skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

Abstract

In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene graphene and graphene substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.

Authors:
 [1];  [2];  [3];  [4];  [1];  [5];  [2];  [1];  [1]
  1. Max Planck Society, Berlin (Germany). Fritz Haber Institute
  2. Hong Kong Polytechnic Univ., Hong Kong (China). Inst. of Textiles and Clothing
  3. Suzhou Inst. of Nano-Tech and NanoBionics (China). 3Vacuum Interconnected Nanotech Workstation
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  5. Chinese Academy of Sciences (CAS), Beijing (China)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1337042
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; graphene; chemical vapor deposition; in situ; interlayer coupling

Citation Formats

Wang, Zhu-Jun, Dong, Jichen, Cui, Yi, Eres, Gyula, Timpe, Olaf, Fu, Qiang, Ding, Feng, Willinger, Marc-Georg, and Schloegl, R. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging. United States: N. p., 2016. Web. doi:10.1038/ncomms13256.
Wang, Zhu-Jun, Dong, Jichen, Cui, Yi, Eres, Gyula, Timpe, Olaf, Fu, Qiang, Ding, Feng, Willinger, Marc-Georg, & Schloegl, R. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging. United States. doi:10.1038/ncomms13256.
Wang, Zhu-Jun, Dong, Jichen, Cui, Yi, Eres, Gyula, Timpe, Olaf, Fu, Qiang, Ding, Feng, Willinger, Marc-Georg, and Schloegl, R. Wed . "Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging". United States. doi:10.1038/ncomms13256. https://www.osti.gov/servlets/purl/1337042.
@article{osti_1337042,
title = {Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging},
author = {Wang, Zhu-Jun and Dong, Jichen and Cui, Yi and Eres, Gyula and Timpe, Olaf and Fu, Qiang and Ding, Feng and Willinger, Marc-Georg and Schloegl, R.},
abstractNote = {In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene graphene and graphene substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.},
doi = {10.1038/ncomms13256},
journal = {Nature Communications},
number = ,
volume = 7,
place = {United States},
year = {2016},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Graphene nano-ribbon electronics
journal, December 2007

  • Chen, Zhihong; Lin, Yu-Ming; Rooks, Michael J.
  • Physica E: Low-dimensional Systems and Nanostructures, Vol. 40, Issue 2, p. 228-232
  • DOI: 10.1016/j.physe.2007.06.020

Energy Band-Gap Engineering of Graphene Nanoribbons
journal, May 2007


Half-Metallicity in Edge-Modified Zigzag Graphene Nanoribbons
journal, April 2008

  • Kan, Er-jun; Li, Zhenyu; Yang, Jinlong
  • Journal of the American Chemical Society, Vol. 130, Issue 13
  • DOI: 10.1021/ja710407t

Chemical doping-induced gap opening and spin polarization in graphene
journal, February 2008


Uniaxial Strain on Graphene: Raman Spectroscopy Study and Band-Gap Opening
journal, October 2008

  • Ni, Zhen Hua; Yu, Ting; Lu, Yun Hao
  • ACS Nano, Vol. 2, Issue 11
  • DOI: 10.1021/nn800459e

Substrate-induced bandgap opening in epitaxial graphene
journal, September 2007

  • Zhou, S. Y.; Gweon, G. -H.; Fedorov, A. V.
  • Nature Materials, Vol. 6, Issue 10
  • DOI: 10.1038/nmat2003

Direct observation of a widely tunable bandgap in bilayer graphene
journal, June 2009

  • Zhang, Yuanbo; Tang, Tsung-Ta; Girit, Caglar
  • Nature, Vol. 459, Issue 7248
  • DOI: 10.1038/nature08105

Biased Bilayer Graphene: Semiconductor with a Gap Tunable by the Electric Field Effect
journal, November 2007


Controlling the Electronic Structure of Bilayer Graphene
journal, August 2006


Observation of an Electric-Field-Induced Band Gap in Bilayer Graphene by Infrared Spectroscopy
journal, June 2009


Energy of Cohesion, Compressibility, and the Potential Energy Functions of the Graphite System
journal, October 1956

