Zero dimensional(0-D):These nanomaterials have Nanodimensions in all the three directions.

Metallic nanoparticles
including gold and silver nanoparticles and semiconductor
such as quantam dots are the perfect example of this kind
of nanoparticles. Most of these nanoparticles are spherical
in size and the diameter of these particles will be in the1-50
nm range. Cubes and polygons shapes are also found for
this kind of nanomaterials.

highly scattered in terms of energy

-easily controllable and accessible, yet poor inherent
performance

One dimensional(1-D):In these nanostructures, one

dimension of the nanostructure will be outside the
nanometer range. These include nanowires, nanorods, and
nanotubes. These materials are long (several micrometer in
length), but with diameter of only a few nanometer.
Nanowire and nanotubes of metals, oxides and other
materials are few examples of this kind of materials

Answer: take advantage of both semiconductors and atomic

systems Semiconductor quantum dot material

Two dimensional(2-D):In this type of nanomaterials, two

dimensions are outside the nanometer range. These include
different kind of Nano films such as coatings and thin-filmmultilayers, nano sheets or nano-walls. The area of the
nano films can be large (several square micrometer),but
the thickness is always in nano scale range
Three Dimensional(3-D):All dimensions of these are
outside the nano meter range. These include bulk materials
composed of the individual blocks which are in the
nanometer scale (1-100 nm)
A summary on electron behaviour
Free space
-plane wave with inherent electron mass
-continued parabolic dispersion (E~k) relation density of
states in terms of E: continues square root dependence
Bulk semiconductor
-plane wave like with effective mass, two different type of
electrons identified with opposite sign of their effective
mass, i.e., electrons and holes
-parabolic band dispersion (E~k) relation density of states
in terms of E: continues square root dependence, with
different parameters for electrons/holes in different band
Quantum well
-discrete energy levels in 1D for both electrons and holes
-plane wave like with (different) effective masses in 2D
parallel plane for electrons and holes
-dispersion (E~k) relation: parabolic bands with discrete
states inside the stop-band
-density of states in terms of E: additive staircase functions,
with different parameters for electrons/holes in different
band
Quantum wire
-discrete energy levels in 2D cross-sectional plane for both
electrons and holes
-plane wave like with (different) effective masses in 1D for
electrons and holes
-dispersion (E~k) relation: parabolic bands with discrete
states inside the stop-band
-density of states in terms of E: additive staircase decayed
functions, with different parameters for electrons/holes in
different band
Quantum dot
-discrete energy levels for both electrons and holes
-dispersion (E~k) relation: atomic-like k-independent
discrete energy states only
-density of states in terms of E: -functions for
electrons/holes
Why we are interested in nano-material?
Electrons in semiconductors:
-highly mobile, easily transportable and correlated, yet

Electrons in atomic systems:

-highly regulated in terms of energy, but not mobile
-excellent inherent performance, yet hardly controllable or
accessible

0D Nanomaterials : Quantum dots

-Quantum dots are small devices that contain a tiny droplet
of free electrons.
-Typical dimensions are between nanometers to a few
microns.
-A quantum dot can have anything from a single electron to
a collection of several thousands.
-The size ,shape and number of electrons can be precisely
controlled
-Just as in an atom, the energy levels are quantized due to
the confinement of electrons.
-The 3D spatial confinement is observed in the quantum
dots.
-In quantum dots even if one electron leaves the structure
there is a significant change in the properties.
-Unlike atoms however, quantum dots can be easily
connected to electrodes and are therefore excellent tools to
study atomic-like properties.
-The potential of nearby metal gate is changed.
-The atomic structure might behave as a lead one minute
and gold next minute
-The fanciful idea of designer materials might be realized
0D Fullerenes
In the mid-1980s a new class of carbon material was
discovered called carbon 60 (C60) (Kroto et al 1985). These
are spherical molecules about 1nm in diameter, comprising
60 carbon atoms arranged as 20 hexagons and 12
pentagons: the configuration of a football. The C60 species
was named Buckminsterfullerene in recognition of the
architect Buckminster Fuller, who was well-known for
building geodesic domes, and the term fullerenes was then
given to any closed carbon cage. In 1990, a technique to
produce larger quantities of C60 was developed by
resistively heating graphite rods in a helium atmosphere
(Krtschmer et al 1990). Several applications are envisaged
for fullerenes, such as miniature ball bearings to lubricate
surfaces, drug delivery vehicles and in electronic circuits.
0D Dendrimers
Dendrimers are spherical polymeric molecules, formed
through a nanoscale hierarchical self-assembly process.
There are many types of dendrimer; the smallest is several
nanometres in size. Dendrimers are used in conventional
applications such as coatings and inks, but they also have a
range of interesting properties which could lead to useful
applications. For example, dendrimers can act as nanoscale
carrier molecules and as such could be used in drug
delivery. Environmental clean-up could be assisted by
dendrimers as they can trap metal ions, which could then
be filtered out of water with ultra-filtration techniques.
1D Carbon nanotubes
Carbon nanotubes (CNTs) were first observed by Sumio
Iijima in 1991. CNTs are extended tubes of rolled graphene
sheets. There are two types of CNT: single-walled (one
tube) or multi-walled (several concentric tubes) Both of
these are typically a few nanometres in diameter and
several micrometres (10-6m) to centimetres long. CNTs
have assumed an important role in the context of
nanomaterials, because of their novel chemical and
physical properties. They are mechanically very strong

