Chemical vapour Deposition

2. CHEMICAL VAPOR DEPOSITION

 Uses a carbon source in the gas phase and a plasma or a heated coil, to transfer the
energy to gaseous carbon molecule.
 Sources – CH4, CO, acetylene.
 The energy source cracks the atomic carbon.
 The carbon then diffuses towards the substrate, which is coated with a catalyst Fe, Ni or Co
and binds to it.
 Use of preferential catalyst is essential.

TWO STEPS IN CVD

1. Catalyst Preparation step.
2. Synthesis of Nanotubes.

Catalyst Preparation Step: Sputtering of transition metal onto a substrate, followed by etching
by chemicals to induce the nucleation of catalyst particles.

Thermal Annealing : Metal cluster formation on the substrate – on which nanotubes grow.
Temperature : 650 – 900o C.
 TYPES OF CVD

1. Plasma Enhanced CVD.

2. Thermal Chemical CVD.
3. Alcohol Catalytic CVD.
4. Aerogel supported CVD.
5. Laser assisted CVD.
a. PLASMA ENHANCED CHEMICAL VAPOR DEPOSITION
 Involves a glow discharge in a
chamber or a reaction furnace thro’ a high
frequency voltage applied to both the
electrodes.
 A substrate is placed – grounded
electrode.
 The reaction gas is supplied from the
opposite plate. (Uniform film)
 Fe, Ni and Co are deposited on Si,
SiO2 or glass by thermal CVD or
sputtering
 Carbon gases like C2H2, CH4, is
supplied
 The CNT grow on the metal particles
on the substrate by glow discharge.
 Ni – Aligned CNTs. Dia ( 15 nm)
 b. THERMAL CHEMICAL VAPOR DEPOSITION

Fe, Ni or Co or an alloy of these metals is deposited on a substrate.

The substrate is etched by dilute HF.
Kept in CVD apparatus.
Etching of the catalytic film by NH3 gas at 750-10500C – Nanometric sized particles are formed.
BY CVD, CNTs grow on the film.
The diameter – thickness of the film.
Film Thickness – 13 nm, dia – 30-40 nm
Film Thickness – 27 nm, dia – 100-200 nm
3. PYROLYSIS OR VAPOUR PHASE DEPOSITION
Dilute hydrocarbon-organometallic mixtures yield SWCNTs.
Pyrolysis of a mixture of a metallocene-acetylene mixtures at 1100o C.
Diameter – 1.4 nm.
Pyrolysis of a mixture of a Ferrocene-CH4 at 1100o C.

4. CHEMICAL VAPOUR DEPOSITION (CVD)

Industrial production
Water assisted synthesis
Selective growth of metallic and SC nanotubes.
Preferential growth of SWCNTs is possible in a plasma enhanced CVD

1. Alcohol catalytic Chemical Vapour deposition.

2. Aerogel supported Chemical Vapour Deposition.
3. Laser Assisted Thermal Chemical Vapour Deposition.
 1. Alcohol catalytic Chemical Vapour deposition.
(Large Scale production of SWCNTs at low cost)
 Evaporated alcohols (methanol & ethanol) passed over Fe and Co
catalyst supported on zeolites (550oC)
 Hydroxyl radicals of alcohol eliminate eliminate carbon atoms with dangling bonds,
which are obstacles in forming high purity SWCNTs
 Dia – 1 nm. Low temperature suggests that direct growth of SWCNTs on semiconductor surfaces.

2. Aerogel Supported Chemical Vapour Deposition

 Decomposition of CO on an aerogel supported Fe/Mo catalyst, 860oC.
 Surface area of the supporting material , reaction temperature and feed gas affect the yield.
 Aerogels have high Surface area, so yield can be increases.
 Dia – 1-1.5 nm

3. Laser assisted Thermal Chemical Vapour Deposition

 A medium power CW CO2 laser perpendicular to the substrate pyrolyses Fe(CO)5 vapor and
acetylene in a flow reactor.
 Using a mixture of Fe(CO)5 vapor + ethylene and acetylene, SWCNTS & MWCNTS
 Si – Substrate
 Dia – 0.7 – 2.5 nm (SWCNTS) and 30 -80 nm (MWCNTs).
4. CoMoCat Process

