Electrically continuous graphene from single crystal copper verified by terahertz conductance spectroscopy and micro four-point probe.

The electrical performance of graphene synthesized by chemical vapor deposition and transferred to insulating surfaces may be compromised by extended defects, including for instance grain boundaries, cracks, wrinkles, and tears. In this study, we experimentally investigate and compare the nano- and microscale electrical continuity of single layer graphene grown on centimeter-sized single crystal copper with that of previously studied graphene films, grown on commercially available copper foil, after transfer to SiO2 surfaces. The electrical continuity of the graphene films is analyzed using two noninvasive conductance characterization methods: ultrabroadband terahertz time-domain spectroscopy and micro four-point probe, which probe the electrical properties of the graphene film on different length scales, 100 nm and 10 μm, respectively. Ultrabroadband terahertz time-domain spectroscopy allows for measurement of the complex conductance response in the frequency range 1-15 terahertz, covering the entire intraband conductance spectrum, and reveals that the conductance response for the graphene grown on single crystalline copper intimately follows the Drude model for a barrier-free conductor. In contrast, the graphene grown on commercial copper foil shows a distinctly non-Drude conductance spectrum that is better described by the Drude-Smith model, which incorporates the effect of preferential carrier backscattering associated with extended, electronic barriers with a typical separation on the order of 100 nm. Micro four-point probe resistance values measured on graphene grown on single crystalline copper in two different voltage-current configurations show close agreement with the expected distributions for a continuous 2D conductor, in contrast with previous observations on graphene grown on commercial copper foil. The terahertz and micro four-point probe conductance values of the graphene grown on single crystalline copper shows a close to unity correlation, in contrast with those of the graphene grown on commercial copper foil, which we explain by the absence of extended defects on the microscale in CVD graphene grown on single crystalline copper. The presented results demonstrate that the graphene grown on single crystal copper is electrically continuous on the nanoscopic, microscopic, as well as intermediate length scales.

[1]  Xu Xie,et al.  Coherent control of THz wave generation in ambient air. , 2006, Physical review letters.

[2]  Carl W. Magnuson,et al.  Improved electrical conductivity of graphene films integrated with metal nanowires. , 2012, Nano letters.

[3]  David G. Cooke,et al.  Transient terahertz conductivity in photoexcited silicon nanocrystal films , 2006 .

[4]  P. Ajayan,et al.  Graphene: pushing the boundaries. , 2011, Nature materials.

[5]  A. Meldrum,et al.  Ultrafast percolative transport dynamics in silicon nanocrystal films , 2011 .

[6]  Yihong Wu,et al.  Graphene thickness determination using reflection and contrast spectroscopy. , 2007, Nano letters.

[7]  S. Pei,et al.  Control and characterization of individual grains and grain boundaries in graphene grown by chemical vapour deposition. , 2010, Nature materials.

[8]  R. Hochstrasser,et al.  Intense terahertz pulses by four-wave rectification in air. , 2000, Optics letters.

[9]  Kentaro Nomura,et al.  Quantum transport of massless Dirac fermions. , 2007, Physical review letters.

[10]  P. Bøggild,et al.  Static contact micro four-point probes with <11nm positioning repeatability , 2008 .

[11]  A. Ferreira,et al.  Effect of charged line defects on conductivity in graphene : Numerical Kubo and analytical Boltzmann approaches , 2013, 1304.3472.

[12]  P. Bøggild,et al.  Graphene conductance uniformity mapping. , 2012, Nano letters.

[13]  R Rymaszewski,et al.  Relationship between the correction factor of the four-point probe value and the selection of potential and current electrodes , 1969 .

[14]  P. Jepsen,et al.  Ultrabroadband terahertz conductivity of Si nanocrystal films , 2012 .

[15]  Robert M. Wallace,et al.  Uniform Wafer-Scale Chemical Vapor Deposition of Graphene on Evaporated Cu (111) Film with Quality Comparable to Exfoliated Monolayer , 2012 .

[16]  Masayoshi Tonouchi,et al.  Terahertz and infrared spectroscopy of gated large-area graphene. , 2012, Nano letters.

[17]  E. Rosseel,et al.  Comparative study of size dependent four-point probe sheet resistance measurement on laser annealed ultra-shallow junctions , 2008 .

[18]  M. R. Freeman,et al.  Terahertz conductivity of thin gold films at the metal-insulator percolation transition , 2007 .

[19]  D. W. Koon Nonlinearity of resistive impurity effects on van der Pauw measurements , 2006 .

[20]  P. Jepsen,et al.  Experimental three-dimensional beam profiling and modeling of a terahertz beam generated from a two-color air plasma , 2013 .

[21]  Kwang S. Kim,et al.  Large-scale pattern growth of graphene films for stretchable transparent electrodes , 2009, Nature.

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

[23]  Pinshane Y. Huang,et al.  Supplementary Materials for Tailoring Electrical Transport Across Grain Boundaries in Polycrystalline Graphene , 2012 .

[24]  Carl W. Magnuson,et al.  The Role of Surface Oxygen in the Growth of Large Single-Crystal Graphene on Copper , 2013, Science.

