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Graphene
One of the most promising material
3
Andrei Geim and Kostya Novoselov extracted the graphene
from a piece of graphite such as is found in ordinary pencils by
playing with a sticky tape (University of Manchester).
Friday night experiments
Using regular adhesive tape they managed to obtain a flake of
carbon with a thickness of just one atom.
This at a time when many believed it was impossible for such
thin crystalline materials to be stable.
Andre Geim, Dutch citizen. Born
1958 in Sochi, Russia. Ph.D. 1987
from Institute of Solid State
Physics, Russian Academy of
Sciences, Chernogolovka, Russia.
Director of Manchester Centre for
Meso-science & Nanotechnology,
Langworthy Professor of Physics
and Royal Society 2010
Anniversary Research Professor,
University of Manchester, UK.
By the way ,he got another noble
prize named the most funny
noble prize.
Konstantin Novoselov,British and Russiancitizen. Born 1974 inNizhny Tagil, Russia.
Ph.D. 2004 fromRadboud UniversityNijmegen, TheNetherlands. Professorand Royal SocietyResearch Fellow,University ofManchester, UK.
7
8
Carbon allotropes
9
WH
Y
GR
AP
H
ENE
(discovered 2004)
c
ab
Graphene: extraordinary thermal conductivity
~ 3000-5000 W/mK [Nano Lett. 8, 902–907, 2008]
(highest among materials – responsible for the high
thermal conductivity of graphite (ab-plane) and CNT!
• Graphene: building block
for most carbon materials
---incl. graphite and
carbon nanotubes(CNT)
• Recently, carbon materials
(incl. both graphite and CNT)
investigated as attractive
thermal interface material
(TIM) motivated by their
high thermal conductivity
Other advantages of graphene:
•High packing density [due to 2D]
•rich shapes/geometry
•Easily functionalized
•Possibilities to bond to surface
11
12
Atomic force microscopy image of a graphene crystal on top of an oxidized Si
substrate. Folding of the flake can be seen. The measured thickness of
graphene corresponds to the interlayer distance in graphite. Scale
bar = 1 µm.
13
First observations of graphene date back to at least 1962.
H. P. Boehm et al. Zeitschrift für Naturforschung B 17, 150 (1962).
With TEM
14
15
Single sheet of Carbon atoms: monolayer graphite.
Honeycomb structure.
Nearest neighbour distance a=1.42A.
Two Carbon sub-lattices.
Carbon → 4 valence electrons: 3 for sp2 bonds.
The 4th one is in a pz orbital ( band).
The pz orbital is perpendicular to the plane and rotational symmetric around z-axis.
Condensed-matter systems usually described accurately by the Schrödinger equation.
Quantum relativistic effects are usually minute.
Electron transport in graphene is governed by Dirac’s (relativistic) equation.
Charge carriers in graphene mimic relativistic particles with zero rest mass and effective speed of light vF≈106 m/s.
Variety of unusual phenomena characteristic of 2D Dirac fermions.
Graphene is a one-atom-thick planar sheet of sp2-bonded carbon atoms that are
densely packed in a honeycomb crystal lattice
The name ‘graphene’ comes from graphite + -ene = graphene
High resolution transmission electron microscope images
(TEM) of graphene
Introduction to graphene
Molecular structure of graphene
A. K. Geim & K. S. Novoselov. The rise of graphene. Nature Materials Vol . 6 ,183-191 (2007).
10/2004
10/2002
(Quoted from “Cambridge IP”)
“
”
Very stable
Even at room temperature, electrons in graphene are more than 100 times more mobile than in silicon.
97.3 percent transparent
Graphene is stronger and stiffer than diamond
Good thermal conductivity
The poperties of it.
22
- Electronic properties
- Thermal properties
- Mechanical properties
- Optical properties
- Relativistic charge carriers
- Anomalous quantum Hall effect
Material Electrical Conductivity (S·m-1) Notes
Graphene ~ 108
Silver 63.0 × 106 Best electrical conductor of any known metal
Copper 59.6 × 106Commonly used in electrical wire applications due to
very good conductivity and price compared to silver.
Annealed Copper 58.0 × 106
Referred to as 100% IACS or International Annealed
Copper Standard. The unit for expressing the
conductivity of nonmagnetic materials by testing using
the eddy-current method. Generally used for temper and
alloy verification of aluminium.
Gold 45.2 × 106Gold is commonly used in electrical contacts because it
does not easily corrode.
