Orientation‐Dependent Strain Relaxation and Chemical Functionalization of Graphene on a Cu(111) Foil

Epitaxial graphene grown on single crystal Cu(111) foils by chemical vapor deposition is found to be free of wrinkles and under biaxial compressive strain. The compressive strain in the epitaxial regions (0.25–0.40%) is higher than regions where the graphene is not epitaxial with the underlying surface (0.20–0.25%). This orientation‐dependent strain relaxation is through the loss of local adhesion and the generation of graphene wrinkles. Density functional theory calculations suggest a large frictional force between the epitaxial graphene and the Cu(111) substrate, and this is therefore an energy barrier to the formation of wrinkles in the graphene. Enhanced chemical reactivity is found in epitaxial graphene on Cu(111) foils as compared to graphene on polycrystalline Cu foils for certain chemical reactions. A higher compressive strain possibly favors lowering the formation energy and/or the energy gap between the initial and transition states, either of which can lead to an increase in chemical reactivity.

[1]  R. Ruoff,et al.  Ultrafast epitaxial growth of metre-sized single-crystal graphene on industrial Cu foil. , 2017, Science bulletin.

[2]  R. Ruoff,et al.  Role of Graphene in Water-Assisted Oxidation of Copper in Relation to Dry Transfer of Graphene , 2017 .

[3]  R. Ruoff,et al.  Sodide and Organic Halides Effect Covalent Functionalization of Single-Layer and Bilayer Graphene. , 2017, Journal of the American Chemical Society.

[4]  V. Valeš,et al.  Tuning the Reactivity of Graphene by Surface Phase Orientation. , 2017, Chemistry.

[5]  Dong Jin Kim,et al.  Strain Relaxation of Graphene Layers by Cu Surface Roughening. , 2016, Nano letters.

[6]  Zhirong Liu,et al.  Substrate‐Induced Graphene Chemistry for 2D Superlattices with Tunable Periodicities , 2016, Advanced materials.

[7]  M. Arnold,et al.  Electronic and Mechanical Properties of Graphene-Germanium Interfaces Grown by Chemical Vapor Deposition. , 2015, Nano letters.

[8]  H. Ago,et al.  Growth Dynamics of Single-Layer Graphene on Epitaxial Cu Surfaces , 2015 .

[9]  H. Johnson,et al.  Strain Relaxation in CVD Graphene: Wrinkling with Shear Lag. , 2015, Nano letters.

[10]  Zhiyong Zhang,et al.  Governing Rule for Dynamic Formation of Grain Boundaries in Grown Graphene. , 2015, ACS nano.

[11]  Feng Ding,et al.  Seamless Stitching of Graphene Domains on Polished Copper (111) Foil , 2015, Advanced materials.

[12]  Edward B. Lochocki,et al.  Polycrystalline graphene with single crystalline electronic structure. , 2014, Nano letters.

[13]  J. Krieg,et al.  Chemical vapor deposition of graphene on a "peeled-off" epitaxial Cu(111) foil: a simple approach to improved properties. , 2014, ACS nano.

[14]  L. Kavan,et al.  Interaction between graphene and copper substrate: The role of lattice orientation , 2014, 1401.8089.

[15]  Feng Liu,et al.  First-principles calculations on the effect of doping and biaxial tensile strain on electron-phonon coupling in graphene. , 2013, Physical review letters.

[16]  S. Okada,et al.  Enhanced chemical reactivity of graphene induced by mechanical strain. , 2013, ACS nano.

[17]  H. Mizuseki,et al.  Modification of graphene as active hydrogen storage medium by strain engineering , 2012 .

[18]  R. Piner,et al.  Selective surface functionalization at regions of high local curvature in graphene. , 2012, Chemical communications.

[19]  J. Xin,et al.  How the Orientation of Graphene Is Determined during Chemical Vapor Deposition Growth , 2012 .

[20]  Y. Kawazoe,et al.  Controlled catalytic properties of platinum clusters on strained graphene , 2012 .

[21]  J. Tersoff,et al.  Structure and electronic transport in graphene wrinkles. , 2012, Nano letters.

[22]  P. Kim,et al.  Large physisorption strain in chemical vapor deposition of graphene on copper substrates. , 2012, Nano letters.

[23]  M. Batzill.  The surface science of graphene: Metal interfaces, CVD synthesis, nanoribbons, chemical modifications, and defects , 2012 .

[24]  K. Novoselov,et al.  Raman spectroscopy of graphene and bilayer under biaxial strain: bubbles and balloons. , 2012, Nano letters.

[25]  S. Ryu,et al.  Optical separation of mechanical strain from charge doping in graphene , 2012, Nature Communications.

[26]  Q. Fu,et al.  Repeated growth and bubbling transfer of graphene with millimetre-size single-crystal grains using platinum , 2012, Nature Communications.

[27]  J. Maassen,et al.  Raman spectroscopy of the internal strain of a graphene layer grown on copper tuned by chemical vapor deposition , 2011 .

[28]  Wei Zhao,et al.  Graphene on Ni(111): Coexistence of Different Surface Structures , 2011 .

[29]  J. Hone,et al.  Probing strain-induced electronic structure change in graphene by Raman spectroscopy. , 2010, Nano letters.

[30]  Y. Mei,et al.  Stretchable graphene: a close look at fundamental parameters through biaxial straining. , 2010, Nano letters.

[31]  J. Maultzsch,et al.  Splitting of the Raman 2 D band of graphene subjected to strain , 2010, 1008.1488.

[32]  K. Novoselov,et al.  Compression behavior of single-layer graphenes. , 2010, ACS nano.

[33]  F. Guinea,et al.  Energy gaps and a zero-field quantum Hall effect in graphene by strain engineering , 2009, 0909.1787.

[34]  A. Varykhalov,et al.  Graphene grown on Co(0001) films and islands: Electronic structure and its precise magnetization dependence , 2009 .

[35]  G. Flynn,et al.  Structure and electronic properties of graphene nanoislands on Co(0001). , 2009, Nano letters.

[36]  T. Michely,et al.  In situ observation of stress relaxation in epitaxial graphene , 2009, 0906.0896.

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

[38]  N. Marzari,et al.  Uniaxial Strain in Graphene by Raman Spectroscopy: G peak splitting, Gruneisen Parameters and Sample Orientation , 2008, 0812.1538.

[39]  J. Vergés,et al.  First-principles calculation of the effect of stress on the chemical activity of graphene , 2008, 0907.3806.

[40]  C. Oshima,et al.  Atomic structure of monolayer graphite formed on Ni(111) , 1996 .