(their Youngs modulus is over 1 terapascal, making CNTs as

stiff as diamond), flexible (about their axis), and can
conduct electricity extremely well (the helicity of the
graphene sheet determines whether the CNT is a
semiconductor or metallic). All of these remarkable
properties give CNTs a range of potential applications: for
example, in reinforced composites, sensors,
nanoelectronics and display devices.
1D Nanowires
Nanowires are ultrafine wires or linear arrays of dots,
formed by self-assembly. They can be made from a wide
range of materials. Semiconductor nanowires made of
silicon, gallium nitride and indium phosphide have
demonstrated remarkable optical, electronic and magnetic
characteristics (for example, silica nanowires can bend light
around very tight corners). Nanowires have potential
applications in high-density data storage, either as
magnetic read heads or as patterned storage media, and
electronic and opto-electronic nanodevices, for metallic
interconnects of quantum devices and nanodevices. The
preparation of these nanowires relies on sophisticated
growth techniques, which include self assembly processes,
where atoms arrange themselves naturally on stepped
surfaces, chemical vapour deposition (CVD) onto patterned
substrates, electroplating or molecular beam epitaxy (MBE).
The molecular beams are typically from thermally
evaporated elemental sources.
One-dimensional structure Diameter: 1-100
nanometers (10-9 m)
Length: microns (10-6 m),
Exhibits crystal structure, Unlike quantum dots (0dimensional)
Many different materials, Metals, semiconductors,
oxides

(The resistivity : 106 cm)

(Mobility: 200,000 cm2 V-1 s-1)
But, weak bonding between layers
Separated by mechanical exfoliation of 3D graphite crystals
-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
Properties of graphene
- Electronic properties, Thermal properties, Mechanical
properties, Optical properties, Relativistic charge carriers,
Anomalous quantum Hall effect
- High electron mobility (at room temperature ~ 200.000
cm2/(Vs),, ex. Si at RT~ 1400 cm2/(Vs), carbon nanotube:
~ 100.000 cm2/(Vs), organic semiconductors (polymer,
oligomer): <10 cm2/(Vs)
Where d is the drift velocity in m/s (SI units) E is the
applied electric field in V/m (SI) is the mobility in m2/
(Vs), in SI units.
Resistivity of the graphene sheet ~106 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 (sigma), of the
material, or

The Discovery, Development, and Applications of

Fullerenes

2D Thin film, layers and surfaces

Two-dimensional nanomaterials, such as thin films and
engineered surfaces, have been developed and used for
decades in fields such as electronic device manufacture,
chemistry and engineering. In the silicon integrated-circuit
industry, for example, many devices rely on thin films for
their operation, and control of film thicknesses approaching
the atomic level is routine. Monolayers (layers that are one
atom or molecule deep) are also routinely made and used
in chemistry. The formation and properties of these layers
are reasonably well understood from the atomic level
upwards, even in quite complex layers (such as lubricants).
Advances are being made in the control of the composition
and smoothness of surfaces, and the growth of films.
Engineered surfaces with tailored properties such as large
surface area or specific reactivity are used routinely in a
range of applications such as in fuel cells and catalysts. The
large surface area provided by nanoparticles, together with
their ability to self assemble on a support surface, could be
of use in all of these applications.
What is graphene?
In late 2004, graphene was discovered by Andre Geim and
Kostya Novoselov (Univ. of Manchester).- 2010 Nobel Prize
in Physics
Q1. How thick is it?
a million times thinner than paper
(The interlayer spacing : 0.33~0.36 nm)
Q2. How strong is it?
stronger than diamond
(Maximum Young's modulus : ~1.3 TPa)
Q3. How conductive is it?
better than copper

