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MTN 530:

Nanomaterials & Applications

Carbon Nanostructures

Indranil Lahiri
Nanocarbon

• Fullerene
• Tubes
• Sheets
• Cones
• Carbon black
• Horns
• Rods
• Foams
• Nanodiamonds
Bonding

Graphite – sp2 Diamond – sp3


Formation of C Nanostructures
2D graphene sheet

bucky ball CNT 3D graphite


Why do Carbon Nanotubes form?

Carbon Graphite (Ambient conditions)


sp2 hybridization: planar

Diamond (High temperature and pressure)


sp3 hybridization: cubic

Nanotube/Fullerene (certain growth conditions)


sp2 + sp3 character: cylindrical

Finite size of graphene layer has dangling bonds. These dangling


bonds correspond to high energy states.
Eliminates dangling bonds
Nanotube formation + Total Energy
Increases Strain Energy decreases
Nanocarbon

Shenderova et al. Nanotechnology


12 (2001) 191.
Fullerene
”The most symmetrical large molecule”
• Discovered in 1985
- Nobel prize Chemistry 1996, Curl, Kroto, and Smalley

• C60, also 70, 76 and 84.


- 32 facets (12 pentagons and 20 hexagons) Epcot center, Paris
- prototype

~1 nm

Architect: R. Buckminster Fuller


Fullerene
• Symmetric shape
→ lubricant
• Large surface area
→ catalyst
• High temperature (~500oC)
• High pressure
• Hollow
→ caging particles
• Ferromagnet?
- polymerized C60
- up to 220oC
Fullerene
• Chemically stable as graphite
- most reactive at pentagons
• Crystal by weak van der Waals force
• Superconductivity
- K3C60: 19.2 K
- RbCs2C60: 33 K

Kittel, Introduction to Solid State


Physics, 7the ed. 1996.
Synthesis (discovery) of C60

The experimental set-up used to discover C60. The graphite disk is


evaporated with a Nd:YAG laser and the evaporated carbon plasma is
cooled by a stream of helium coming from a pulsed valve. The clusters of
carbon are produced in the integration cup and are expanded into
vacuum. The ions are detected by time of flight mass spectrometry
Synthesis and purification of fullerenes

Schematic illustration of the processes involved in the synthesis and


purification of fullerenes. Graphite rods are evaporated in an arc, under He
atmosphere. The soot collected is extracted with toluene and subjected to
chromatography.
Carbon Nanotubes
Carbon Nanotube
• Discovered 1991, Iijima

Roll-up vector:
 
Ch = n a1 + m a2
Carbon Nanotube
Electrical conductance depending on helicity
  2n + m
Ch = n a1 + m a2 If = i , then metallic
3
• Current capacity else semiconductor
Carbon nanotube 1 GAmps / cm2
Copper wire 1 MAmps / cm2

• Heat transmission
Comparable to pure diamond (3320 W / m.K)

• Temperature stability
Carbon nanotube 750 oC (in air)
Metal wires in microchips 600 – 1000 oC

• Caging
May change electrical properties
→ sensor
Carbon Nanotube
High aspect ratio:
Length: length
typical few μm
 1000
diameter
→ quasi 1D solid

Diameter:
as low as 1 nm
Extreme carbon nanotubes
•The longest carbon nanotubes (18.5 cm long) was reported in 2009. These
nanotubes were grown on Si substrates using an improved chemical vapor
deposition (CVD) method and represent electrically uniform arrays of single-
walled carbon nanotubes

•The thinnest carbon nanotube is armchair (2,2) CNT with a diameter of 3 Å

•The thinnest free standing single-walled carbon nanotube is about 4.3 Å


in diameter. Researchers suggested that it can be either (5,1) or (4,2)
SWCNT, but exact type of carbon nanotube remains questionable.
Carbon Nanotubes: Mechanical Properties
Carbon nanotubes are the strongest ever known material.