  • Girifalco, L. A.; Lad, R. A.
  • The Journal of Chemical Physics, Vol. 25, Issue 4
  • DOI: 10.1063/1.1743030

Microscopic determination of the interlayer binding energy in graphite
journal, April 1998


Semiempirical approach to the energetics of interlayer binding in graphite
journal, November 2004


Nature and Strength of Interlayer Binding in Graphite
journal, November 2009


Direct Growth of Bilayer Graphene on SiO2 Substrates by Carbon Diffusion through Nickel
journal, September 2011

  • Peng, Zhiwei; Yan, Zheng; Sun, Zhengzong
  • ACS Nano, Vol. 5, Issue 10, p. 8241-8247
  • DOI: 10.1021/nn202923y

Formation of Bilayer Bernal Graphene: Layer-by-Layer Epitaxy via Chemical Vapor Deposition
journal, March 2011

  • Yan, Kai; Peng, Hailin; Zhou, Yu
  • Nano Letters, Vol. 11, Issue 3
  • DOI: 10.1021/nl104000b

Synthesis and Characterization of Large-Area Graphene and Graphite Films on Commercial Cu–Ni Alloy Foils
journal, September 2011

  • Chen, Shanshan; Cai, Weiwei; Piner, Richard D.
  • Nano Letters, Vol. 11, Issue 9
  • DOI: 10.1021/nl201699j

Graphene on Pt(111): Growth and substrate interaction
journal, December 2009


Epitaxial graphene on ruthenium
journal, April 2008

  • Sutter, Peter W.; Flege, Jan-Ingo; Sutter, Eli A.
  • Nature Materials, Vol. 7, Issue 5, p. 406-411
  • DOI: 10.1038/nmat2166

Growth from Below: Graphene Bilayers on Ir(111)
journal, February 2011

  • Nie, Shu; Walter, Andrew L.; Bartelt, Norman C.
  • ACS Nano, Vol. 5, Issue 3
  • DOI: 10.1021/nn103582g

Twisting Bilayer Graphene Superlattices
journal, March 2013

  • Lu, Chun-Chieh; Lin, Yung-Chang; Liu, Zheng
  • ACS Nano, Vol. 7, Issue 3
  • DOI: 10.1021/nn3059828

Growth Mechanism and Controlled Synthesis of AB-Stacked Bilayer Graphene on Cu–Ni Alloy Foils
journal, August 2012

  • Wu, Yaping; Chou, Harry; Ji, Hengxing
  • ACS Nano, Vol. 6, Issue 9
  • DOI: 10.1021/nn301689m

Role of Hydrogen in Graphene Chemical Vapor Deposition Growth on a Copper Surface
journal, February 2014

  • Zhang, Xiuyun; Wang, Lu; Xin, John
  • Journal of the American Chemical Society, Vol. 136, Issue 8
  • DOI: 10.1021/ja405499x

Growth of Adlayer Graphene on Cu Studied by Carbon Isotope Labeling
journal, January 2013

  • Li, Qiongyu; Chou, Harry; Zhong, Jin-Hui
  • Nano Letters, Vol. 13, Issue 2
  • DOI: 10.1021/nl303879k

Growth mechanism of graphene on platinum: Surface catalysis and carbon segregation
journal, April 2014

  • Sun, Jie; Nam, Youngwoo; Lindvall, Niclas
  • Applied Physics Letters, Vol. 104, Issue 15
  • DOI: 10.1063/1.4871978

Direct Observation of Graphene Growth and Associated Copper Substrate Dynamics by in Situ Scanning Electron Microscopy
journal, January 2015

  • Wang, Zhu-Jun; Weinberg, Gisela; Zhang, Qiang
  • ACS Nano, Vol. 9, Issue 2
  • DOI: 10.1021/nn5059826

Interaction of hydrogen with Pt(111): The role of atomic steps
journal, November 1976


Thickness contrast of few-layered graphene in SEM: Thickness contrast of few-layered graphene in SEM
journal, April 2012

  • Park, Min-Ho; Kim, Tae-Hoon; Yang, Cheol-Woong
  • Surface and Interface Analysis, Vol. 44, Issue 11-12
  • DOI: 10.1002/sia.4995

