Chemical Modification of Epitaxial Graphene

Elena Bekyarova, Mikhail E Itkis, Palanisamy Ramesh, Robert C Haddon

University of California-Riverside
Claire Berger, Michael Sprinkle, Walt A de Heer
Georgia Institute of Technology
NO2

Advantages:
• Extremely mild conditions
O2 N N N , BF4
• Minimum perturbation to electronic structure of EG
0.1 M [Bu4N] PF6
(conversion of C sp2 to sp3)
ACN; RT, Ar, 20 h • Simple, Fast, Versatile

Fig. 1 Spontaneous grafting of aryl groups to epitaxial Fig. 2 Temperature dependence of sheet resistance of pristine
graphene (EG) and nitrophenyl functionalized graphene (NP-EG).

Sponsored by NSF-MRSEC through contract DMR-0820382

Bekyarova, E.; Itkis, M. E.; Ramesh, P.; Berger, C.; Sprinkle, M.; de Heer, W. A.; Haddon, R. C.,
Chemical Modification of Epitaxial Graphene: Spontaneous Grafting of Aryl Groups.
J. Am. Chem. Soc. 2009, 131, 1336-1337.
First Epitaxial Graphene Workshop

Workshop covered importance and 
future of epitaxial graphene.  Advances 
described by GT MRSEC investigators 
facilitated discussion of future research 
directions and promoted additional 
international collaborations.
Sponsored by NSF-MRSEC through contract DMR-0820382
 Georgia Institute of Technology NSF MRSEC Highlight:
Graphene-based Transparent Electrodes for Organic Electronics
Samuel Graham, School of Mechanical Engineering, Georgia Tech
Robert Haddon, School of Chemistry, University of California Riverside

Before Annealing Fig. 2 Optical image showing the

graphene oxide-carbon nanotube
composite prior to annealing
Fig. 3 Transparency data from the electrodes.

This research is developing a low cost, solution processible

After Annealing
Fig. 1 Images showing graphene-CNT
electrodes on quartz substrates.
transparent electrode for use in future flexible electronics.
Recent results have suggested that the films will have
properties which will surpass the currently used electrode in the
electronics industry and will be applicable to a wide range of
devices including solar cells and LEDs for next generation light
sources.

Sponsored by NSF-MRSEC through contract DMR-0820382

 Georgia Institute of Technology NSF MRSEC Highlight:
High quality graphene grown on silicon carbide
Ming Ruan, Yike Hu, Mike Sprinkle, Claire Berger, Walt A. de Heer

Researchers at Georgia are the pioneers of

graphene based electronics, that has the
potential for unprecedented capabilities.
They have developed methods to produce
the highest quality graphene material in the
world. The graphene layer extends over the
entire surface of the silicon carbide chip.
This is an critical breakthrough in graphene
based electronics.

Fig.1 Atomic force microscopy image of a graphene layer grown on

an electronics grade silicon carbide crystal. The graphene layer is
extremely flat and shows a few pleats (the white lines) that are few
nanometers high, much like the pleats on a bed sheet.

Sponsored by NSF-MRSEC through contract DMR-0820382

 Georgia Institute of Technology NSF MRSEC Highlight:

New Material Developed for Post Si-CMOS Electronics

Michael Sprinkle, Claire Berger, Walt A de Heer, Edward Conrad
School of Physics, Georgia Tech

Fig. 2 The expected

Dirac Cones for a single
graphene sheet.

A new form of graphene was discovered at the GT

Fig. 1 Multiple Dirac Cones Measured by Angle
Resolved Photoemission.
MRSEC for new electronic materials that makes an
all graphene electronics circuit possible. Figure 1
shows multiple Dirac Cones from a 10-layer
graphene film. These undoped Dirac Cone shows
that multilayer graphene grown on the carbon face
of SiC is “effectively” an electronic single graphene
sheet. This remarkable results means that
controlling graphene thickness to get large single
layer films is no longer a requirement in graphene
electronics and opens the way to a whole new way
of thinking about graphene electronics.

Sponsored by NSF-MRSEC through contract DMR-0820382

 Quantization of Zero-Mass Particles in Graphene
D. L. Miller*, K. D. Kubista*, M. Ruan, W. A. de Heer, and P. N. First
School of Physics, Georgia Institute of Technology
G. M. Rutter and J. A. Stroscio
NIST Center for Nanoscale Science and Technology
* These authors contributed equally to this work.

Tunneling spectroscopy of graphene in

Due to the wave nature of matter, the circular magnetic fields from 0-6 T. Background
"cyclotron" orbits of electrons in a magnetic field shows predicted Landau level energy
must join on to themselves after a full revolution; spectrum.
like a dog catching its tail.

