Water-gated charge doping of graphene induced by mica substrates.

We report on the existence of water-gated charge doping of graphene deposited on atomically flat mica substrates. Molecular films of water in units of ~0.4 nm thick bilayers were found to be present in regions of the interface of graphene/mica heterostacks prepared by micromechanical exfoliation of kish graphite. The spectral variation of the G and 2D bands, as visualized by Raman mapping, shows that mica substrates induce strong p-type doping in graphene with hole densities of (9 ± 2) × 10(12) cm(-2). The ultrathin water films, however, effectively block interfacial charge transfer, rendering graphene significantly less hole-doped. Scanning Kelvin probe microscopy independently confirmed a water-gated modulation of the Fermi level by 0.35 eV, which is in agreement with the optically determined hole density. The manipulation of the electronic properties of graphene demonstrated in this study should serve as a useful tool in realizing future graphene applications.

[1]  Wi Hyoung Lee,et al.  Control of Graphene Field‐Effect Transistors by Interfacial Hydrophobic Self‐Assembled Monolayers , 2011, Advanced materials.

[2]  Pablo Jarillo-Herrero,et al.  Scanning tunnelling microscopy and spectroscopy of ultra-flat graphene on hexagonal boron nitride. , 2011, Nature materials.

[3]  Pablo Jarillo-Herrero,et al.  STM Spectroscopy of ultra-flat graphene on hexagonal boron nitride , 2011, 1102.2642.

[4]  J. Heath,et al.  Atomic force microscopy characterization of room-temperature adlayers of small organic molecules through graphene templating. , 2011, Journal of the American Chemical Society.

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

[6]  Richard Martel,et al.  Probing charge transfer at surfaces using graphene transistors. , 2011, Nano letters.

[7]  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.

[8]  G. Flynn,et al.  Atmospheric oxygen binding and hole doping in deformed graphene on a SiO₂ substrate. , 2010, Nano letters.

[9]  M. Katsnelson,et al.  Graphene adhesion on mica: Role of surface morphology , 2010, 1009.2669.

[10]  J. Heath,et al.  Graphene Visualizes the First Water Adlayers on Mica at Ambient Conditions , 2010, Science.

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

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

[13]  K. Shepard,et al.  Boron nitride substrates for high-quality graphene electronics. , 2010, Nature nanotechnology.

[14]  J. Coleman,et al.  Are there fundamental limitations on the sheet resistance and transmittance of thin graphene films? , 2010, ACS nano.

[15]  H. Klauk,et al.  Graphene on a hydrophobic substrate: doping reduction and hysteresis suppression under ambient conditions. , 2009, Nano letters.

[16]  M. Hossain,et al.  Chemistry at the graphene-SiO2 interface , 2009 .

[17]  Kwang S. Kim,et al.  Tuning the graphene work function by electric field effect. , 2009, Nano letters.

[18]  Michael Grätzel,et al.  Recent advances in sensitized mesoscopic solar cells. , 2009, Accounts of chemical research.

[19]  Lain-Jong Li,et al.  Doping single-layer graphene with aromatic molecules. , 2009, Small.

[20]  H. Dai,et al.  N-Doping of Graphene Through Electrothermal Reactions with Ammonia , 2009, Science.

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

[22]  Klaus von Klitzing,et al.  Four-terminal magneto-transport in graphene p-n junctions created by spatially selective doping. , 2009, Nano letters.

[23]  Peng Chen,et al.  Effective doping of single-layer graphene from underlying SiO2 substrates , 2009 .

[24]  Yoshio Watanabe,et al.  Dependence of electronic properties of epitaxial few-layer graphene on the number of layers investigated by photoelectron emission microscopy , 2009 .

[25]  T. Heinz,et al.  Probing the intrinsic properties of exfoliated graphene: Raman spectroscopy of free-standing monolayers. , 2009, Nano letters.

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

[27]  Klaus Kern,et al.  Atomic hole doping of graphene. , 2008, Nano letters.

[28]  G. Flynn,et al.  Graphene oxidation: thickness-dependent etching and strong chemical doping. , 2008, Nano letters.

[29]  H. R. Krishnamurthy,et al.  Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor. , 2008, Nature nanotechnology.

[30]  J. Brink,et al.  Doping graphene with metal contacts. , 2008, Physical review letters.

[31]  Alfred B. Anderson,et al.  Charge Transfer Equilibria Between Diamond and an Aqueous Oxygen Electrochemical Redox Couple , 2007, Science.

[32]  S. Xiao,et al.  Intrinsic and extrinsic performance limits of graphene devices on SiO2. , 2007, Nature nanotechnology.

[33]  K. Novoselov,et al.  Raman Fingerprint of Charged Impurities in Graphene , 2007, 0709.2566.

[34]  Wei Chen,et al.  Surface transfer p-type doping of epitaxial graphene. , 2007, Journal of the American Chemical Society.

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

[36]  Taisuke Ohta,et al.  Symmetry breaking in few layer graphene films , 2007, 0705.3705.

[37]  E. Williams,et al.  Atomic structure of graphene on SiO2. , 2007, Nano letters.

[38]  G. Flynn,et al.  High-resolution scanning tunneling microscopy imaging of mesoscopic graphene sheets on an insulating surface , 2007, Proceedings of the National Academy of Sciences.

[39]  M I Katsnelson,et al.  Intrinsic ripples in graphene. , 2007, Nature materials.

[40]  D. Basko,et al.  Theory of resonant multiphonon Raman scattering in graphene monolayers , 2007, 0804.3304.

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

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

[43]  K. Novoselov,et al.  Detection of individual gas molecules adsorbed on graphene. , 2006, Nature materials.

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

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

[46]  M. A. De la Rosa,et al.  Electron transfer between membrane complexes and soluble proteins in photosynthesis. , 2003, Accounts of chemical research.

[47]  M. Ratner,et al.  Electron Transport in Molecular Wire Junctions , 2003, Science.

[48]  M. Salmeron,et al.  Formation of dipole-oriented water films on mica substrates at ambient conditions , 2000 .

[49]  Ernst Meyer,et al.  Separation of interactions by noncontact force microscopy , 2000 .

[50]  K. Seki,et al.  ENERGY LEVEL ALIGNMENT AND INTERFACIAL ELECTRONIC STRUCTURES AT ORGANIC/METAL AND ORGANIC/ORGANIC INTERFACES , 1999 .

[51]  P. Campbell,et al.  Atomic force microscopy evidence for K+ domains on freshly cleaved mica , 1998 .

[52]  J. Yates,et al.  Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results , 1995 .

[53]  S. Nishimura,et al.  Molecular-Scale Structure of the Cation Modified Muscovite Mica Basal-Plane , 1994 .

[54]  D. Abraham,et al.  High resolution atomic force microscopy potentiometry , 1991 .

[55]  Takahashi,et al.  Angle-resolved ultraviolet photoelectron spectroscopy of the unoccupied band structure of graphite. , 1985, Physical review. B, Condensed matter.

[56]  C. K. Chiang,et al.  Electrical Conductivity in Doped Polyacetylene. , 1977 .

[57]  R. Giese.  Surface energy calculations for muscovite , 1974, Nature.

[58]  C. C. Chang,et al.  Electric dipoles on clean mica surfaces , 1969 .

[59]  G. V. Chester,et al.  Solid-State Physics , 1962, Nature.

[60]  Taylor Francis Online.  Advances in physics , 1952 .