• Young Modulus (stiffness):


Carbon nanotubes 1250 GPa
Carbon fibers 425 GPa (max.)
High strength steel 200 GPa

• Tensile strength (breaking


strength)
Carbon nanotubes 11- 63 GPa
Carbon fibers 3.5 - 6 GPa
High strength steel ~ 2 GPa

• Elongation to failure : ~ 20-30 %


• Density:
Carbon nanotube (SW) 1.33 – 1.40 gram / cm3
Aluminium 2.7 gram / cm3
Carbon Nanotubes: Mechanical Properties
▪ Carbon nanotubes are very flexible

Nanoscience Research Group


University of North Carolina (USA)
http://www.physics.unc.edu/~rsuper/research/
Synthesis of Carbon Nanotube
1 Laser Ablation – Experimental Devices
- graphite pellet
containing the catalyst put
in an inert gas filled quartz
tube;
-oven maintained at a
temperature of 1,200 ◦C;
-energy of the laser beam
focused on the pellet;
-vaporize and sublime the
graphite

Sketch of an early laser vaporization apparatus

The carbon species are there after deposited as soot in different regions:
water-cooled copper collector, quartz tube walls.
2 Synthesis with CO2 laser
Vaporization of a target at a
fixed temperature by a
continuous CO2 laser beam (λ =
10.6μm). The power can be varied
from 100Wto 1,600 W.

The synthesis yield is controlled


by three parameters: the
cooling rate of the medium
where the active, secondary
catalyst particles are formed,
the residence time, and the
temperature (in the 1,000–
2,100K range) at which SWNTs
nucleate and grow.

Fig. 3.10 Sketch of a synthesis reactor with a


continuous CO2 laser device
3 Electric-Arc Method – Experimental Devices
After the triggering of the arc
between two electrodes, a
plasma is formed consisting
of the mixture of carbon
vapor, the rare inert gas
(helium or argon), and the
vapors of catalysts.
The vaporization is the
consequence of the energy
transfer from the arc to the
anode made of graphite
doped with catalysts.

Sketch of an electric arc reactor. It consists


of a cylinder of about 30 cm in diameter
and about 1m in height.
Electric-Arc Method – Experimental Devices

• In view of the numerous results obtained with this electric-arc


technique, it appears clearly that both the nanotube
morphology and the nanotube production efficiency strongly
depend on
– the experimental conditions and, in particular,
– the nature of the catalysts.
4 Solar energy reactor

Sketch of a solar
energy reactor in use
in Odeilho (France).
(a) Gathering of sun rays,
focused in F;
(b) Example of Pyrex®
chamber placed in (a)
so that the graphite
crucible is at the
point F.

The high temperature of about 4,000K permits both the carbon and the catalysts
to vaporize. The vapors are then dragged by the neutral gas and condense onto
the cold walls of the thermal screen.
CNT Growth by CVD
CVD System

Precursor Gas Substrate


C2H2, CH4, H2

✓ Easy process control


✓ Most popular process for CNT growth
24
Vapour Liquid Solid Method
Basics about phase diagrams

Alloys have phase diagrams


Lever rule:

g s
− g tot
al = s
T g − gl
liquid
liquid and solid
liquidus al + a s = 1

solidus

mixed crystal

gl gtot gs
A B

25
Vapour Liquid Solid Method
Eutectic:
-coexistence of 3 phases
- lowest temperature where system is still totally liquid
-minimum of liquidus curve
- solid in solid + liquid phase consists of only one material
liquidus

T
liquid

Eutectic A + liquid B+ liquid

Mixed crystal

A
solidus B
26
Vapour Liquid Solid Method
• Mix of semiconductor and metal at eutectic
• Melting point of Semiconductor with metal lower - growth of one pure
material
T
→ metal as catalyst l

A+l B+ l

Mixed crystal

Growth procedure: A B

reactant vapour reactant vapour reactant vapour reactant vapour

metal metal +Sc metal +Sc metal +Sc Sc

Liquid catalytic Nanowire Nanowire


nanocluster supersaturating nucleation growth
27
Vapour Liquid Solid method
Synthesis of multicomponent semiconductor, like
binary III-V materials (GaAs, GaP, InAs, InP)
ternary III-V materials (GaAs/P, InAs/P)
binary II-VI materials ( ZnS, ZnSe, CdS, CdSe)
binary Si Ge alloys

Pseudobinary phase diagram

T
liquid
E.g. Au - GaAs pseudobinary phase
Au + GaAs+ liquid
diagram
liquid
Au + GaAs

Au GaAs 28
Vapour Liquid Solid Method
➢In general, the nanowires grown by VLS
- cylindrical morphology
- without facets on the side surface
- uniform diameter

➢Growth rate is much faster


(60 times for Si nanowire using a liquid Pt-Si alloy than directly on the silicon
substrate at 900C)
- liquid acts as a sink for the growth species
- act as a catalyst for the heterogeneous nucleation

