Rapid identification of stacking orientation in isotopically labeled chemical-vapor grown bilayer graphene by Raman spectroscopy.

The growth of large-area bilayer graphene has been of technological importance for graphene electronics. The successful application of graphene bilayers critically relies on the precise control of the stacking orientation, which determines both electronic and vibrational properties of the bilayer system. Toward this goal, an effective characterization method is critically needed to allow researchers to easily distinguish the bilayer stacking orientation (i.e., AB stacked or turbostratic). In this work, we developed such a method to provide facile identification of the stacking orientation by isotope labeling. Raman spectroscopy of these isotopically labeled bilayer samples shows a clear signature associated with AB stacking between layers, enabling rapid differentiation between turbostratic and AB-stacked bilayer regions. Using this method, we were able to characterize the stacking orientation in bilayer graphene grown through Low Pressure Chemical Vapor Deposition (LPCVD) with enclosed Cu foils, achieving almost 70% AB-stacked bilayer graphene. Furthermore, by combining surface sensitive fluorination with such hybrid (12)C/(13)C bilayer samples, we are able to identify that the second layer grows underneath the first-grown layer, which is similar to a recently reported observation.

[1]  A. Dolocan,et al.  Growth of adlayer graphene on Cu studied by carbon isotope labeling. , 2013, Nano letters.

[2]  D. L. Mafra,et al.  Unraveling the interlayer-related phonon self-energy renormalization in bilayer graphene , 2012, Scientific Reports.

[3]  R. Saito,et al.  Observation of layer-breathing mode vibrations in few-layer graphene through combination Raman scattering. , 2012, Nano letters.

[4]  R. Piner,et al.  Growth mechanism and controlled synthesis of AB-stacked bilayer graphene on Cu-Ni alloy foils. , 2012, ACS nano.

[5]  X. Duan,et al.  High-yield chemical vapor deposition growth of high-quality large-area AB-stacked bilayer graphene. , 2012, ACS nano.

[6]  L. Kavan,et al.  The control of graphene double-layer formation in copper-catalyzed chemical vapor deposition , 2012, 1208.5608.

[7]  M. Treviño,et al.  Noradrenergic ‘Tone’ Determines Dichotomous Control of Cortical Spike-Timing-Dependent Plasticity , 2012, Scientific Reports.

[8]  M. Ge,et al.  Vapor trapping growth of single-crystalline graphene flowers: synthesis, morphology, and electronic properties. , 2012, Nano letters.

[9]  S. Nie,et al.  Growth from below: bilayer graphene on copper by chemical vapor deposition , 2012, 1202.1031.

[10]  S. Louie,et al.  Raman spectroscopy study of rotated double-layer graphene: misorientation-angle dependence of electronic structure. , 2012, Physical review letters.

[11]  Ting Yu,et al.  Raman characterization of ABA- and ABC-stacked trilayer graphene. , 2011, ACS nano.

[12]  P. Ajayan,et al.  Growth of bilayer graphene on insulating substrates. , 2011, ACS nano.

[13]  Jin Sung Park,et al.  Raman spectra of out-of-plane phonons in bilayer graphene , 2011 .

[14]  L. Kavan,et al.  Raman spectroscopy and in situ Raman spectroelectrochemistry of bilayer ¹²C/¹³C graphene. , 2011, Nano letters.

[15]  K. Loh,et al.  Interface Engineering of Layer‐by‐Layer Stacked Graphene Anodes for High‐Performance Organic Solar Cells , 2011, Advanced materials.

[16]  R. Saito,et al.  Observation of out-of-plane vibrations in few-layer graphene using combination and overtone Raman modes , 2011, 1204.1702.

[17]  M. Dresselhaus,et al.  Second-order overtone and combination Raman modes of graphene layers in the range of 1690-2150 cm(-1). , 2011, ACS nano.

[18]  A. Bostwick,et al.  Growth from below: graphene bilayers on Ir(111). , 2011, ACS nano.

[19]  Hui Li,et al.  Formation of bilayer bernal graphene: layer-by-layer epitaxy via chemical vapor deposition. , 2011, Nano letters.

[20]  Luigi Colombo,et al.  Large-area graphene single crystals grown by low-pressure chemical vapor deposition of methane on copper. , 2011, Journal of the American Chemical Society.

[21]  Z. Zhong,et al.  Wafer scale homogeneous bilayer graphene films by chemical vapor deposition. , 2010, Nano letters.

[22]  Kwang S. Kim,et al.  Roll-to-roll production of 30-inch graphene films for transparent electrodes. , 2010, Nature nanotechnology.

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

[24]  Yi Cui,et al.  Dynamic observation of layer-by-layer growth and removal of graphene on Ru(0001). , 2010, Physical chemistry chemical physics : PCCP.

[25]  F. Xia,et al.  Graphene field-effect transistors with high on/off current ratio and large transport band gap at room temperature. , 2010, Nano letters.

[26]  Xue-wei Cao,et al.  Vibrational properties of graphene and graphene layers , 2009 .

[27]  H. Htoon,et al.  Observation of the Kohn anomaly near the K point of bilayer graphene , 2009, 0907.3322.

[28]  Luigi Colombo,et al.  Evolution of graphene growth on Ni and Cu by carbon isotope labeling. , 2009, Nano letters.

[29]  A. Reina,et al.  Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition. , 2009, Nano letters.

[30]  S. Louie,et al.  A tunable phonon-exciton Fano system in bilayer graphene. , 2009, Nature nanotechnology.

[31]  T. Tang,et al.  Direct observation of a widely tunable bandgap in bilayer graphene , 2009, Nature.

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

[33]  D. L. Mafra,et al.  Group theory analysis of electrons and phonons in N-layer graphene systems , 2008, 0812.1293.

[34]  J. Flege,et al.  Epitaxial graphene on ruthenium. , 2008, Nature materials.

[35]  M. Chou,et al.  Phonon dispersions and vibrational properties of monolayer, bilayer, and trilayer graphene: Density-functional perturbation theory , 2008, 0901.3093.

[36]  S. Akita,et al.  Visualization of Horizontally-Aligned Single-Walled Carbon Nanotube Growth with 13C/12C Isotopes , 2008 .

[37]  J. Nilsson,et al.  Probing the electronic structure of bilayer graphene by Raman scattering , 2007, 0708.1345.

[38]  L. Vandersypen,et al.  Gate-induced insulating state in bilayer graphene devices. , 2007, Nature materials.

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

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

[41]  Jannik C. Meyer,et al.  The structure of suspended graphene sheets , 2007, Nature.

[42]  T. Ohta,et al.  Controlling the Electronic Structure of Bilayer Graphene , 2006, Science.

[43]  Kenji Watanabe,et al.  Carbon Nanofilm with a New Structure and Property , 2003 .