Buckyball Discovery
-1985: British chemist Harry Kroto studied molecules with
exactly sixty carbon atoms found near red giant stars
-Kroto collaborated with Richard Smalley and Robert Curl to
recreate the conditions in the laboratory and form C60
molecules by laser vaporization of graphite
-The scientists hypothesized that the molecules were made
of hexagonal carbon rings blasted apart from the graphite
structure, and that the molecule must be spheroid to satisfy
valence requirements
Determining the C60 Structure
-After considerable work, Kroto, Smalley, and Curl
determined that the structure of the C60 buckyball was a
combination of 12 pentagonal and 20 hexagonal rings,
forming a spheroid shape with 60 vertices for the 60
carbons.
-The pentagonal rings sit at the vertices of an icosahedron
such that no 2 pentagonal rings are next to each other
-Curl, Kroto, and Smalley received the Nobel Prize in 1996
for their work.
-The architect R. Buckminster Fuller designed a geodesic
dome for the 1967 Montreal World Exhibition with the same
structure; the scientists thus named the new molecule
Buckminsterfullerene, which was shortened to fullerene
when referring to the family of molecules
Haymets Prediction
-Independently, near the same time, Tony Haymet of the
University of California at Berkeley published a paper
predicting the existence of a compound of this kind, which

he called footballene.
-The molecule corannulene, with a similar nonplanar
assembly of carbons in pentagonal and hexagonal rings, led
Haymet to predict the existence of a similar spheroid
molecule, with sixty carbons in twelve pentagons and
twenty hexagons.
Bond Structure and Reactivity
-The bonding pattern of the C60 fullerene is shown here,
with yellow bonds representing double bonds and red
bonds representing single bonds.
-The pentagonal rings contain only single bonds; double
bonds have a shorter bond length and lead to instability in
the pentagonal ring.
-The limitations on double bond locations lead to poor
delocalization of electrons, increasing the molecules
reactivity.
Fullerene Reactions
Possible reactions C60 and C70 (to a lesser extent) may
undergo
Additions
Polymerization
Substitutions also possible (doping with boron)
Conventional Synthesis
-Kroto, Smalley, and Curl used laser vaporization of
graphite to produce the carbon soot from which the
fullerenes could be isolated in microscopic quantities
-Krtschmer and colleagues developed a contact arc
discharge method for macroscopic production, known as
the Krtschmer-Huffman method.
1. Graphite electrodes kept in gentle contact are arc
passing alternating current through them in an atmosphere
of helium
2. The evaporated graphite takes the form of soot, which is
dissolved in a nonpolar solvent. The solvent is dried away
and the C60 and C70 fullerenes can be separated from the
residue.
3. Optimizing current and helium pressure and flow rate
leads to yields of up to 15% with this method.
Selective-Size Synthesis
There is a desire to control the size of the fullerenes for
various applications.
-Example: to increase the size of molecules to encage in
fullerenes creates the need for a larger cage
-Currently the mechanism by which fullerenes form is
unknown
-In conventional fullerene formation only C60 and C70 are
produced due to their stability
Two groups (Rubin and Tobe) independently investigated
cyclic polyynes as precursors to fullerenes.
-Neither group were able to produce C60 by flash vacuum
pyrolysis (FVP) of the cyclic polyyne
-They still believe this synthesis will work
Proposed Mechanism
-Cyclic polyyne folds onto itself so tightly the new carbon
bonds can form (dotted lines)

Fullerene Engineering
Exohedral Fullerenes
-Atoms, molecules, and complexes are attached to the
exterior of the cage
Endohedral Fullerenes
-Molecules are enclosed within the cage
Nanopeapods
-Fullerene molecules contained in carbon nanotubes

Exohedral Fullerenes--Application for Hydrogen

Storage
-Hydrogen storage for fuel-cell powered vehicles; USDOE
says need 9 wt% hydrogen storage density
-Organometallic molecules based upon C60 and borondoped C48B12
-Complexes of transition metals with hydrogen on
pentadiene rings can store up to six dihydrogen species
May polymerize when the hydrogen is removed,
rendering the process irreversible.
-Arranging the complexes on buckyballs, such as
C60[ScH2]12 and C48B12[ScH]12, leads to stable species
which can reversibly absorb additional hydrogen.
Hydrogen Storage
-Nearly 9 wt% can be retrieved reversibly and room
temperature and near ambient pressure.
-Doping with boron
Reduces the fullerene weight
Enhances the complexs stability by increasing the
binding energy
Allows the binding of an additional H2 molecule per Sc,
increasing the amount of retrievable H2
Endohedral Fullerenes
-Fullerene cages with encapsulated molecule have many
potential applications. For example scientists believe they
will be able to encage a radioactive tracer and inject that
safely into the human body.
-Currently various molecules can be encaged in the
fullerene cage.
1. Metal (La@C82), noble gas (He@C60),
multimetallofullerene (Sc2@C66)
2. Product yields are less than 2% in all cases
-Endohedral fullerenes have presented a lot of new
information to researchers.
For metallofullerenes there is a charge transfer between
the cage and enclosed metal, Sc2@C66 stabilizing what
may not be a stable cage alone