29
VLS – Diameter of Nanostructures

30
VLS – Diameter of Nanostructures
Critical Diameter- liquid catalyst clusters are stable in equilibrium

= surface free energy


= molar Volume
4
dc = R = gas constant
 C  T = absolute temperature
RTln  C = concentration of semiconductor component in liquid alloy
 C  C = equilibrium concentration

Problem:
in fluid at according to temperature → critical diameter
Typical value - d = 0.2 mm
Goal:
finding methods to get smaller metal clusters to start NW growth
31
Chemical Vapour Deposition
Fine catalyst particles can be formed by
- Thin film deposition – which cracks to small island upon
heating
- Colloidal suspension of metallic nanocrystals – dried on
substrate
- Evaporated growth species or precursor gas introduced to
reaction chamber
- Supersaturation in Catalyst particle
- Precipitation as nanowire or naontube

32
GaN nanowires grown in CVD reactor
CVD: Principle and Mechanism

1. Generation of active gaseous reactant species


CVD: Principle and Mechanism

2. Transport of the gaseous species into reaction chamber


CVD: Principle and Mechanism

3. Gaseous reactants undergo gas phase reactions forming intermediate species


CVD: Principle and Mechanism

4. Absorption of gaseous reactants onto heated substrate, heterogeneous reaction at


gas–solid interface, produces deposit and by-product species
CVD: Principle and Mechanism

5. Absorption of gaseous reactants onto heated substrate, heterogeneous reaction at


gas–solid interface, produces deposit and by-product species
CVD: Principle and Mechanism

6. Gaseous by-products removed from boundary layer through diffusion or convection


CVD: Principle and Mechanism

7. Unreacted gaseous precursors and by-products taken away from chamber


CNT Growth by CVD
1. Hydrocarbon vapor comes in contact with the “hot” metal nanoparticles,
2. Hydrocarbon decomposes into carbon and hydrogen species,
3. Hydrogen flies away and carbon gets dissolved into the metal,
4. After reaching the carbon-solubility limit in the metal at that temperature, as-
dissolved carbon precipitates out and crystallizes in the form of a cylindrical network
having no dangling bonds and hence energetically stable.

❑ Hydrocarbon decomposition (being an exothermic process) releases some heat to the


metal’s exposed zone,
❑ carbon crystallization (being an endothermic process) absorbs some heat from the
metal’s precipitation zone.
❑ This precise thermal gradient inside the metal particle keeps the process on.
CNT Growth by CVD

❑ Two basic growth mechanisms proposed – depending on the catalyst-substrate


interaction
❑ Weak catalyst-substrate interaction – “Tip Growth” model
❑ Strong catalyst-substrate interaction – “Base or Root Growth” model
CNT Growth by CVD: Tip Growth

1. CxHy decomposes on the top surface of the metal, C diffuses down through the
metal, and CNT precipitates out across the metal bottom, pushing the whole
metal particle off the substrate (step (i)).
2. As long as the metal’s top is open for fresh hydrocarbon decomposition
(concentration gradient exists in the metal allowing carbon diffusion), CNT
continues to grow longer and longer (step (ii)).
3. Once the metal is fully covered with excess carbon, its catalytic activity ceases
and the CNT growth is stopped (step (iii)).
CNT Growth by CVD: Root Growth

1. CxHy decomposition and C diffusion – as before, but CNT precipitation fails to


push the metal particle up; so the precipitation is compelled to emerge out from
the metal’s apex (farthest from the substrate, having minimum interaction with
the substrate). First, carbon crystallizes out as a hemispherical dome (the most
favorable closed-carbon network on a spherical nanoparticle) which then extends
up in the form of seamless graphitic cylinder.
2. Subsequent hydrocarbon deposition takes place on the lower peripheral surface
of the metal, and as-dissolved C diffuses upward. Thus CNT grows up with the
catalyst particle rooted on its base.
CNT Growth by CVD: Parameters

1. Nature of hydrocarbon,
2. Type of catalyst, catalyst size
3. Temperature,
4. Pressure,
5. Gas-flow rate,
6. Deposition time,
7. Reactor geometry

