Structure, Property and Relationship in

Nanomaterials
A report by Aditya Upasani 17CHE201

Ajay Verma 17CHE202

Akash Patel 17CHE203

Bharat Honmane 16CHE423

Contents
LIST OF FIGURES ........................................................................................................................ 4
LIST OF TABLES .......................................................................................................................... 4
ABSTRACT .................................................................................................................................... 5
1. INTRODUCTION TO NANOMATERIALS......................................................................... 6
1.1 CLASSIFICATION OF NANOMATERIALS ................................................................ 7
1.2 SYNTHESIS METHODS ................................................................................................ 9
1.2.1 Bottom Up approach: ................................................................................................ 9
1.2.2 Top Down approach:.................................................................................................... 15
1.3 CHARACTERIZATION TECHNIQUES: .................................................................... 17
2. NANOWIRES....................................................................................................................... 19
2.1 STRUCTURE RELATIONSHIPS OF NANOWIRES.................................................. 21
2.2 PROPERTIES OF NANOWIRES ................................................................................. 22
Physical properties of Nanowires ......................................................................................... 23
Magnetic properties of Nanowires ........................................................................................ 23
Electrical properties of Nanowires........................................................................................ 24
Optical properties of Nanowires ........................................................................................... 26
Mechanical properties of Nanowires .................................................................................... 27
3. CARBON NANOTUBES ..................................................................................................... 28
3.1 CLASSIFICATION: ...................................................................................................... 28
Single Walled Carbon Nanotube .......................................................................................... 28
Multi-walled Carbon Nanotube ............................................................................................ 29
3.2 PROPERTIES ................................................................................................................ 32
Physiochemical properties of CNTs ..................................................................................... 32
Electrical & structural properties of CNTs ........................................................................... 32
Mechanical properties of CNTs ............................................................................................ 33
Optical properties of CNTs ................................................................................................... 34
3.3 APPLICATIONS ................................................................................................................ 34
Carbon Nanotube Composites: ............................................................................................. 35
Electrochemical Devices:...................................................................................................... 35
Hydrogen Storage: ................................................................................................................ 35
 Field Emission Devices: ....................................................................................................... 36
Nanometer-Sized Electronic Devices: .................................................................................. 36
Sensors and Probes: .............................................................................................................. 36
4. FULLERENES ..................................................................................................................... 36
4.1 BUCKMINSTERFULLERENE ................................................................................. 38
4.2 SYNTHESIS OF BUCKMINSTERFULLERENE .................................................... 39
4.3 PROPERTIES ..................................................................................................................... 41
Molecular Properties ............................................................................................................. 41
Chemical properties- ............................................................................................................. 42
Physical Properties- .............................................................................................................. 42
Optical Properties- ................................................................................................................ 42
Solution properties-............................................................................................................... 42
Band Structure and Superconductivity ................................................................................. 43
4.3 APPLICATIONS ........................................................................................................... 44
Solar Cells ............................................................................................................................. 44
Fullerene Strengthening/Hardening of Metals- .................................................................... 44
Optical Application of Fullerene- ......................................................................................... 44
Fullerenes as Molecular Wires- ............................................................................................ 45
Fullerene in Medicine- .......................................................................................................... 45
5. REFERENCES: ........................................................................................................................ 47
LIST OF FIGURES
Figure 1: Nanotechnology in nature. Biological features such as DNA, cells and membranes are
of nanoscale. ................................................................................................................................... 6
Figure 2: Classification of nanomaterials. (The boundary regions of the first and second family
are indicated in black to emphasise the different atomic arrangements in the crystallites and
boundaries). ..................................................................................................................................... 7
Figure 3: Schematic inert gas condensation unit for the synthesis of nanocrystalline particles. .. 10
Figure 4: Schematic diagram of the plasma enhanced chemical vapour deposition (PECVD)
setup for growing directional CNTs. ............................................................................................ 11
Figure 5: Sol-gel processing methodology (C.J. Brinker and G.W. Scherer 1990). .................... 12
Figure 6: Multistage synthesis of porous Co3O4 nanosheets by a wet-chemical method............ 13
Figure 7: Schematic illustration of the formation process of the Fe3O4 nanoflakes by self
assembly. ....................................................................................................................................... 14
Figure 8: Schematic of the different stages during MA of a nominally ductile powder material:
a)starting powder b)flattened, layered composite particles c)homogeneous equiaxed particles. . 15
Figure 9: Layout of the sample and the process steps with AFM lithography ............................. 17
Figure 10: Various Characterization Techniques and its Applications. ....................................... 18
Figure 11: SEM image of Yittrium oxide nanowires.................................................................... 19
Figure 12: ZnO nanowhiskers and nanorods ................................................................................ 21
Figure 13:The variation of squareness of hysteresis loops of Co nanowire arrays with applied
magnetic field (H) parallel (||) and perpendicular () to the wire axes: (a) nanowire diameter, 78
nm and (b) nanowire diameter, 18 nm. ......................................................................................... 24
Figure 14: Conductance, G (2e2/h) of silver nanowires with........................................................ 25
Figure 15: Various Single Walled Carbon Nanotubes. ................................................................. 29
Figure 16: Multi Walled Carbon Nanotube. ................................................................................. 30
Figure 17: Buckminsterfullerene and Carbon Nanotube. ............................................................. 37
Figure 18: High-vacuum electrolysis of a C60-fullerene derivative. Slow diffusion into the anode
(right side) yields the characteristic purple color of pure C60...................................................... 39
Figure 19: Close view of Buckminsterfullerene. .......................................................................... 41
Figure 20: Solution of Pure C60 having purple color. ................................................................... 43
Figure 21: Fullerenes on a Porphyrin wire. .................................................................................. 45
Figure 22: Schematic of a Fullerene encapsulating another particle. ........................................... 46