[25]  Kyle M. Diederichsen,et al.  Giant secondary grain growth in Cu films on sapphirea) , 2013, 1305.5218.

[26]  Daniel R. Grischkowsky,et al.  Characterization of optically dense, doped semiconductors by reflection THz time domain spectroscopy , 1998 .

[27]  N. V. Smith,et al.  Classical generalization of the Drude formula for the optical conductivity , 2001 .

[28]  K. Shepard,et al.  Graphene field-effect transistors with gigahertz-frequency power gain on flexible substrates. , 2013, Nano letters.

[29]  K. Loh,et al.  Electrochemical delamination of CVD-grown graphene film: toward the recyclable use of copper catalyst. , 2011, ACS nano.

[30]  S. Sarma,et al.  Electronic transport in two-dimensional graphene , 2010, 1003.4731.

[31]  Kai Yan,et al.  Toward clean and crackless transfer of graphene. , 2011, ACS nano.

[32]  Michael Seadle Measurement , 2007, The Measurement of Information Integrity.

[33]  F. Stavale,et al.  Quantifying defects in graphene via Raman spectroscopy at different excitation energies. , 2011, Nano letters.

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

[35]  Markus Kress,et al.  Terahertz-pulse generation by photoionization of air with laser pulses composed of both fundamental and second-harmonic waves. , 2004, Optics letters.

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

[37]  D. Veksler,et al.  Measurement of the optical absorption spectra of epitaxial graphene from terahertz to visible , 2008, 0801.3302.

[38]  Carl W. Magnuson,et al.  Transfer of CVD-grown monolayer graphene onto arbitrary substrates. , 2011, ACS nano.

[39]  Masashi Yamaguchi,et al.  Coherent heterodyne time-domain spectrometry covering the entire “terahertz gap” , 2008 .

[40]  M. C. Martin,et al.  Broadband electromagnetic response and ultrafast dynamics of few-layer epitaxial graphene , 2009, 0903.0577.

[41]  A. M. van der Zande,et al.  Chemical vapor deposition-derived graphene with electrical performance of exfoliated graphene. , 2012, Nano letters.

[42]  R. Koch,et al.  Epitaxial Growth and Electronic Properties of Large Hexagonal Graphene Domains on Cu(111) Thin Film , 2013 .

[43]  Shi-Li Zhang,et al.  Finite-size scaling in stick percolation. , 2009, Physical review. E, Statistical, nonlinear, and soft matter physics.

[44]  Ole Hansen,et al.  Three-way flexible cantilever probes for static contact , 2011 .

[45]  T. Booth,et al.  Fast and direct measurements of the electrical properties of graphene using micro four-point probes , 2011, Nanotechnology.

[46]  Hugen Yan,et al.  Observation of a transient decrease in terahertz conductivity of single-layer graphene induced by ultrafast optical excitation. , 2013, Nano letters.

[47]  Kang L. Wang,et al.  Atomic-scale characterization of graphene grown on copper (100) single crystals. , 2011, Journal of the American Chemical Society.

[48]  Peter Uhd Jepsen,et al.  Ultrabroadband terahertz spectroscopy of chalcogenide glasses , 2012 .

[49]  S. Sarma,et al.  Carrier transport in two-dimensional graphene layers. , 2006, Physical review letters.

[50]  Xu Xie,et al.  Detection of broadband terahertz waves with a laser-induced plasma in gases. , 2006, Physical review letters.

[51]  Sune Thorsteinsson,et al.  Accurate microfour-point probe sheet resistance measurements on small samples. , 2009, The Review of scientific instruments.

[52]  J. Coutaz,et al.  Determination of the DC Electrical Conductivity of Multiwalled Carbon Nanotube Films and Graphene Layers from Noncontact Time-Domain Terahertz Measurements , 2014 .

[53]  H. Bechtel,et al.  Drude Conductivity of Dirac Fermions in Graphene , 2010, 1007.4623.

[54]  P. Bøggild,et al.  Revealing origin of quasi-one dimensional current transport in defect rich two dimensional materials , 2014 .

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

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

[57]  Matthew C. Beard,et al.  Carrier Localization and Cooling in Dye-Sensitized Nanocrystalline Titanium Dioxide , 2002 .

[58]  Josef Náhlík,et al.  Study of quantitative influence of sample defects on measurements of resistivity of thin films using van der Pauw method , 2011 .

[59]  V. Sundström,et al.  Far-infrared response of free charge carriers localized in semiconductor nanoparticles , 2009 .

[60]  C. J. Knickerbocker,et al.  What do you measure when you measure resistivity , 1992 .

[61]  K. L. Shepard,et al.  One-Dimensional Electrical Contact to a Two-Dimensional Material , 2013, Science.

[62]  A. Ferrari,et al.  Raman spectroscopy of graphene and graphite: Disorder, electron phonon coupling, doping and nonadiabatic effects , 2007 .

[63]  F. Krebs,et al.  Direct observation of sub-100 fs mobile charge generation in a polymer-fullerene film. , 2012, Physical review letters.