Formation of SWCNT or MWCNT – dictated by CVD parameters


CNT Growth by CVD: Precursors
Linear hydrocarbons such as methane, ethylene,
1. Methane,
acetylene, thermally decompose into atomic
2. Ethylene carbons or linear dimers/trimers of carbon, and
generally produce straight hollow CNTs.
3. Acetylene
4. Benzene Cyclic hydrocarbons such as benzene, xylene,
cyclohexane, fullerene, produce relatively
5. Carbon Monoxide
curved/hunched CNTs with the tube walls often
bridged inside
Formation of SWCNT or MWCNT – low-temperature CVD (600–900 C) yields
MWCNTs, whereas high-temperature (900–1200 C) reaction favors SWCNT
growth
Formation of SWCNT or MWCNT – SWCNTs grow from selected hydrocarbons
(viz. carbon monoxide, methane, etc.) which have a reasonable stability in the
temperature range of 900–1200 C).

Commonly efficient precursors of MWCNTs (viz. acetylene, benzene, etc.) are


unstable at higher temperature and lead to the deposition of large amounts of
carbonaceous compounds other than nanotubes
CNT Growth by CVD: Catalysts
(i) High solubility of carbon in these metals at high
1. Fe, temperatures;
(ii) high carbon diffusion rate in these metals.
2. Co
(iii) High melting point and low equilibrium-vapor
3. Ni pressure of these metals offer a wide temperature
window of CVD for a wide range of carbon
precursors.
(iv) Fe, Co, and Ni have stronger adhesion with the
growing CNTs (than other transition metals do)

Solid organometallocenes (ferrocene, cobaltocene, nickelocene) – widely used as


CNT catalyst, as they liberate metal nanoparticles in-situ which catalyze the
hydrocarbon decomposition more efficiently

Formation of SWCNT/MWCNT – catalyst-particle size dictates the tube diameter


CNT Growth by CVD: Substrates
1. Graphite,
Catalyst–substrate reaction (chemical bond
2. Quartz formation) – affects catalytic behavior of the metal.
3. Si
The substrate material, its surface morphology and
4. SiC textural properties greatly affect the yield and
quality of the resulting CNTs.
5. Silica
6. Alumina
7. Alumino-silicate
8. CaCO3
9. MgO

SWCNT growth on a Fe catalyst, as observed in ab initio simulations. (i) Diffusion


of single C atoms (red spheres) on the surface of the catalyst. (ii) Formation of
an sp2 graphene sheet floating on the catalyst surface with edge atoms
covalently bonded to the metal. (iii) Root incorporation of diffusing single C
atoms (or dimers).
CNT Growth by CVD: Challenges
1. Growing fixed diameter of CNTs,
2. Chirality control
3. Controlling number of walls in MWCNTs
4. Even a single CNT has different diameter and chirality!!
5. Lowering CVD temperature
6. Understanding growth mechanism
7. Improving crystallinity of CVD grown CNTs

Mukul Kumar and Yoshinori Ando, Chemical Vapor Deposition of Carbon Nanotubes:
A Review on Growth Mechanism and Mass Production, J. Nanosci. Nanotechnol.
10, 3739–3758, 2010
Graphene
Introduction to graphene

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

Molecular structure of graphene High resolution transmission electron microscope images


(TEM) of graphene
Introduction
Properties of graphene

- Electronic properties
- Thermal properties
- Mechanical properties
- Optical properties
- Relativistic charge carriers
- Anomalous quantum Hall effect

Electronic properties
- High electron mobility (at room temperature ~ 200.000 cm2/(V·s),, ex. Si at RT~ 1400 cm2/(V·s),
carbon nanotube: ~ 100.000 cm2/(V·s), organic semiconductors (polymer, oligomer): <10 cm2/(V·s)
Where υd is the drift velocity in m/s (SI units)
E is the applied electric field in V/m (SI)
µ is the mobility in m2/(V·s), in SI units.

- Resistivity of the graphene sheet ~10−6 Ω·cm, less than the resistivity of silver (Ag), the lowest
resistivity substance known at room temperature (electrical resistivity is also as the inverse of the
conductivity σ (sigma), of the material, or
Material Electrical Conductivity (S·m-1) Notes
Graphene ~ 108
Silver 63.0 × 106 Best electrical conductor of any known metal

Commonly used in electrical wire applications due to


Copper 59.6 × 106
very good conductivity and price compared to silver.

Referred to as 100% IACS or International Annealed


Copper Standard. The unit for expressing the
Annealed Copper 58.0 × 106 conductivity of nonmagnetic materials by testing
using the eddy-current method. Generally used for
temper and alloy verification of aluminium.