LIST OF TABLES
Table 1: Differences between SWNT and MWNT....................................................................... 30
ABSTRACT

Nanomaterials refer to the class of materials with at least one of their dimensions in the nanometric
range. They are classified according to number of dimension which are there in nanometric scale.
The main methods to produce nanomaterials are based on the Bottom Up and Top Down
approaches. Characterization of nanomaterials is important to obtain information about their
properties and different techniques have been developed for it. Nanomaterials have different
properties than their bulk counterparts due to difference in behavior of the material at the
nanometric scale. Hence, for various materials, the properties such as mechanical strength, thermal
and electric conductivities, optical and magnetic properties show a great deal of deviation from
their bulk counterparts. These properties have been described for nanowires, nanotubes and
fullerenes.
 1. INTRODUCTION TO NANOMATERIALS

Nanomaterials are any materials which have at least one of their dimensions in the nanometric
scale i.e. between 1-100 nanometers. There are many examples of naturally occurring and
artificially occurring nanomaterials.

An example of nanomaterials is the Wootz steel, which is an extremely strong steel developed in
India around 300 BC. This steel has been extensively used for making swords as it could cut a
metal helmet into two pieces (popularly known as Damascus steel). Recently (Nature, 2006)
Pauflers group from Technical University Dresden, Germany, reported the presence of carbon
nanotubes and nanowires in Damascus steel.

The cell membranes, and several other functional organelles within the biological cell of living
beings, are in fact of nanometric size (Fig. 1). Proteins and enzymes together account for all the
metabolic activities in the body, an excellent illustration of the power of nanostructures. We are
all aware that life on earth could not have been sustained without the life-saving phenomenon of
photosynthesis that enables plant species to convert solar energy into biochemical energy forms.
Photosynthesis is enabled in plants by nanoscale molecular machinery, consisting of pigment
molecules like chlorophyll arranged inside stacked structures called thylakoid disks housed inside
micrometre-sized chloroplast cells.

Figure 1: Nanotechnology in nature. Biological features such as DNA, cells and membranes are of nanoscale.
 1.1 CLASSIFICATION OF NANOMATERIALS

Siegel classified nanostructured materials into four categories according to their dimensionality:
0D: nanoclusters, 1D: multilayers, 2D: nanograined layers and 3D: equiaxed bulk solids. Gleiter
further classified nanostructured materials according to the composition, morphology and
distribution of the nanocrystalline component. This classification includes many possible
permutations of materials and is quite broad. According to the shape of the crystallites, three
categories of nanostructured materials are distinguished (Fig. 2):

Rod-shaped crystallites (with layer thickness or rod diameter of the order of a few
nanometres)
Layer-shaped crystallites
Nanostructures composed of equiaxed nanometre-sized crystallites.

Figure 2: Classification of nanomaterials. (The boundary regions of the first and second family are indicated in black to
emphasise the different atomic arrangements in the crystallites and boundaries).

Depending on the chemical composition of the crystallites, the three categories of nanostructured
materials may be grouped into four families. The simplest case is where all crystallites and
interfacial regions have the same chemical composition. Examples of this family are
semicrystalline polymers or nanostructured materials made up of equiaxed nanometresized
crystals.