TNT Synthesis
-Improved synthesis of endohedral formation came in 1999
by introducing nitrogen to conventional KrtschmerHuffman generator
1. Sc3N@C80 trimetal nitride fullerene
2. Increased yields to ~5%
-This new process was named trimetal nitride template
(TNT) and applied to form a variety of products.
1. M3N@C80 where M=Sc, Y, Tb, Ho, and Er
-Dunsch and co-workers enhanced the synthesis by using
NH3 as the reactive gas in the generator. Endohedral
fullerenes were formed as the major product for the first
time.
-C80 and Sc3N are not stable individually
-Very restricting, it can only apply to trimetal nitrides.
Nanopeapods
-Single-walled carbon nanotubes (SWNTs) encapsulating
C60
-Conventional synthesis of nanopeapods had a lot of
challenges. Reactions had to be run under very difficult
conditions and were very restricting.
1. Vaporization of thermally stable fullerene molecules
2. At least 350C in high vacuum
-Theoretical studies showed the activation barrier for this
reaction to be only ~0.37eV.
1.The reaction should proceed at room temperature
Various Nanopeapod Syntheses
-Khlobystov and group attempted numerous synthesis
methods at or near room temperature (30-50C) with a
yield <1%

1. Mechanical mixing
2. Adding SWNTs to concentrated solution of fullerenes
3. Adding fullerenes to SWNTs solution
-Supercritical fluids, most important scCO2, was the next
used in the process
1. SWNTs and fullerenes mixed in solvent, evaporated
solvent, put in supercritical CO2 under high pressure for 10
days
2. Produced yields ~30%
scCO2 Properties
-Investigating why scCO2 increases product yield compared
to other solvents
1. The interaction with carbon 60 can vary between
favorable and repulsive by changing the molar density of
CO2, a function of temp and pressure
2. Carbon dioxide has the smallest critical diameter
Mechanism for Nanopeapod Formation
-scCO2 can carry the fullerene into the SWNT because of
the attraction between the molecules
-Varying temperature and pressure can create a repulsive
interaction encouraging the solvent molecule to diffuse out
of the SWNT

Summary
-C60, buckyball, was the first fullerene discovered
1. It is the third form of pure carbon (graphite, diamond,
buckyballs)
-Variations of fullerenes include exohedral, endohedral and
nanopeapods
-Synthesis challenges still exist for all variations of
fullerenes because the mechanism of formation is still
unknown
-Potential applications in medicine, nanoelectronics, and
energy

Carbon Nanotubes
What Are They?
-Allotropes of carbon with a cylindrical structure
-Can be capped on the ends with buckyballs or open ended
-Composed entirely of sp2 bonds
Graphite
Hexagonal graphite:
1. Graphite has a structure containing layers of atoms
arranged at the corners of contiguous hexagons.
2. (not to be confused with hexagonal close packed).
3. The ease with which layers slide against each other is
consistent with the much larger distance between carbon
atoms in different layers (335 pm) than between carbon
atoms in the same layer (142 pm).
4. The lattice constant a = 246.6 pm
5. C=669 pm
What is tube rolled out of ?
-An ideal nanotube can be thought of as a hexagonal
network of carbon atoms that has been rolled up to make a
cylinder.
-width: nanometer: "capped" with half of a fullerene

molecule.
-length: microns
What is a Carbon Nanotube?
-CNT is a tubular form of carbon with diameter as small as
1nm.
-Length: few nm to microns.
-CNT is configurationally equivalent to a two dimensional
graphene sheet rolled into a tube.
-A CNT is characterized by its Chiral Vector: Ch = n 1 + m
2,
teta - Chiral Angle with respect to the zigzag axis.
Types of CNTs
-Single Wall CNT (SWCNT)
-Multiple Wall CNT (MWCNT)
-Can be metallic or semiconducting depending on their
geometry.

Chapter 5