Gold is commonly used in electrical contacts because


Gold 45.2 × 106
it does not easily corrode.
Commonly used for high voltage electricity
Aluminium 37.8 × 106
distribution cables[citation needed]
Corresponds to an average salinity of 35 g/kg at
Sea water 4.8
20 °C.[1]
This value range is typical of high quality drinking
Drinking water 0.0005 to 0.05
water and not an indicator of water quality

Conductivity is lowest with monoatomic gases present;


changes to 1.2 × 10-4 upon complete de-gassing, or to
Deionized water 5.5 × 10-6
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
Electronic properties
Graphene’s band structure yields unusual properties

EF

The velocity of an electron


at the Fermi level (vF)
Is inversely related to meff

Effective mass (m*) ~ [dE2/dk2]-1

Most semiconductors, 0.1 m0 < m* < 1 me


Castro-Neto, et al. Rev.
Graphene, m* < 0.01 m0 (depending on number of carriers)
Mod. Phys. 81 (2009)
Therefore, expect VERY high mobility in graphene
109
Both holes and electrons can be carriers 53
Thermal properties
Thermal conductivity
Material
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
237 (pure)
Aluminium
120—180 (alloys)
Gold 318
Copper 401
Silver 429
Diamond 900 - 2320
Graphene (4840±440) - (5300±480)
Properties of graphene

Mechanical properties

- High Young’s modulus (~1,100 Gpa)


High fracture strength (125 Gpa)
A representation of a diamond tip with a two nanometer radius
indenting into a single atomic sheet of graphene (Science, 321 (5887):
385)

- Graphene is considered as the strongest material ever measured, almost 200 times
stronger than structural steel
Properties of graphene
Optical properties
- Monolayer graphene absorbs πα ≈ 2.3% of white light (97.7 % transmittance),
where α is the fine-structure constant.

F. Bonaccorso et al. Nat. Photon. 4, 611 (2010)


Preparation and characterization graphene
Preparation methods

Top-down approach Bottom up approach


(From graphite) (from carbon precursors)
- Micromechanical exfoliation of graphite (Scotch - By chemical vapour deposition (CVD)
tape or peel-off method) of hydrocarbon
- Creation of colloidal suspensions from graphite - By epitaxial growth on electrically
oxide or graphite intercalation compounds (GICs) insulating surfaces such as SiC

Ref: Carbon, 4 8, 2 1 2 7 –2 1 5 0 ( 2 0 1 0 )
Characterization methods

Scanning Probe Raman Transmission electron X-ray diffraction


Microscopy (SPM): Spectroscopy Microscopy (TEM) (XRD)

- Atomic force microscopes (AFMs)


- Scanning tunneling microscopy (STM)

Atomic force microscopy images of a graphite oxide


film deposited by Langmuir-Blodgett assembly
Characterization methods

Raman
Spectroscopy

Transmission electron
Microscopy (TEM)

TEM images show the nucleation of (c) one, (d) three, or (e) four
layers during the growth process
Characterization methods

X-ray diffraction
(XRD)

XRD patterns of 400 um diameter graphite flakes oxidized for various lengths of time.
The Big problem with graphene: an imagined conversation:

A. OK: Graphene is great, lots of interesting properties for devices!

B. How do you make a device?

A. You need a sheet of graphene!

B. OK, how do you get a sheet of graphene?

A. HOPG, scotch tape, and tweezers!

B. !@#$%%

62
Preparation methods

Top-down approach
(From graphite)

Direct exfoliation of Graphite intercalation compound Graphite oxide method


graphite
Direct exfoliation of graphite

Dispersions of microcrystalline synthetic graphite have a concentration of 0.03 mg


mL-1. Dispersions of expanded graphite and HOPG are less concentrated (0.02
mg mL-1).
Direct exfoliation of graphite

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).
Graphite intercalation compound

J. Mater. Chem. 2005, 15, 974.


Micromechanical cleavage

SiO2 Fig. 1. Graphene films.


Si
(A) Photograph (in normal
3 nm
white light) of a large multi-
3 nm
layer graphene flake on top
of an oxidized Si wafer.
(B) AFM image of 2 mm by
2 mm area of this flake near
2.5 nm its edge. Colors: dark brown,
0.8 nm
SiO2 surface; orange, 3 nm
height above the SiO2
SiO2
surface. (C) AFM image of
1.2 nm
single-layer graphene.

