Nanoscale chemical imaging of single-layer graphene.

Electronic properties in different graphene materials are influenced by the presence of defects and their relative position with respect to the edges. Their localization is crucial for the reliable development of graphene-based electronic devices. Graphene samples produced by standard CVD on copper and by the scotch-tape method on gold were investigated using tip-enhanced Raman spectroscopy (TERS). A resolution of <12 nm is reached using TERS imaging with full spectral information in every pixel. TERS is shown to be capable of identifying defects, contaminants, and pristine graphene due to their different spectroscopic signatures, and of performing chemical imaging. TERS allows the detection of smaller defects than visible by confocal Raman microscopy and a far more precise localization. Consecutive scans on the same sample area show the reproducibility of the measurements, as well as the ability to zoom in from an overview scan onto specific sample features. TERS images can be acquired in as few as 5 min with 32 × 32 pixels. Compared to confocal Raman microscopy, a high sensitivity for defects, edges, hydrogen-terminated areas or contaminated areas (in general for deviations from the two-dimensional structure of pristine graphene) is obtained due to selective enhancement as a consequence of the orientation in the electromagnetic field.

[1]  Valentinas Snitka,et al.  Novel gold cantilever for nano-Raman spectroscopy of graphene , 2011 .

[2]  Jifa Tian,et al.  Atomic-scale investigation of graphene grown on Cu foil and the effects of thermal annealing. , 2011, ACS nano.

[3]  Kai Yan,et al.  Defect-like structures of graphene on copper foils for strain relief investigated by high-resolution scanning tunneling microscopy. , 2011, ACS nano.

[4]  Lianfeng Sun,et al.  Raman scattering of monolayer graphene: the temperature and oxygen doping effects , 2011 .

[5]  Zhongfan Liu,et al.  Scanning tunneling microscope observations of non-AB stacking of graphene on Ni films , 2011 .

[6]  K. Novoselov,et al.  Strain mapping in a graphene monolayer nanocomposite. , 2011, ACS nano.

[7]  P. Ajayan,et al.  Ultrathin planar graphene supercapacitors. , 2011, Nano letters.

[8]  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.

[9]  Mark W. B. Wilson,et al.  Atomic resolution imaging of the edges of catalytically etched suspended few-layer graphene. , 2011, ACS nano.

[10]  Rui Wang,et al.  Control of carrier type and density in exfoliated graphene by interface engineering. , 2011, ACS nano.

[11]  A. Krasheninnikov,et al.  Structural defects in graphene. , 2011, ACS nano.

[12]  X. Jia,et al.  Graphene edges: a review of their fabrication and characterization. , 2011, Nanoscale.

[13]  M. Dresselhaus,et al.  Defect characterization in graphene and carbon nanotubes using Raman spectroscopy , 2010, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.

[14]  C G Smith,et al.  Nanoanalysis of graphene layers using scanning probe techniques , 2010, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.

[15]  S. Kazarian,et al.  Finding a needle in a chemical haystack: tip-enhanced Raman scattering for studying carbon nanotubes mixtures , 2010, Nanotechnology.

[16]  R Zenobi,et al.  Nanoscale chemical imaging using top-illumination tip-enhanced Raman spectroscopy. , 2010, Nano letters.

[17]  Achim Hartschuh,et al.  Tip-enhanced Raman spectroscopic imaging of localized defects in carbon nanotubes , 2010 .

[18]  T. Korn,et al.  Scanning Raman spectroscopy of graphene antidot lattices: Evidence for systematic p-type doping , 2010, 1006.2067.

[19]  T. Yu,et al.  Raman study on the g mode of graphene for determination of edge orientation. , 2010, ACS nano.

[20]  Zhenhua Ni,et al.  Probing layer number and stacking order of few-layer graphene by Raman spectroscopy. , 2010, Small.

[21]  F. Xia,et al.  Ultrafast graphene photodetector. , 2009, Nature nanotechnology.

[22]  D. Goldhaber-Gordon,et al.  Disorder-induced gap behavior in graphene nanoribbons , 2009, 0909.3886.

[23]  F. Schwierz Graphene transistors. , 2010, Nature nanotechnology.

