SYNTHESIS OF CARBON
NANOTUBES BY CHEMICAL VAPOR
DEPOSITIONS
INTRODUCTION
• Among several techniques of CNT synthesis available today, chemical vapor deposition
(CVD) is most popular and widely used because of its low set-up cost, high production
yield at low temperature and ambient pressure .
• In yield and purity, CVD beats the arc-discharge and laser methods. And, when it comes
to structure control or CNT architecture, CVD is the only answer.
• CNT synthesis involves many parameters such as hydrocarbon, catalyst, temperature,
pressure, gas-flow rate, deposition time, reactor geometry.
• CVD enables the use of various substrates, and allows CNT growth in a variety of forms,
such as powder, thin or thick films, aligned or entangled, straight or coiled nanotubes, or
a desired architecture of nanotubes on a patterned substrate. It also offers better control
on the growth parameters.
• Chemical vapor deposition (CVD) is a process of
depositing a solid material from a vapor by a chemical
reaction occurring on or in the vicinity of a normally
heated substrate surface.
• The solid material is obtained as a coating, a powder, or
as single crystals.
• By varying the experimental conditions like substrate
material, substrate temperature, composition of the
reaction gas mixture, pressure, gas flow rate etc.,
materials with different properties can be grown.
Fig: Schematic diagram of a CVD setup in its simplest form.
CNT SYNTHESIS:
• The process involves passing a hydrocarbon vapor (typically 15–60 min) through a
tubular reactor in which a catalyst material is present at sufficiently high temperature
(600–1200 C) to decompose the hydrocarbon.
• CNTs grow on the catalyst in the reactor, which are collected upon cooling the system to
room temperature.
• In the case of a liquid hydrocarbon (benzene, alcohol, etc.), the liquid is heated in a flask
and an inert gas is purged through it, which in turn carries the hydrocarbon vapor into
the reaction zone.
• If a solid hydrocarbon is to be used as the CNT precursor, it can be directly kept in the
low-temperature zone of the reaction tube.
• Like the CNT precursors, also the catalyst in CVD may be used in any form: solid, liquid
or gas, which may be suitably placed inside the reactor or fed from outside.
• Pyrolysis of the catalyst vapor at a suitable temperature liberates metal nanoparticles
(such a process is known as floating catalyst method). Alternatively, catalyst coated
substrates can be placed in the hot zone of the furnace to catalyze the CNT growth.
• Hydrocarbon vapor when comes in contact with the “hot” metal nanoparticles, first
decomposes into carbon and hydrogen species; hydrogen flies away and carbon gets
dissolved into the metal.
• Hydrocarbon decomposition (being an exothermic process) releases some heat to the
metal’s exposed zone, while carbon crystallization (being an endothermic process)
absorbs some heat from the metal’s precipitation zone. This thermal gradient inside the
metal particle keeps the process on.
CNT CATALYST AND SUBSTRATES
• Most commonly-used metals are Fe, Co, Ni, because of two main reasons: (i) high
solubility of carbon in these metals at high temperatures; and (ii) high carbon diffusion
rate in these metals.
• Apart from popularly used transition metals (Fe, Co, Ni), a range of other metals (Cu, Pt,
Pd, Mn, Mo, Cr, Sn, Au, Mg, Al) has also been successfully used for horizontally-aligned
SWCNT growth on quartz substrates.
• Thin films of catalyst coated on various substrates are good in getting uniform CNT
deposits. The key factor to get pure CNTs is achieving hydrocarbon decomposition on
the catalyst surface alone.
• Commonly used substrates in CVD are graphite, quartz, silicon, silicon carbide, silica,
alumina, alumino-silicate (zeolite),CaCO3, magnesium oxide etc.
• Metal-substrate reaction (chemical bond formation) would cease the catalytic behavior
of the metal. The substrate material, its surface morphology and textural properties
greatly affect the yield and quality of the resulting CNTs.
SWCNT OR MWCNT
• Formation of single- or multi-wall CNT (SWCNT or MWCNT, respectively) is
governed by the size of the catalyst particle. when the particle size is a few nm,
SWCNT forms; whereas particles a few tens nm wide favour MWCNT formation.
• low-temperature CVD (600–900 C) yields MWCNTs, whereas high-temperature
(900–1200 C) reaction favors SWCNT growth. MWCNTs are easier to grow from
most of the hydrocarbons, while SWCNTs grow from selected hydrocarbons (viz.
carbon monoxide, methane, etc. which have a reasonable stability in the temperature
range of 900–1200 C).
INTRODUCTION
Schematic diagram of the CVD coating. Standard experimental setup used in
chemical vapor deposition method.
CHEMICAL VAPOR DEPOSITION STEPS:-
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.
CHEMICAL VAPOUR DEPOSITION FOR CNT
GROWTH
• Carbon source in gaseous form is allowed to flow over a
heated substrate coated with a catalyst.
• Reactive carbon atoms diffuse towards the substrate and
binds on to it.
• When proper conditions are maintained, CNT grows on the
surface of catalyst.
• Control over diameter and growth rate can be maintained.
• Usually results in SWNT and rarely MWNT.
• In CNT hydrocarbon is broken to generate reactive carbon species
which diffuses in to the catalytic substrate.
• Temperature between 550 to 750OC (sometimes even upto 1200OC) is
manitained.
• Electron beam or resistive heating techniques are used to impart energy
to the hydrocarbon to break.
• Various researchers have grown various dimensions of CNT (both
SWNT and MWNT) at various pressure, temperature range using
different catalysts.
• Note worthy is that Vohs [Link] has synthesized MWNT at just 175OC
using metal encapsulated dendrimers.
SPECIFICS OF CNT GROWTH
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 Substrate growth
(The catalyst formation (Catalyst Nanoparticles or metal
and nanotube growth Precursors are deposited
occur literally in mid air) on the substrate as SiO2)
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)
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
TWO TYPES OF 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
• When the catalyst – substrate interaction is weak (metal has an acute
contact angle with the substrate)
• when the catalyst–substrate interaction is strong (metal has an
obtuse contact angle with the substrate)
Tip-Growth Mechanism Base-Growth Mechanism
Magnified SEM image revealing the Magnified SEM image revealing the
catalytic nanoparticles in the CNT tips. catalytic nanoparticles in the CNT base.
PROS-
• Easiest to scale up to industrial production; long length, simple process, SWNT diameter
controllable, quite pure
CONS-
• CNTs are usually MWNTs and often riddled with deffects.
THANK YOU!!!!!
