ETE444 :: Lecture 4

Dr. Mashiur Rahman

Introduction to Carbon Nanotubes

Springer Handbook of
Nanotechnology (Page 39-)
 Introduction
• Carbon nanotubes are among the amazing objects that
science sometimes creates by accident, without meaning
to, but that will likely revolutionize the technological
landscape of the century ahead. Our society stands to
be significantly influenced by carbon nanotubes, shaped
by nanotube applications in every aspect, just as silicon-
based technology still shapes society today.
• The world already dreams of spaceelevators tethered by
the strongest of cables, hydrogen-powered vehicles,
artificial muscles, and so on – feasts that would be made
possible by the emerging carbon nanotube science.
 History
• Some of the first evidence that the nanofilaments thus
produced were actually nanotubes – i. e., exhibiting an
inner cavity – can be found in the transmission electron
microscope micrographs published by Hillert et al. in
1958.
• The worldwide enthusiasm came unexpectedly in 1991,
after the catalyst-free formation of nearly perfect
concentric multiwall carbon nanotubes (c-MWNTs) was
reported as by-products of the formation of fullerenes by
the electric-arc technique.
• single-wall carbon nanotubes (SWNTs) simultaneously
by Iijima et al. and Bethune et al.
 Carbon bond
There are three significant reasons for the wide range of properties of
materials containing carbon:
• Carbon atoms can bond together with many types of atoms, using a
process called covalent bonding. When carbon atoms bond with
different types of atoms, they form molecules with properties that vary
according to the atoms they’ve bonded with.
• Each carbon atom can form these covalent bonds with four other
atoms at a time. This four-bond capability allows carbon atoms to
bond to other carbon atoms to make chains of atoms — and to bond
with other kinds of atoms at various points along such chains. This
wide range of potential combinations of atoms in a molecule allows
for a correspondingly wide range of potential properties.
• There’s no other element in the periodic table that bonds as strongly
to itself and in as many ways as the carbon atom. Carbon atoms can
bond together in short chains, in which case they may have the
properties of a gas. They may bond together as long chains, which
might give you a solid, like a plastic. Or, they can bond together in 2-
or 3-dimensional lattices, which can make for some very hard
materials, such as a diamond.
 graphite

The structure of carbon atoms connected by

covalent bonds in a sheet of graphite.
 Buckyball

Sixty carbon atoms in the shape of a sphere — a buckyball.

Source: Nanotechnology For Dummies

Desperately seeking buckyballs
• Richard Smalley at Rice University
• University of Sussex, Harry Kroto
• Bob Curl, Rice University
• August of 1985
 Buckyball
• A buckyball (short for buckminsterfullerene) is a
molecule containing 60 carbon atoms. Each
carbon atom is bonded to three adjacent carbon
atoms, just as in graphite. However the carbon
atoms in a buckyball form a teensy-weensy
sphere that’s about 1 nanometer in diameter, as
shown in Figure. Because one of the properties
of carbon atoms is that they can bond to many
other types of atoms, researchers can use them
to create customized molecules, useful in
various applications.
 Structure of Carbon
Nanotubes
• Single-wall carbon nanotube (SWNT)
• Multiwall Nanotubes (MWNT)
Structure of Carbon Nanotubes
Real images
 Multiwall Nanotubes
• Such nanotubes are generally formed either by
the electric-arc technique (without need of any
catalyst) or by catalyst-enhanced thermal
cracking of gaseous hydrocarbons or CO
disproportionation.
• The number of walls (or number of coaxial
tubes) can be anything, starting from two, with
no upper limit. The intertube distance is
approximately that of the intergraphene distance
in turbostratic, polyaromatic solids, i. e. 0.34 nm.
 c-MWNT

