Transformations of carbon adsorbates on graphene substrates under extreme heat.

We describe new phenomena of structural reorganization of carbon adsorbates as revealed by in situ atomic-resolution transmission electron microscopy (TEM) performed on specimens at extreme temperatures. In our investigations, a graphene sheet serves as both a quasi-transparent substrate for TEM and as an in situ heater. The melting of gold nanoislands deposited on the substrate surface is used to evaluate the local temperature profile. At annealing temperatures around 1000 K, we observe the transformation of physisorbed hydrocarbon adsorbates into amorphous carbon monolayers and the initiation of crystallization. At temperatures exceeding 2000 K the transformation terminates in the formation of a completely polycrystalline graphene state. The resulting layers are bounded by free edges primarily in the armchair configuration.

[1]  T. Kamino,et al.  Development of a technique for high resolution electron microscopic observation of nano-materials at elevated temperatures. , 2005, Journal of electron microscopy.

[2]  M. Malac,et al.  Radiation damage in the TEM and SEM. , 2004, Micron.

[3]  Henny W. Zandbergen,et al.  Atomic-Scale Electron-Beam Sculpting of Defect-Free Graphene Nanostructures , 2011, Microscopy and Microanalysis.

[4]  K. Suenaga,et al.  Atom-by-atom spectroscopy at graphene edge , 2010, Nature.

[5]  A. Reina,et al.  Controlled Formation of Sharp Zigzag and Armchair Edges in Graphitic Nanoribbons , 2009, Science.

[6]  Maximilian Haider,et al.  Aberration correction in a low voltage SEM by a multipole corrector , 1995 .

[7]  J. Meyer,et al.  From graphene constrictions to single carbon chains , 2009, 0905.3090.

[8]  Z. Hu,et al.  Phase transition and particulate growth of laser synthesized ultrafine amorphous silicon nitride powders , 1994 .

[9]  T. Richardson,et al.  Direct imaging of soft-hard interfaces enabled by graphene. , 2009, Nano letters.

[10]  W. Dobelle,et al.  CHEMICALLY CLEAVED GRAPHITE SUPPORT FILMS FOR ELECTRON MICROSCOPY , 1968, The Journal of cell biology.

[11]  Pekka Koskinen,et al.  Self-passivating edge reconstructions of graphene. , 2008, Physical review letters.

[12]  David J. Smith,et al.  Imaging of atomic clouds outside the surfaces of gold crystals by electron microscopy , 1985, Nature.

[13]  Grégory Pandraud,et al.  Atomic-scale electron-beam sculpting of near-defect-free graphene nanostructures. , 2011, Nano letters.

[14]  P. Lu,et al.  In situ observation of graphene sublimation and multi-layer edge reconstructions , 2009, Proceedings of the National Academy of Sciences.

[15]  J. W. Menter The direct study by electron microscopy of crystal lattices and their imperfections , 1956, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[16]  M. Haider,et al.  Information Transfer in a TEM Corrected for Spherical and Chromatic Aberration , 2010, Microscopy and Microanalysis.

[17]  T. Ichihashi,et al.  Motion of Surface Atoms on Small Gold Particles Revealed by HREM with Real-Time VTR System , 1985 .

[18]  Feng Wang,et al.  High‐temperature stability of suspended single‐layer graphene , 2010 .

[19]  R. Rosenfeld Nature , 2009, Otolaryngology--head and neck surgery : official journal of American Academy of Otolaryngology-Head and Neck Surgery.

[20]  L. Allard,et al.  On the behavior of Ag nanowires under high temperature: in situ characterization by aberration-corrected STEM , 2011 .

[21]  Pinshane Y. Huang,et al.  Grains and grain boundaries in single-layer graphene atomic patchwork quilts , 2010, Nature.

[22]  K. Novoselov,et al.  Macroscopic graphene membranes and their extraordinary stiffness. , 2008, Nano letters.

[23]  Bernd Kabius,et al.  Electron microscopy image enhanced , 1998, Nature.

[24]  Jannik C. Meyer,et al.  Experimental analysis of charge redistribution due to chemical bonding by high-resolution transmission electron microscopy. , 2011, Nature materials.

[25]  Ondrej L. Krivanek,et al.  Towards sub-Å electron beams , 1999 .

[26]  J. Biskupek,et al.  Self-assembly of a sulphur-terminated graphene nanoribbon within a single-walled carbon nanotube. , 2011, Nature materials.

[27]  Jannik C. Meyer,et al.  Imaging and dynamics of light atoms and molecules on graphene , 2008, Nature.

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

[29]  M F Crommie,et al.  Direct imaging of lattice atoms and topological defects in graphene membranes. , 2008, Nano letters.

[30]  S. Louie,et al.  Electronic transport in polycrystalline graphene. , 2010, Nature materials.

[31]  Conversion of self-assembled monolayers into nanocrystalline graphene: structure and electric transport. , 2011, ACS nano.

[32]  J. Kysar,et al.  Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene , 2008, Science.

[33]  J. Meyer,et al.  Graphene-based sample supports for in situ high-resolution TEM electrical investigations , 2011 .

[34]  V. Nicolosi,et al.  Gentle STEM: ADF imaging and EELS at low primary energies $ , 2010 .

[35]  A. Kirkland,et al.  Nanogold: a quantitative phase map. , 2009, ACS nano.

[36]  H. Sawada,et al.  Visualizing and identifying single atoms using electron energy-loss spectroscopy with low accelerating voltage. , 2009, Nature chemistry.

[37]  U Kaiser,et al.  Transmission electron microscopy at 20 kV for imaging and spectroscopy. , 2011, Ultramicroscopy.

[38]  P. Buffat,et al.  Size effect on the melting temperature of gold particles , 1976 .

[39]  A. Fedorov,et al.  Analysis of electron beam induced deposition (EBID) of residual hydrocarbons in electron microscopy , 2007 .

[40]  E. Sutter,et al.  Assembly and interaction of Au/C core-shell nanostructures: in situ observation in the transmission electron microscope. , 2005, Nano letters.

[41]  Ju Li,et al.  In situ observations of the nucleation and growth of atomically sharp graphene bilayer edges , 2010 .

[42]  H. Kataura,et al.  Analysis of the reactivity and selectivity of fullerene dimerization reactions at the atomic level. , 2010, Nature chemistry.