D. L. Miller, Georgia Tech

Foreground: cartoon, Background: STM data.

The wave continuity (tail-

catching) condition requires
an integer number of
wavelengths around the orbit.
This leads to special orbit
K. D. Kubista, Georgia Tech

sizes and a discrete spectrum

of allowed orbit energies.
For massless particles in
graphene, these “Landau
levels” have energies that
vary as the square-root of the
magnetic field, except for a
special field-independent
state at zero energy.

NSF Support: DMR-0804908 and facilities of the Georgia Tech MRSEC (DMR-0820382).
 Quantization of Zero-Mass Particles in Graphene
D. L. Miller*, K. D. Kubista*, M. Ruan, W. A. de Heer, and P. N. First
School of Physics, Georgia Institute of Technology
G. M. Rutter and J. A. Stroscio
NIST Center for Nanoscale Science and Technology
* These authors contributed equally to this work.

Tunneling spectroscopy of graphene in

Due to the wave nature of matter, the circular magnetic fields from 0-6 T. Background
"cyclotron" orbits of electrons in a magnetic field shows predicted Landau level energy
must join on to themselves after a full revolution;
spectrum.
like a dog catching its tail.

D. L. Miller, Georgia Tech

Foreground: cartoon, Background: STM data.

The wave continuity (tail-

catching) condition requires
an integer number of
wavelengths around the orbit.
This leads to special orbit
K. D. Kubista, Georgia Tech

sizes and a discrete spectrum

of allowed orbit energies.
For massless particles in
graphene, these “Landau
levels” have energies that
vary as the square-root of the
magnetic field, except for a
special field-independent
state at zero energy.

1
NSF Support: DMR-0804908 and facilities of the Georgia Tech MRSEC (DMR-0820382).

Due to the wave nature of matter, the circular "cyclotron" orbits of electrons in a magnetic
field must join on to themselves after a full revolution; like a dog catching its tail. For
electrons in graphene, researchers at the Georgia Institute of Technology (D. L. Miller, K. D.
Kubista, M. Ruan, W. A. de Heer and P. N. First) and the NIST Center for Nanoscale
Science and Technology (G. M. Rutter and J. A. Stroscio) have resolved the discrete
spectrum of electron energies resulting from this wave-matching condition. Their low-
temperature (4.3 K) scanning tunneling microscopy (STM) and spectroscopy
measurements allow detailed comparison with the predicted energy structure of graphene,
a one-atom-thick honeycomb of carbon atoms. The spectra show two signatures unique to
graphene: A sqrt(B) dependence of the magnetic-quantization energy states (Landau
levels) and a Landau level that remains fixed at zero energy, independent of the applied
magnetic field. The team also developed a new technique based on “tunneling magneto-
conductance oscillations,” that was used to determine the energy versus momentum
relation in graphene with high precision. All measurements utilized multilayer epitaxial
graphene (MEG) synthesized at Georgia Tech; a material whose unusual rotated layer-
stacking results in electrical decoupling of neighboring graphene sheets.
(Left) Cartoon of quantized circular orbits of graphene electrons in a magnetic field.
Background honeycomb is an STM image of multilayer epitaxial graphene (MEG). Yellow
areas are raised (0.01 nm) regions created by the Moiré alignment of slightly rotated
graphene layers.
(Right) Tunneling differential conductance (dI/dV) spectra from the top layer of a 10-layer
MEG sample taken for magnetic fields from 0-6 T. Background curves show the predicted
Landau-level spectrum of graphene.
NSF Support: DMR-0804908 and facilities of the Georgia Tech MRSEC (DMR-0820382).
Related Publication: D. L. Miller*, K. D. Kubista*, G. M. Rutter, M. Ruan, W. A. de Heer, P.
N. First, and J. A. Stroscio, Science 324, 924-7 (2009).
* These authors contributed equally to this work.

1
 Shared Experimental Facilities

Vacuum radio-frequency heated furnaces

The GT MRSEC supports the operation of

Graphene is grown in a high
temperature furnace
the graphene fabrication and analysis
laboratory (Keck Epitaxial Graphene
Laboratory located on the Georgia Tech
Campus). This lab produces graphene
samples and conducts pre- and post-
testing of samples for all MRSEC members
and collaborators.

Dr. Walt de Heer, Dr. Claire Berger, Dr. Edward Conrad, School of Physics, Georgia Tech

Associated with work sponsored by NSF-MRSEC through contract DMR-0820382