Nanostructured materials belonging to the second family consist of crystallites with different
chemical compositions. Quantum well structures are well-known examples of this case. If the
compositional variation occurs primarily between the crystallites and the interfacial regions, the
third family of nanostructured materials is obtained. Nanostructured materials consisting of
nanometre-sized W crystals with Ga atoms segregated to the grain boundaries are an example of
this type. An interesting new example of such materials was recently produced by co-milling Al2O3
and Ga. The fourth family of nanostructured materials is formed by nanometre-sized crystallites
dispersed in a matrix of different chemical composition.
 1.2 SYNTHESIS METHODS

There are different ways of classifying the synthesis routes for nanostructured materials. One of
them is based on the starting state of material, namely, gas, liquid and solid. Techniques such as
vapour condensation [physical vapour deposition (PVD) and chemical vapour deposition (CVD)
and variants of these techniques] use the gaseous state of matter as the starting material for
synthesizing nanoparticles. Techniques such as solgel, chemical and electrochemical
(electrolytic) deposition and rapid solidification processing use liquids as the starting material.
Severe plastic deformation processes such as high-energy ball milling, equichannel angular
extrusion, etc., and nano-lithography, start with solids for synthesizing nanocrystalline materials.
However, the most popular way of classifying the synthesis routes is based on how the
nanostructures are built, and such an approach leads to two routes, namely, the bottom-up and
the top-down approaches.

1.2.1 Bottom Up approach:

Individual atoms and molecules are brought together or self-assembled to form

nanostructured materials in at least one dimension.
All the starting materials are either liquids or gases.
Usually, the bottom-up techniques can give very fine nanostructures of individual
nanoparticles, nanoshells, etc., with narrow size distributions, if the process parameters are
effectively controlled.
Many of the Bottom Up techniques have difficulties in scaling up.

Physical Vapor Deposition: PVD is a versatile synthesis method and is capable of preparing thin
film materials with control at the nanometre scale by careful monitoring of the processing
conditions. PVD involves the generation of vapour phase either via evaporation, sputtering, laser
ablation or by using an ion beam. In evaporation, atoms are removed from the source, usually by
heating it above its melting point. On the other hand, in sputtering, atoms are ejected from the
target surface by the impact of energetic ions.

Inert gas condensation:

(IGC) combined with thermal evaporation is commonly used to synthesise metallic and metal
oxide nanopowders with a well-defined and narrow size distribution. This technique was originally
introduced by Ganqvist and Buhrman in 1976 and later developed by Gleiter in 1981. In this
process, a metal is evaporated inside an ultra-high vacuum (UHV) chamber filled with inert gas,
typically helium (Fig. 3). The vapourised species then loses energy via collisions with helium
molecules. As collisions limit the mean free path, supersaturation can be achieved above the
vapour source. At high supersaturation, the vapours rapidly form large numbers of clusters that
grow via coalescence and agglomeration. The clusters in the condensing gas are transported by
convective flow to a vertical cold finger surface filled with liquid nitrogen. The removal of
particles from the cold finger is carried out by a scraper assembly. They are collected via a funnel
and transported to an in situ compaction device or coated with a surfactant agent that prevents
them from agglomeration. The scraping and consolidation of particles are carried out under UHV
conditions to prevent oxidation of the metallic nanoparticles. The size, morphology and yield of
the clusters in gas condensation are dependent on three fundamental parameters:
Rate of supply of atoms to the region of supersaturation where condensation occurs
Rate of energy removal from the hot atoms via the condensing gas medium
Rate of removal of clusters once nucleated from the supersaturated region
Particle nucleation, coalescence and growth during condensation also play key roles in forming
small particles in large numbers.

Figure 3: Schematic inert gas condensation unit for the synthesis of nanocrystalline particles.

Chemical Vapor Deposition: Chemical vapour deposition (CVD) is a process where one or more
gaseous adsorption species react or decompose on a hot surface to form stable solid products. The
main steps that occur in the CVD process can be summarized as follows:
1. Transport of reacting gaseous species to the surface
2. Adsorption of the species on the surface
3. Heterogeneous surface reaction catalysed by the surface
4. Surface diffusion of the species to growth sites
5. Nucleation and growth of the film
6. Desorption of gaseous reaction products and transportation of reaction products away from the
surface.
CVD is a more complicated method than PVD for the formation of thin films and coatings. It
exhibits several distinct advantages, such as the capability to produce highly pure and dense films
or fine particles at reasonably high deposition rates, and the capability of coating complex-shaped
components uniformly due to its nonline-of-sight nature. A variety of metallic, ceramic and
semiconducting thin films are being deposited by CVD. Depending on the activation sources for
the chemical reactions, the deposition process can be categorized into thermally activated, laser-
assisted and plasma-assisted CVD.

Figure 4: Schematic diagram of the plasma enhanced chemical vapour deposition (PECVD) setup for growing directional
CNTs.

Sol Gel Processing: The solgel processing method has been in use for many years for producing
metal oxide and ceramic powders with high purity and high homogeneity. The solgel route offers
a degree of control of composition and structure at the molecular level. The process involves the
generation of a colloidal suspension (sol), which is subsequently converted to viscous gel and
solid material. Ebelman produced the first silica gel in 1846, and Cossa synthesized alumina gel
in 1870. Since then, aerogels of zirconia, silazane, borate and other ceramics have been synthesized
using the solgel technique.