Materials: HOPG
Preparation:
1. prepared 5 mm-deep mesas on top of the platelets (mesas were squares of various
sizes from 20 mm to 2 mm).
2. Pressed the structured surface on a 1-mm-thick layer of a fresh wet photoresist
spun over a glass substrate. After baking, the mesas became attached to the
photoresist layer, which allowed us to cleave them off the rest of the HOPG
sample. Then, using scotch tape to repeatedly peel flakes of graphite off the mesas. 67
3. Thin flakes left in the photoresist were released in acetone.
4. Dipping a Si wafer in the solution and then washed in plenty of water and
propanol, some flakes became captured on the wafer’s surface (chose thick SiO2
with t =300 nm).
5. Used ultrasound cleaning in propanol to remove mostly thick flakes. Thin flakes
(d < 10 nm) were found to attach strongly to SiO2, presumably due to van der
Waals and/or capillary forces.

(Left) Optical photograph in white light of a large Hall bar made from multilayer
graphene (d »5nm). The central wire is 50mm long.
(Right) A short (200 nm) wire made from few-layer graphene.
Advantages : Production of single layer graphene is feasible
68
Drawbacks : Limited quantity
Graphite oxide ( Most common and high yield method)

Oxidation (Hummers’method)
Graphite Oxide
H2SO4/ KMnO4
H2SO4/KClO3
Graphite Or H2SO4/HNO3
……………….
H2O

Ultrasonication (exfoliation

Fuctionalization (for better dispersion)


Graphene Oxide
monolayer or few layers

Chemical reduction to restore graphitic structures

Making composite with polymers


Graphite oxide method

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/Graphene oxide
Hydroxyl group

Epoxy group
Lerf-Klinowski model of graphene oxide

GO : interlayer spacing between 6 and 10 A ° depending on the oxygen content

GO : C:O ratio between 2.1-2.9

r-GO : C:O ratio around 11-12


Bottom up approach
(from carbon precursors)
Epitaxial growth

Production of EG on diced (3 mm by 4 mm)


commercial SiC wafers.

Steps:
(1) hydrogen etching to produce atomically
flat surfaces;
(2) vacuum graphitization to produce an
ultrathin epitaxial graphite layer;
(3) application of metal contacts (Pd, Au),
(4) electron-beam patterning and
development;
(5) oxygen plasma etch to define graphite
structures;
(6) wire bonding.

Advantage: Patterned graphene structure


75
Drawback: Ultra-high vacuum, high cost
Epitaxial growth - SiC decomposition

When SiC substrates are annealed at high temp., Si atoms selectively desorb from the surface
and the C atoms left behind naturally form FLG (few-layer graphene)
Graphene nanoribbons
(from carbon nanotube)

NATURE, Vol , 458, 16 , April (2009)


Potential applications 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
Graphene Growth by CVD
Chemical vapor deposition

Chamber:12-in chamber quartz reactor


Heater: graphite electrodes placed at the top and
bottom with a separating distance of 10 cm
IR detector: temp. measurement
Substrate: A cupper foil was placed on the bottom
heater
Annealing: by H2 and Ar (increase Cu grains)
Deposition: using CH4 and H2 as precursor
Cooling: rapidly cooling under Ar

Mechanisms:
1.Adoption of Cu:(a) low solubility of carbon in Cu,
(b) surface diffusion of carbon atoms on Cu;
2.Absorption and de-absorption of hydrocarbon
molecules on Cu;
3.Decomposition of hydrocarbon to form carbon atoms;
4.Aggregation of carbon atoms on Cu surface to form
graphene nucleation centers;
5.Diffusion and attachment of carbon atoms to
nucleation centers to form graphene film 80
Chemical vapor deposition
Effect of Hydrocarbon precursor and substrate
1.Methane is a relatively stable hydrocarbon compound due to strong C-H bond,
as a result, decomposition occurs at elevated temperature (>1200C);
2.Other hydrocarbon compounds such as ethane and acetylene are not suggested
due to rapid decomposition at high temperature;
3.Other transition metal such as Fe, Co, and Ni are not preferred for mono or
bilayer graphene growth due to their higher-than-desirable capacity to
decompose hydrocarbons.
4.The low decomposition rate of methane on Cu allows the possibility of controlling
the number of graphene layers.

