Atomic resolution imaging of graphene by transmission electron microscopy. , 2013, Nanoscale.

[27]  A. Zettl,et al.  Stability and dynamics of small molecules trapped on graphene , 2010 .

[28]  P. Kim,et al.  Energy band-gap engineering of graphene nanoribbons. , 2007, Physical review letters.

[29]  Thomas H. Bointon,et al.  Nanopatterning of fluorinated graphene by electron beam irradiation. , 2011, Nano letters.

[30]  F. Guinea,et al.  The electronic properties of graphene , 2007, Reviews of Modern Physics.

[31]  D. Neuhauser,et al.  A Mechanistic Study of Graphene Fluorination , 2013 .

[32]  Andre K. Geim,et al.  The rise of graphene. , 2007, Nature materials.

[33]  Ji Won Suk,et al.  Selective-area fluorination of graphene with fluoropolymer and laser irradiation. , 2012, Nano letters.

[34]  W. O. Saxton Recovery of Specimen Information for Strongly Scattering Objects , 1980 .

[35]  Y. Fujii,et al.  On the Structure of Graphite Fluoride , 1987 .

[36]  T. Fukunaga,et al.  Short-range structures of poly(dicarbon monofluoride) (C2F)n and poly(carbon monofluoride) (CF)n , 2004 .

[37]  R. Ruoff,et al.  The chemistry of graphene oxide. , 2010, Chemical Society reviews.

[38]  Y. Fujii,et al.  Chemical composition and crystal structure of graphite fluoride , 1979 .