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

[25]  G. Zerbi,et al.  Raman scattering of molecular graphenes. , 2009, Physical chemistry chemical physics : PCCP.

[26]  R. Piner,et al.  Transfer of large-area graphene films for high-performance transparent conductive electrodes. , 2009, Nano letters.

[27]  Katrin F. Domke,et al.  Tip‐enhanced Raman spectroscopy of 6H‐SiC with graphene adlayers: selective suppression of E1 modes , 2009 .

[28]  M. Chaigneau,et al.  Tip enhanced Raman spectroscopy on azobenzene thiol self-assembled monolayers on Au(111) , 2009 .

[29]  Satoshi Kawata,et al.  Nano‐scale analysis of graphene layers by tip‐enhanced near‐field Raman spectroscopy , 2009 .

[30]  B. Park,et al.  Variations in the Raman Spectrum as a Function of the Number \ofGraphene Layers , 2009 .

[31]  B. Sumpter,et al.  The importance of defects for carbon nanoribbon based electronics , 2009 .

[32]  D. L. Mafra,et al.  Resonance Raman scattering in graphene: Probing phonons and electrons , 2009 .

[33]  Alexander A. Balandin,et al.  Raman nanometrology of graphene: Temperature and substrate effects , 2009 .

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

[35]  Hugen Yan,et al.  Phonon softening and crystallographic orientation of strained graphene studied by Raman spectroscopy , 2009, Proceedings of the National Academy of Sciences.

[36]  Jin Sung Park,et al.  G' band Raman spectra of single, double and triple layer graphene , 2009 .

[37]  P. Eklund,et al.  Probing graphene edges via Raman scattering. , 2009, ACS nano.

[38]  K. Jenkins,et al.  Operation of graphene transistors at gigahertz frequencies. , 2008, Nano letters.

[39]  N. Doltsinis,et al.  Advances in Solid State Physics , 2009 .

[40]  J. Parka,et al.  G 0 band Raman spectra of single , double and triple layer graphene , 2009 .

[41]  A. Jorio,et al.  Electron and phonon renormalization near charged defects in carbon nanotubes. , 2008, Nature materials.

[42]  Ying Ying Wang,et al.  Raman spectroscopy and imaging of graphene , 2008, 0810.2836.

[43]  Zhenhua Ni,et al.  Raman Mapping Investigation of Graphene on Transparent Flexible Substrate: The Strain Effect , 2008 .

[44]  Yihong Wu,et al.  Raman Studies of Monolayer Graphene: The Substrate Effect , 2008 .

[45]  Gunter Georg Gunter Hoffmann,et al.  Micro-Raman and Tip-Enhanced Raman Spectroscopy of Carbon Allotropes , 2008 .

[46]  G. Dresselhaus,et al.  Raman spectroscopy as a probe of graphene and carbon nanotubes , 2008, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.

[47]  E. Williams,et al.  Printed Graphene Circuits , 2007, 0809.1634.

[48]  B. Chakraborty,et al.  Raman spectroscopy of graphene on different substrates and influence of defects , 2007, 0710.4160.

[49]  Christian Hafner,et al.  Nanoscale roughness on metal surfaces can increase tip-enhanced Raman scattering by an order of magnitude. , 2007, Nano letters.

[50]  S. Foteinopoulou,et al.  Optical near-field excitations on plasmonic nanoparticle-based structures. , 2007, Optics express.

[51]  Andre K. Geim,et al.  Raman spectrum of graphene and graphene layers. , 2006, Physical review letters.

[52]  A. Demming,et al.  Plasmon resonances on metal tips: understanding tip-enhanced Raman scattering. , 2005, The Journal of chemical physics.

[53]  K. Novoselov,et al.  Two-dimensional atomic crystals. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[54]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.

[55]  G. Katagiri,et al.  Observation of the out-of-plane mode in the Raman scattering from the graphite edge plane , 1999 .

[56]  Martin Hegner,et al.  Ultralarge atomically flat template-stripped Au surfaces for scanning probe microscopy , 1993 .

[57]  Richard J. Colton,et al.  On the electrochemical etching of tips for scanning tunneling microscopy , 1990 .

[58]  S. C. O'brien,et al.  C60: Buckminsterfullerene , 1985, Nature.