concentric type (c-

MWNT), in which
SWNTs with regularly
increasing diameters
are coaxially
 Producing nanotubes from thin air
• high-pressure carbon monoxide
deposition, or HiPCO
• chemical-vapor deposition, or CVD
• plasma procces
• Laser Ablation
• Electric-Art Method
 high-pressure carbon monoxide
deposition, or HiPCO
• This method involves a heated chamber through
which carbon monoxide gas and small clusters
of iron atoms flow. When carbon monoxide
molecules land on the iron clusters, the iron acts
as a catalyst and helps a carbon monoxide
molecule break up into a carbon atom and an
oxygen atom. The carbon atom bonds with other
carbon atoms to start the nanotube lattice; the
oxygen atom joins with another carbon
monoxide molecule to form carbon dioxide gas,
which then floats off into the air.
chemical-vapor deposition, or CVD
• In this method, a hydrocarbon — say, methane
gas (one carbon atom and four hydrogen atoms)
— flows into a heated chamber containing a
substrate coated with a catalyst, such as iron
particles. The temperature in the chamber is
high enough to break the bonds between the
carbon atoms and the hydrogen atoms in the
methane molecules — resulting in carbon atoms
with no hydrogen atoms attached. Those carbon
atoms attach to the catalyst particles, where they
bond to other carbon atoms — forming a
nanotube.
 plasma process
• A brand-new method uses a plasma
process to produce nanotubes. Methane
gas, used as the source of carbon, is
passed through a plasma torch. Nobody’s
revealed the details of this process yet,
such as what, if any, catalyst is used. One
of the initial claims is that this process is
25 times more efficient at producing
nanotubes than the other two methods.
 Laser Ablation
• In the absence of catalysts in the target, the soot
collected mainly contains multiwall nanotubes (c-
MWNTs). Their lengths can reach 300 nm.
• Their quantity and structure quality are dependent on the
oven temperature. The best quality is obtained for an
oven temperature set at 1,200 ◦C. At lower oven
temperatures, the structure quality decreases, and the
nanotubes start presenting many defects.
• As soon as small quantities (few percents or less) of
transition metals (Ni, Co) playing the role of catalysts are
incorporated into the graphite pellet, products yielded
undergo significant modifications, and SWNTs are
formed instead of MWNTs.
 Electric-Art Method
• The principle of this technique is to vaporize carbon in the
presence of catalysts (iron, nickel, cobalt, yttrium, boron,
gadolinium, and so forth) under reduced atmosphere of inert
gas (argon or helium).
• After the triggering of the arc between two electrodes, a
plasma is formed consisting of the mixture of carbon vapor,
the rare 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. The anode erosion rate is more or less important
depending on the power of the arc and also on the other
experimental conditions. It is noteworthy that a high anode
erosion does not necessarily lead to a high carbon nanotube
production.
Solar Furnace
Synthesis of Aligned Carbon Nanotubes
Several applications (such as field-emission-based
display), require that carbon nanotubes grow
as highly aligned bunches, in highly ordered arrays, or
located at specific positions. In that case, the purpose
of the process is not mass production but controlled
growth and purity, with subsequent control of nanotube
morphology, texture, and structure. Generally speaking,
the more promising methods for the synthesis of aligned
nanotubes are based on CCVD processes, which
involve molecular precursors as carbon source, and
method of thermal cracking assisted by the catalytic
activity of transition metal (Co, Ni, Fe) nanoparticles
deposited onto solid supports.
Properties of Carbon Nanotubes
• General Properties
• SWNT Adsorption Properties
• Transport Properties
• Mechanical Properties
• Reactivity
 General Properties
• SWNT-type carbon nanotube diameters fall in
the nanometer range and can be hundreds of
micrometers long.
• SWNTs are stable up to 750 ◦C in air and up to∼
1,500–1,800 ◦C in inert atmosphere beyond
which they transform into regular, polyaromatic
solids.
• They have half the mass density of aluminum.
While the length of SWNTs can be macroscopic,
the diameter has a molecular dimension.
 SWNT Adsorption Properties
• An interesting feature of SWNTs is their very
high surface area, the highest ever due to the
fact that a single graphene sheet is probably the
unique example of a ma terial energetically
stable in normal conditions while consisting of a
single layer of atoms. Ideally, i. e. not
considering SWNTs in bundles but isolated
SWNTs, and provided the SWNTs have one end
opened (by oxidation treatment for instance), the
real surface area can be equal to that of a
single, flat graphene, i. e.∼ 2,700m2/g.
 Transport Properties
• The narrow diameter of SWNTs has a
strong influence on its electronic
excitations due to its small size compared
to the characteristic length scale of low
energy electronic excitations. Combined
with the particular shape of the electronic
band structure of graphene, carbon
nanotubes are ideal quantum wires.
 Mechanical Properties
• While tubular nano-morphology is also observed for
many two-dimensional solids, carbon nanotubes are
unique through the particularly strong threefolded