 By disproportionation of CO at 700-900oC.
 Co-Mo catalyst formulation that inhibits the
formation of undesired forms of carbon
 Co – reduced from oxidic to metallic state
 Mo is converted to carbidic form (Mo2C)
 Co activates CO and Mo dual role – stabilizes
Co as well as Co2+ avoiding its reduction and act
as a carbon sink to moderate the growth of carbon.
 Fluidic bed reactors – permit continuous addition a
and removal of the product
 High selectivity (80-90% ) SWCNTs
4. High Pressure CO Disproprotionation Process
(HIPCO)
 Bulk Production
 Continuous flow gas phase using “CO” as carbon feed stock & Fe(CO)5 as catalysts
 CO + Fe(CO)5 – Heated Reactor
Size and dia can be tuned by adjusting
the pressure of CO.
Dia – 0.7 nm – 1.1 nm, 97% purity
Nanotubes grow in high pressure, high
temperature flowing CO on Fe
Catalyst formed insitu, by Fe(CO)5 thermal
Decomposition + cold CO and passed
Over hot CO
Fe(CO)5 Fe + 5CO
SWCNTs nucleate and grow
CO Flow tube reactor on these particles in gas
phase via disproportionation
of CO (BOUDOUARD reaction)
Fe
2CO CO2 + C (SWCNT)
Production rate – 450mgh-1
Does not require premade catalyst particles.
To improve the yield, a closed loop reactor is developed. CO is recirculated
thro the system using a compressor rather than being released into the atmosphere.
5. FLAME SYNTHESIS
 Carbon atoms formed from hydrocarbon fuels and metal catalysts.
 Similar to Laser ablation and arc discharge process.
Films of less than 10 nm metal (Co) catalyst was applied to stainless steel mesh by PVD.
 Metal islands resembling droplets form upon the mesh support to serve as catalyst particles.
 These small islands – become aerosol when exposed to flame.
 Burn a filter paper dipped in metal ions – aerosol
 Fuel gas is burnt under controlled conditions (800oC) to form Carbon atoms, for the production
of SWCNTs.

6. SONOCHEMICAL ROUTE
 Ferrocene + p-xylene (‘C’ source)

Si powder (Nucleation site for Nanotube growth)

Ultrasonicate

SWCNTs (1.3 – 1.8 nm)

1. Growth Mechanics
Assumptions in the formation of SWCNTs by CVD
a. An active catalyst particle (Fe, Ni or Co) and ready access to carbon feedstock is essential.
b. Ideally, once a nanotube begins to grow, the diameter is set and will not change.
c. At the onset of growth, the catalyst particle and the resultant nanotube are of similar size.
d. Thus, One particle leads to one nanotube.

Exceptions
a. Nanotubes are produced from nanoparticles of graphitic carbon heated to high temperature
without catalyst.
b. Long nanotubes changes chirality along their length due to defect.
c. Formation of bundles are reported.
 CNT Growth in CVD
Gas phase growth
(The catalyst formation
and nanotube growth
occur literally in mid air)
Mechanism of both Growth
1. Surface Carbon Diffusion
2. Bulk Carbon Diffusion
1. Surface Carbon Diffusion
The metal particles – soild, the cracked carbon
diffuses around the surface, and CNT nucleated on
the side of the metal particle.
Since carbon continuously breaks on the particle,
CNT grows. (LOW TEMPERATURE GROWTH with
Ni catalyst)
Substrate growth
(Catalyst Nanoparticles or metal
Precursors are deposited
on the substrate as SiO2)
2. Bulk Carbon Diffusion
The carbon feedstock is cracked or broken
down on the surface of the metal particles. The
metal particle dissolves the carbon until it
reaches saturation, at which point a CNT with
one or more walls grows from the surface.
Metal – liquid or solid – Liquid – droplet
dissolving carbon until it becomes saturated –
A nanotube begins to extrude and the
continued dissolution of carbon
In substrate growth, once the NT begins to
grow, The CNT growth will be by BASE
GROWTH OR TIP GROWTH
BASE GROWTH – The catalyst particle
attached to the surface and nanotube is
extruded into the air or along the surface.
(SWCNT)
TIP GROWTH – The end of the
nanotube remains stuck to the surface and
the catalyst particle shoots into the air.
(MWCNT)
The growth of CNTs continue until the
hydrocarbon is shut off, either by removing
the feedstock from the reaction. In base
growth, growth may slow down or stop due to
slow diffusion of Hydrocarbons down to the
nanoparticle at the bottom of CNT. If nothing
impedes- CNT grows continuously.
Stiction – fast heating method – Nanoparticle
leaps off the substrate as the CNT grows – TIP
GROWTH
If heated slowly, the particle remains stuck to
the surface and the tube grows from it – BASE
2. Carbon Feedstock
CO, methane, acetylene, ethylene, ethanol and benzene
Reactivity is the major factor in feedstock
Methane is reactive than ethylene or acetylene.
SWCNTs grown from ethylene at 550oC but methane is not reported so far at that temperature.
Oxygen has effect on growth quality and yield.
HIPCP and CoMoCat – CO as feedstock – SWCNTs
Oxygen, OH or H2O – cleanising effect – No amorphous carbon
Ethanol – Longest Nanotube