Aluminium 37.8 × 106Commonly used for high voltage electricity distribution
cables[citation needed]
Sea water 4.8 Corresponds to an average salinity of 35 g/kg at 20 °C.[1]
Drinking water 0.0005 to 0.05This value range is typical of high quality drinking water
and not an indicator of water quality
Deionized water 5.5 × 10-6
Conductivity is lowest with monoatomic gases present;
changes to 1.2 × 10-4 upon complete de-gassing, or to 7.5
× 10-5 upon equilibration to the atmosphere due to
dissolved CO2[2]
Jet A-1 Kerosene 50 to 450 × 10-12 [3]
n-hexane 100 × 10-12
Air 0.3 to 0.8 × 10-14
MaterialThermal conductivity
W/(m·K)
Silica Aerogel 0.004 - 0.04
Air 0.025
Wood 0.04 - 0.4
Hollow Fill Fibre Insulation Polartherm 0.042
Alcohols and oils 0.1 - 0.21
Polypropylene 0.25 [6]
Mineral oil 0.138
Rubber 0.16
LPG 0.23 - 0.26
Cement, Portland 0.29
Epoxy (silica-filled) 0.30
Epoxy (unfilled) 0.59
Water (liquid) 0.6
Thermal grease 0.7 - 3
Thermal epoxy 1 - 7
Glass 1.1
Soil 1.5
Concrete, stone 1.7
Ice 2
Sandstone 2.4
Stainless steel 12.11 ~ 45.0
Lead 35.3
Aluminium237 (pure)
120—180 (alloys)
Gold 318
Copper 401
Silver 429
Diamond 900 - 2320
Graphene (4840±440) - (5300±480)
Thermal properties
We can make Super-Small Transistors with it .In this
way, the moore's law that have worked for 45 years
can effect for decades.
For example ,in 2010, IBM developed a Graphene FET
with a 100G (it can reach to 1T in theory) cut-off
frequency ,while cut-off frequency of FET made by
silicon is lower than 40G.
The university of Pennsylvania made out 4 inch Graphene wifer in recently.
SO
ME
PIC
TUR
ES
SECO
ND
Since this kind of material isstrong, stiff and light, somepeople suppose we can builda tower from earth to thespace.
In fact ,we can use it tomake many mechanicaldevices such as airplane,carand so on.
TH
IRD
We can use it to produce transparent conductive film that can use to make solar battery.
This kind of film have a high conductivity , high transparent rate.We needn't to protect this film because it's strong.
FO
UR
TH
We can develop small senor to
detect the small cell or graphene
quantum dots to detect even one
molecular in the air.
HO
WTO
MA
KE
IT?There are so many way to use
it ,but how can we product it? Nobody have a good way.
If you have one,you will be a billionaire.
The noble prize winner use garphite and tap.They succeed and win noble prize .
Preparation and characterization graphene
Preparation methods
Top-down approach(From graphite)
Bottom up approach (from carbon precursors)
- By chemical vapour deposition (CVD)
of hydrocarbon
- By epitaxial growth on electrically
insulating surfaces such as SiC
- Total Organic Synthesis
- Micromechanical exfoliation of graphite (Scotch
tape or peel-off method)
- Creation of colloidal suspensions from graphite
oxide or graphite intercalation compounds (GICs)
Ref: Carbon, 4 8, 2 1 2 7 –2 1 5 0 ( 2 0 1 0 )
Characterization methods
Scanning Probe Microscopy (SPM):
- Atomic force microscopes (AFMs)- Scanning tunneling microscopy (STM)
Raman Spectroscopy
Transmission electron Microscopy (TEM)
X-ray diffraction (XRD)
Atomic force microscopy images of a graphite oxide
film deposited by Langmuir-Blodgett assembly
Now,some companies or labs use different methods to get it .There are three main methods .
Top-down approach(From graphite)
Graphite oxide methodGraphite intercalation compoundDirect exfoliation of
graphite
Preparation methods and discussions
Direct exfoliation of graphite
Micromechanical exfoliation of graphite (Scotch tape or peel-off method). S
Graphene sheets ionic-liquid-modified by electrochemistry using graphite electrodes.
Liu, N. et al. One-step ionic-liquid-assisted electrochemical synthesis of ionicliquid-
functionalized graphene sheets directly from graphite. Adv. Funct. Mater. 18, 1518–1525 (2008).
Direct exfoliation of graphite
J. Mater. Chem. 2005, 15, 974.
Graphite intercalation compound
Graphite oxide method ( Most common and high yield method)
Graphite
Oxidation (Hummers’method)
H2SO4/ KMnO4
H2SO4/KClO3
Or H2SO4/HNO3
……………….H2O
Ultrasonication (exfoliation)
Graphite Oxide
Graphene Oxide
monolayer or few layers
Fuctionalization (for better dispersion)
Making composite with polymers
Chemical reduction to restore graphitic structures
Tung, V. C., Allen, M. J., Yang, Y. & Kaner, R. B. High-throughput solution
processing of large-scale graphene. Nature Nanotech. 4, 25–29 (2008).