bonding of the curved graphene sheet, which is stronger
than in diamond as revealed by their difference in C−C
bond length (0.142 vs. 0.154 nm for graphene and
diamond respectively).
• This makes carbon nanotubes – SWNTs or c-MWNTs –
particularly stable against deformations. The tensile
strength of SWNTs can be 20 times that of steel and has
actually been measured equal to ∼ 45 GPa.
 Reactivity
• The chemical reactivity of graphite,
fullerenes, and carbon nanotubes exhibits
some common features. Like any small
object, carbon nanotubes have a large
surface with which they can interact with
their environment.
 Applications
• SPM probes
• Gas storage
• Adsorbents of toxic gases
• Bio-Sensors
• Chemical Sensors
SPM probes
 Gas Storage – Hydrogen
• U.S. Department of Energy Hydrogen Plan (the
ratio of H2 weight to system weight) of 6.5 wt%
hydrogen and a volumetric density of 63
kgH2/m3.
• The ideal hydrogen storage system needs to be
light, compact, relatively inexpensive, safe, easy
to use, and reusable without the need for
regeneration.
• For example, liquid hydrogen systems are very
expensive, primarily because the hydrogen must
be cooled to about −252 ◦C
 CNT based H2 storage
• 1998: A group from Northeastern University was the first to
report the supposedly successful hydrogen storage in
carbon layered nanostructures possessing some
crystallinity. The authors claimed that, in platelet nanofibers
(3–50 nm in width), hydrogen can be stored up to 75 wt%,
meaning a C/H ratio of 1/9.
• 1999: Dresselhaus and coworkers reported hydrogen
storage in SWNTs (1.85 nm of average diameter) at room
temperature. A hydrogen storage capacity of 4.2wt% was
achieved reproducibly under 100 bar for a SWNT-containing
material of about 0.5 g. 78% of the adsorbed hydrogen
could be released under ambient pressure at room
temperature, while the release of the residual stored
hydrogen required some heating at 200 ◦C.
 Gas Storage
• Gases other than Hydrogen Encouraged by the potential
applications related to hydrogen adsorption, several
research groups have tried to use carbon nanotubes as
a stocking and transporting mean for other gases such
as: oxygen, nitrogen, noble gases (argon and xenon),
and hydrocarbons (methane, ethane, and ethylene).
These studies have shown that carbon nanotubes could
become the world’s smallest gas cylinders combining
low weight, easy transportability, and safe use with
acceptable adsorbed quantities. Thanks to their nano-
sizes, nanotubes might also be used in medicine where
physically confining special gases (like 133Xe for
instance) prior to injection would be extremely useful.
 Adsorbents
• Carbon nanotubes were recently found to be able to
adsorb some toxic gases such as dioxins (2001), fluo-
ride (2001), lead (2002), or alcohols (2000) better than
the materials used so far, such as activated carbon.
• These pioneering works opened a new field of
applications as cleaning filters for many industrial
processes having hazardous by-products.
• Adsorption of dioxins, which are very common and
persistent carcinogenic by-products of many industrial
processes, is a good example of the interest of
nanotubes in this field.
 Bio-Sensors
• Attaching molecules of biological interest to carbon
nanotubes is an ideal way to realize nanometer-sized
biosensors. Indeed, the electrical conductivity of such
functionalized nanotubes would depend on modifications
of the interaction of the probe with the studied media,
because of chemical changes or as result of their
interaction with target species. The science of attaching
biomolecules to nanotubes is rather recent and was
inspired by similar research in the fullerene area.
 Chemical Sensors
• The electrical conductance of semiconductor
SWNTs was recently demonstrated to be highly
sensitive to the change in the chemical
composition of the surrounding atmosphere at
room temperature, due to the charges transfer
between the nanotubes and the molecules from
the gases adsorbed onto the SWNT surface.
• First tries involved NO2 or NH3 and O2. SWNT-
based chemical NO2 and NH3 sensors are
characterized by extremely short response time,
thus being different from conventionally used
sensors.
 Nanowires

Springer Handbook of Nanotechnology

(Page 99-145)
 Nanowires
• the sizes of nanowires are typically large enough (> 1
nm in the quantum confined direction) having local
crystal structures closely related to their parent
materials.
• Driving forces:
1. these new research and development opportunities
2. the smaller and smaller length scales now being
used in the semiconductor, opto-electronics, and
magnetics industries
3. the dramatic development of the biotechnology
industry where the action is also at the nanoscale,
the nanowire research field has developed with
exceptional speed in the last few years
vapor-liquid-solid (VLS)
SEM images of (a) 6-fold (b) 4-fold
and (c) 2-fold symmetry nanobrushes
made of an In2O3 core and ZnO
nanowire brushes [4.107], and of (d)
ZnO nanonails [4.108]
photo-luminescence (PL) &
electro-luminescence (EL)
Chemical and Biochemical
Sensing Devices
 Selected syntheses
of nanowires by material
Quantum dots
• semiconducting nanocrystals roughly 5nm
in size
• Quantum dots are nanometer-scale
nanocrystals composed of a few hundred
to a few thousand semiconductor atoms
made out of bio-inert materials