3. Catalyst
Fe, Ni or Co – SWCNTs
Bimetallic or multimetallic mixtures of Fe, Co or Ni + Y, Mo, Ru and Pt – Yield is increased.
Co/Mo catalyst is active in ethanol and slow yield in methane and reverse for Fe/Mo catalyst
TYPES OF CATALYST
(i) Unsupported (ii) Supported (iii) Vapor phase Catalyst
(i) UNSUPPORTED CATALYST

Discrete Nanoparticles lie directly on

the growth substrates to individually
Nucleate nanotube growth- high vacuum
thermal evaporation or dipping the
substrate in metal salts.
(i) SUPPORTED CATALYST
To increase the surface area
Eg. Fe/Mo catalyst supported on
an MgO support.
Impregnating catalyst with support
material like zeolite, silica,
alumina or MgO
Uisng photolithography also, it can be
patterned.
Three dimensional meso structured
supports – diameter control is possible.
(iii) VAPOR PHASE CATALYST

A volatile Fe or Ni containing compound is

vaporized and released into the furnace
(900-1000OC) along with the feedstock gas.

The nanotubes form in the vapor phase and

condense out onto cold surfaces. - Gas phase
Growth – catalyst particles are continuously
aggregating in the hot zone of the furnace,
While producing nanotubes.
1.Location and Orientation control
1.1 Catalyst Patterning
1.2 Suspended aligned SWCNTs
1.3 Aligned SWCNTs on substrates
2. Growth of ultralong SWCNTs
3. Water assisted high yield growth of SWCNTs
4. Diameter and chirality control
4.1 Nanoparticle production for narrow diameter SWCNTs
4.2 CoMoCat – Chirality Selectivity in bulk production of SWCNTs
4.3 PECVD produciton of narrow diameter and chirality SWCNTs
1. Location and Orientation control
1.1 Catalyst Patterning

E-beam or photolithography is used to

pattern
Well defined holes in the resist.
Supported or unsupported catalyst is
deposited
The resist is lifted off, leaving isolated
catalyst islands
Growth is then performed on the substrate
Producing nanotubes only from the
Predefined islands.
1.2 Surface aligned SWCNTs
For applications like interconnects etc, CNTs has to be grown between Silicon pillars.
CONTACT PRINTING was used to selectively place Fe/Mo catalyst on top of the pillars.
During CVD, CNTs grow between the pillars. Use of electric field uptp 1 V/micrometre. This
alignment is due to the large polarizability of SWCNTs – experience a strong dipole producing
- Thus align with the field.

1.3 Aligned SWCNTs on Substrates

Electric field alignment
Fast heating method – hot furnace
The catalyst particles leap off the surface and enter the laminar flow of growth gases, producing
SWCNTs as they travel.
The nanotube adheres to the substrate via vander Waals interaction, producing long and aligned
nanotubes
2. Growth of Ultralong SWCNTs
CVD – long nanotubes (4 cm)
Using CH4/C2H4/H2 and Ferritin derived Fe catalyst, 400 micrometer SWCNT was synthesized
Conditions for optimizations – Carrier gas concentrations, temperature and catalyst.

3. Water Assisted high yield growth of SWCNTs

Water + ethylene/Ar, 2.5 mm SWCNT growth is achieved.
Water etches amorphous carbon without etching SWCNTs at 750oC

4. Diameter and Chirality control

4.1 Nanoparticle production for narrow diameter SWCNTs
By controlling the size of nanoparticle, diameter of CNT can be controlled.
Ferritin (Fe containinf protein – narrow diameter

4.2 CoMoCat – Chirality Selectivity in bulk production of SWCNTs

4.3 PECVD produciton of narrow diameter and chirality SWCNTs