Decomposition of hydrocarbon
1.Cu foil: Cu foil is usually not single crystal possessing grain boundaries and steps;
2.The sites have much higher chemical activation energy than those of the flat
regions of Cu; as a result, hydrocarbons prefer to decompose on the sites to form
nucleation centers;
3.Cu foil with smooth surface is preferred: pre-polish and in-situ polish.

81
(a) Schematic of graphene growth process at low-pressure CVD condition:
(1) Nucleation starts at the steps and grain boundaries,
(2) Growth process after nucleation.
(b) Graphene domains on the Cu surface. Arrow indicates the direction of polish lines.
(c) Image of a single tetragonal graphene domain. 82
(d) OM image of a grown graphene sheet verifying the growth mechanism outlined in (a).
Processing parameters-substrate pretreatment
1.Treated by dilute acid
2.Ultrasonic Cu foil in acetone
3.Annealing at lower pressure (due to sublimation of Cu at low pressure)

Fig. (a)-(c): Treated in relatively high pressure


Fig. (d)-(f): Treated in lower pressure 83
Fig. (g):OM of Fig.(a); (i):OM of Fig.(d),
Processing parameters-hydrocarbon concentration

1. After low pressure annealing, the Cu surface becomes smoother and has low-index
planes (such as (1 0 0) plane). due to the restructuring of the Cu atoms enabled by
increased diffusivity at high temperatures during the low pressure annealing.
2. Low partial pressure of hydrocarbon decrease the size of nucleation centers.
84
Processing parameters-purity of the Cu substrate

1.The impurity in the catalyst greatly enhances the catalytic capability of the catalyst.
Could the purity of the Cu foil affect the number of layers?*
2.Cu foil with lesser purity: 2638–2641 cm-1, I2D/IG: over 3: monolayer
Cu foil with higher purity: 2641–2646 cm-1, I2D/IG:1.8-2.4:bilayer.**
85
Graphene Growth by CVD
1. Graphitic structure starts forming at temperature over 2500C – difficult to
control process, energetically unfavorable – needs catalyst
2. Catalysts lower temperature significantly – but can introduce CNT growth
Graphene Growth by CVD – on Ni and Cu

Cu is more sensitive to oxidation than Ni

Cu can evaporate more than Ni (due to lower M.P.) – frequent chamber cleaning
required
Congqin Miao, Churan Zheng, Owen Liang and Ya-Hong Xie,
Chemical Vapor Deposition of Graphene, www.intechopen.com
Grain Boundaries
• Grain Boundaries give rise to surface roughness.
• On precipitation, carbon prefers to stay in the areas with
higher surface energy, such as grain boundaries, surface
trenches and so on.
• These areas have more atomic dangling bonds that could
easily attract precipitated carbon atoms.
• Deposited graphene exhibits non-uniformity with thick
graphene around grain boundaries and other surface defects,
and thin sheet on the other areas.
• Thus important to pre-anneal catalyst substrates in order to
have large grains to reduce total length of grain boundaries, as
well as other minor surface defects.
Congqin Miao, Churan Zheng, Owen Liang and Ya-Hong Xie,University of California, Los Angeles,United States: Chemical Vapor
Deposition of Graphene
Rate Of Cooling(in case of Nickel)
• At elevated temperature, dissociated carbon atoms on the catalyst surface
may dissolve into the bulk due to the finite solubility.
• As these dissolved carbon atoms precipitate back onto Ni surface as
temperature drops and hence unwanted carbon deposition may occur from
bottom.
• Different cooling rate suggests the different thickness of graphene.
• Hence the control of deposition is of more difficulties.
• Figure (next slide) shows the schematic drawing of graphene grown on Ni with
different cooling rate.
▪ Extreme fast cooling leads to little carbon precipitation, because not
sufficient time is allowed for carbon to precipitate.
▪ Medium cooling gives graphene, and
▪ Slow cooling has nothing on the surface in that carbon atoms diffuse
deep into the bulk catalyst.

Congqin Miao, Churan Zheng, Owen Liang and Ya-Hong Xie,University of California, Los Angeles,United States: Chemical Vapor
Deposition of Graphene
Illustration of carbon segregation at metal(Ni) surface
Congqin Miao, Churan Zheng, Owen Liang and Ya-Hong Xie,University of California, Los Angeles,United States: Chemical Vapor Deposition
of Graphene
Copper As Catalyst
• Copper is put into a furnace and heated under low vacuum to
around 1000°C. The heat anneals the copper, increasing its
domain size.
• The hydrogen catalyzes a reaction between methane and the
surface of the metal substrate, causing carbon atoms from the
methane to be deposited onto the surface of the metal through
chemical adsorption (see Figure).
• The furnace is quickly cooled to keep the deposited carbon layer
from aggregating into bulk graphite, which crystallizes into a
contiguous graphene layer on the surface of the metal.