Graphite oxide method
More intercalation for better exfoliation to monolayers
Graphite oxide
Graphite oxide method
Bottom up approach (from carbon precursors)
Yang, X. Y.; Dou, X.; Rouhanipour, A.; Zhi, L. J.; Rader, H. J.;
Mullen, K. J. Am. Chem. Soc. 2008, 130, 4216.
Total Organic Synthesis
Graphene nanoribbons(from carbon nanotube)
NATURE, Vol , 458, 16 , April (2009)
Potential application of graphene
- Single molecule gas detection
- Graphene transistors
- Integrated circuits
- Transparent conducting electrodes for the replacement of ITO
- Ultracapacitors
- Graphene biodevices
- Reinforcement for polymer nanocomposites: Electrical, thermally conductive nanocomposites, antistatic coating, transparent conductive composites..ect
Why graphene? Unusual properties
Surface EM waves in graphene
Radiation patterns: surface plasmons and free-space fields
A point source: the fundamental problem
Possible applications
Optical solutions: possible future of Electronics?
Thin metallic optical interconnectors
Graphene optical interconnectors
Atomic structure and electronic properties
• One atomic layer-thick
• Zero mass of electrons
• High electron mobility
• Pronounced response to external voltage
Graphene transistors and integrated circuits
H. B. Heersche et al., Nature 446, 56 (2007)
Y.-M. Lin et al. (IBM), Science 327, 662 (2010)
cutoff frequency of 100 GHz for a gate length of 240 nm supercurrent transistor
Unusual optical properties
Optical properties
Extremely thin, but seen with the naked eye
• It absorbs of white light
• Conductivity is sensible to external fields
• Saturable absorption
• Could be made luminescent
• Supports surface electromagnetic waves
F. Bonaccorso et al., Nature Phot. 4, 611 (2010)
Graphene-based optoelectronics
LEDSolar cell
Flexible smart window
2.3%
Unusual optical properties
Surface EM waves in graphene
Surface plasmons (SPs) in metallic surafces
W. L. Barnes et al., Nature 424, 824 (2003)
~ iqxe
~ x Le
q
qqq
Surface EM waves in graphene
Conductivity of graphene
300T K
0.2eV
Surface EM waves in graphene
Surface waves in graphene
~ iqxe
~ x Le
Im( ) 0
Im( ) 0
Surface EM waves in graphene
Graphene metamaterials and Transformation Optics
Spatial varying voltage 2D graphene plasmonic prism
2D graphene plasmonic waveguide Transformation Optics devices
Surface EM waves in graphene
A point source: the fundamental problem
A point source: the fundamental problem
Possible sources for local excitation
molecule
quantum dot
Josephson qubit
A point source: the fundamental problem
Electric dipole
( )?E r
A point source: the fundamental problem
Computational difficulties: asymptotic approach
2( )
1
iqx
zp
eE x dq
q q
polebranch cutpole
branch cut
L. P. Felsen and N. Marcuvitz, Radiation and Scattering of Waves (IEEE Press, Piscataway, NJ, 1994)
Radiowave propagation problems
graphene
oscillating factor
Radiation patterns: SPs and free-space fields
Density of electromagnetic states
( ) ~ iqxE x dq DOS e
0.024 1.12
Radiation patterns: surface plasmonsand free-space fields
Radiation patterns: SPs and free-space fields
Vertical dipole
0.31 , 0.97mm THz
SP characteristics:
SP 200L
Radiation patterns: SPs and free-space fields
Vertical dipole
41.3 , 7.2m THz
SP characteristics:
0.1SP 3L
Radiation patterns: SPs and free-space fields
Vertical dipole
1( 6.2 , 48.4 )m THz
2 ( 3.1 , 96.7 )m THz No SP excited
SP characteristics:
0.01SP 0.1L
No SP excited
Radiation patterns: SPs and free-space fields
Horizontal dipole
SP characteristics:• long propagation length• wavelength close to the vacuum one
0.31 , 0.97mm THz
Radiation patterns: SPs and free-space fields
Horizontal dipole
15.5 , 19.3m THz SP characteristics:
• medium propagation length (of order of several wavelengths)• wavelength is quite less than the vacuum one
Radiation patterns: SPs and free-space fields
Horizontal dipole
No SP excited
3.1 , 96.7m THz
Possible applications
Possible applications
A. Gonzalez-Tudela et al., PRL 106, 020501 (2011)
Qubits coupling through graphene SPs waveguides
A. Vakil et al.,arXiv: optics/1101.3585
EM fields created by apertures in graphene
A. Yu. Nikitin et al., PRL 105, 073902 (2010)