Determination of the Number of Graphene Layers: Discrete Distribution of the Secondary Electron Intensity Stemming from Individual Graphene Layers
journal, August 2010

  • Hiura, Hidefumi; Miyazaki, Hisao; Tsukagoshi, Kazuhito
  • Applied Physics Express, Vol. 3, Issue 9
  • DOI: 10.1143/APEX.3.095101

Growth and Raman Spectra of Single-Crystal Trilayer Graphene with Different Stacking Orientations
journal, October 2014

  • Zhao, Haiming; Lin, Yung-Chang; Yeh, Chao-Hui
  • ACS Nano, Vol. 8, Issue 10
  • DOI: 10.1021/nn5044959

Decay of isolated surface features driven by the Gibbs-Thomson effect in an analytic model and a simulation
journal, January 1997


Interlayer cohesive energy of graphite from thermal desorption of polyaromatic hydrocarbons
journal, April 2004


The influence of intercalated oxygen on the properties of graphene on polycrystalline Cu under various environmental conditions
journal, January 2014

  • Blume, Raoul; Kidambi, Piran R.; Bayer, Bernhard C.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 47
  • DOI: 10.1039/C4CP04025B

Graphene on Ru(0001): A 25 × 25 Supercell
journal, September 2008


Single Terrace Growth of Graphene on a Metal Surface
journal, May 2011

  • Günther, S.; Dänhardt, S.; Wang, B.
  • Nano Letters, Vol. 11, Issue 5
  • DOI: 10.1021/nl103947x

Edge state in graphene ribbons: Nanometer size effect and edge shape dependence
journal, December 1996


Edge-Catalyst Wetting and Orientation Control of Graphene Growth by Chemical Vapor Deposition Growth
journal, August 2014

  • Yuan, Qinghong; Yakobson, Boris I.; Ding, Feng
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 18
  • DOI: 10.1021/jz5015899

Sublattice Localized Electronic States in Atomically Resolved Graphene-Pt(111) Edge-Boundaries
journal, March 2014

  • Merino, Pablo; Rodrigo, Lucía; Pinardi, Anna L.
  • ACS Nano, Vol. 8, Issue 4
  • DOI: 10.1021/nn500105a

Equilibrium at the edge and atomistic mechanisms of graphene growth
journal, September 2012

  • Artyukhov, V. I.; Liu, Y.; Yakobson, B. I.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 38
  • DOI: 10.1073/pnas.1207519109

Dislocation theory of chirality-controlled nanotube growth
journal, February 2009

  • Ding, Feng; Harutyunyan, Avetik R.; Yakobson, Boris I.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 8
  • DOI: 10.1073/pnas.0811946106

Edge Structural Stability and Kinetics of Graphene Chemical Vapor Deposition Growth
journal, March 2012

  • Shu, Haibo; Chen, Xiaoshuang; Tao, Xiaoming
  • ACS Nano, Vol. 6, Issue 4
  • DOI: 10.1021/nn300726r

The edge termination controlled kinetics in graphene chemical vapor deposition growth
journal, January 2014

  • Shu, Haibo; Chen, Xiaoshuang; Ding, Feng
  • Chem. Sci., Vol. 5, Issue 12
  • DOI: 10.1039/C4SC02223H

Edge-controlled growth and kinetics of single-crystal graphene domains by chemical vapor deposition
journal, December 2013

  • Ma, T.; Ren, W.; Zhang, X.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 51
  • DOI: 10.1073/pnas.1312802110

Breaking of Symmetry in Graphene Growth on Metal Substrates
journal, March 2015


Equilibrium and growth shapes of crystals: how do they differ and why should we care?
journal, April 2005


The solubility of carbon in palladium and platinum
journal, September 1968


Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

Ab initio molecular dynamics for open-shell transition metals
journal, November 1993


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


    Works referencing / citing this record:

    Syntheses of Large-Sized Single Crystal Graphene: a Review of Recent Developments
    journal, February 2019


    Syntheses of Large-Sized Single Crystal Graphene: a Review of Recent Developments
    journal, February 2019