Benjamin Pollard
Department of Physics, Pomona College : Growing Graphene via Chemical Vapor
Deposition
Diagram of CVD growth on copper.

Benjamin Pollard
Department of Physics, Pomona College : Growing Graphene via Chemical Vapor
Deposition
Graphene Growth by CVD – Low Temp

1. Solid PMMA and polystyrene precursors, centimeter-scale monolayer


graphene films are synthesized at a growth temperature down to 400 C.
2. Benzene as the hydrocarbon source, monolayer graphene flakes with excellent
quality are achieved at a growth temperature as low as 300 C.

Zhancheng Li, Ping Wu, Chenxi Wang, Xiaodong Fan, Wenhua Zhang, Xiaofang Zhai, Changgan Zeng,*
Zhenyu Li,* Jinlong Yang, and Jianguo Hou, Low-Temperature Growth of Graphene by Chemical Vapor
Deposition Using Solid and Liquid Carbon Sources, ACS Nano, VOL. 5 ’ NO. 4 ’ 3385–3390 ’ 2011
Graphene Growth by CVD – Challenges
1. Controlling number of layers
2. Control of domain size
3. Uniformity
4. Transfer – causing defects
5. Effect of substrate texture
6. Understanding growth mechanism
Graphene growth: Comparison

SiC sublimation Metal catalysis


CVD
Ni: non uniform multi➔ Cu: uniform single ➔ Cu:
layer by layer growth

Current
Status Solid Carbon : Low temp.

Nat.mat.2009.203. Ar1atm,1450~1650°C
Terrace size increase.

Nat.2010.549. ACS nano,2011

High temperature growth


:1200~1500°C Low temperature growth
Non-uniform growth :below 1000°C
Pros& in Step edge and terrace. Unform growth : Capet like (Large area)
Cons High cost SiC wafer Si CMOS compatible process.
: SiC growth on Si
No transfer required
“Transfer required”

95
Motivation: Direct Growth on Dielectric Substrates: Toward Industrially
Practical, Scalable Graphene—Based Devices
Graphene Growth: Conventional Approaches
transfer
CVD graphene monolayer

Result: graphene
SiO2 monolayer, interfacial inhomogeneities
Metal or HOPG Si
Si evaporation Result: graphene
> 1500 K
monolayer or multilayer
SiC(0001) SiC(0001) on SiC(0001)

FET: Band gap


Focus: Direct Charge-based devices
Top Gate
CVD, PVD or MBE n
graphene
On Dielectrics
Spintronics MgO(111)
Si(100)
Co3O4(111)
graphene
Coherent-Spin FET: Multi-functional, non-
volatile devices

96
Direct Growth of Graphene on Dielectric Substrates: Summary

Substrate Growth Method Remarks References


Temperature
MgO(111) ~ 1000 K CVD, PVD Interfacial L. Kong, et al. J. Phys. Chem.
reaction, band C. 114 (2010) 21618
gap
Co3O4(111) 1000 K MBE Incommensurate M. Zhou, et al., J. Phys.:
interface, Cond. Matt. 24 (2012) 072201
Ferromagnetism1
Mica ~1000 K MBE Oxidation at G. Lippert, et al. Phys. Stat.
C(111) edge Sol. B. 248 (2011) 2619
sites?
Al2O3(0001) 1800 K CVD High temp. M. Fanton,et al., Conf.
required for few- Abstract (Graphene 2011,
defect films Bilbao, Spain)
BN(0001) 1000 K CVD Monolayer BN C. Bjelkevig, et al., J. Phys.:
by ALD, strong Cond. Matt. 22 (2010) 302002
BN→ graph
charge transfer
1
Unpublished result

97
Generalization, Directly Grown Graphene and Charge Transfer: Oxides
(p-type) vs. Metals (n-type)

e- graphene EF
n-type; metal to
Transition metals graphene charge transfer
(Ru, Ni, Cu, Ir…)

e- graphene p-type; graphene to


substrate charge
Oxides, SiC transfer

EF
98