In the process, reactive metal precursors were initially hydrolysed, followed by condensation and
polymerization reactions. Metal alkoxides are metalorganic compounds with an organic ligand
attached to a metal or metallic atom. They are the result of direct or indirect reactions between a
metal M and an alcohol ROH. Typical examples are methoxide (OMe; MOCH3) and ethoxide
(OEt; MOC2H5). During hydrolysis, the alkoxy group OR is replaced by hydroxo ligands (OH),
i.e., M(OR)z + H2O M(OH)(OR)z1 + ROH
where R is an alkyl group, CnH2n+1. The mechanism of this reaction involves the addition of a
negatively charged HO group to the positively charged metal centre (M+) followed by the
removal of ROH.
The factors that influence the hydrolysis reaction are:
Nature of the alkyl group
Nature of the solvent
Concentration of each species in the solvent
Temperature
Water to alkoxide molar ratio
Presence of acid or base catalysts
The most commonly studied metal alkoxide is silicon tetraethyl orthosilicate [TEOS;
Si(OC2H5)4]. The TEOS precursor can react readily with water via the following reaction:
Si(OR)4 + H2O Si(OR)3(OH) + ROH
As the hydrolysis of silicon alkoxides is very slow, the conversion of metal precursor
molecules into trialkoxy silanol, Si(OR)3(OH) proceeds more rapidly by adding acid or base
catalysts. Depending on the amount of water and catalyst present, hydrolysis may proceed
partially, in which the metal alkoxides convert into Si(OR)4n(OH)n, or may go to completion in
which all OR groups of alkoxides are replaced by OH:
Si(OR)4 + 4H2O Si(OH)4 + 4ROH
Subsequent condensation reaction sequences produce cluster species with SiOSi (siloxane)
bonds and water or alcohol as the by-products:
(OR)3Si OH + HO Si(OR)3 (OR)3 Si O Si(OR)3 + H2O
(OR)3 Si OR + HO Si (OR)3 (OR)3 Si O Si(OR)3 + ROH.

Figure 5: Sol-gel processing methodology (C.J. Brinker and G.W. Scherer 1990).
Wet Chemical Synthesis: Solution-based processing routes used for the synthesis of nanoparticles
include precipitation of solids from a supersaturated solution, homogeneous liquid phase chemical
reduction and ultrasonic decomposition of chemical precursors. These processes are attractive due
to their simplicity, versatility and availability of low cost precursors. Inorganic salt compounds
used in the wet chemical synthesis routes are more versatile and economical than alkoxides
employed in the solgel process. A typical example is the formation of nanocrystalline titania
powders via hydrolysis of TiCl4 at lower temperatures:
TiCl4 + 2H2O TiO2 + 4HCl
Once the solution becomes saturated, crystallization of titania takes place either through
homogeneous or heterogeneous nucleation. In the latter case, crystal seeds are added to the
solutions to promote the crystallization of titania nanoparticles.
Salt reduction is one of the most commonly adopted methods to generate the metal colloid
particles. The process involves the dissolution of metal salts in aqueous or non-aqueous
environments followed by the reduction of metal cations to the zero-valent state. The nature of the
metal salts determines the kind of reducing agent to be applied. To produce transition metal
nanoparticles, group 6 metal chlorides such as CrCl3, MoCl3 and WCl4 are reduced with NaBEt3 in
toluene solution at room temperature to form metal colloids of high yield.

Figure 6: Multistage synthesis of porous Co3O4 nanosheets by a wet-chemical method.

Self assembly: Self-assembly is a nanofabrication technique that involves aggregation of colloidal

nanoparticles into the final desired structure. This aggregation can be either spontaneous (entropic)
and due to the thermodynamic minima (energy minimization) energy minimization constraints, or
chemical and due to the complementary binding of organic molecules and supramolecules
(molecular self-assembly). Molecular self-assembly is one of the most important techniques used
in biology for the development of complex functional structures.
Since these techniques require that the target structures be thermodynamically stable, they tend to
produce structures that are relatively defect-free and self-healing. Self-assembly is by no means
limited to molecules or the nano-domain and can be carried out on just about any scale, making it
a powerful bottom-up assembly and manufacturing method (multi-scale ordering). Another
attractive feature of this technique relates to the possibility of combining the self-assembly
properties of organic molecules with the electronic, magnetic and photonic properties of inorganic
components.
Deoxyribonucleic acid (DNA), the framework on which all life is built, can be used to selfassemble
nanomaterials into useful macroscopic aggregates that display a number of desired physical
properties. DNA has a double-helix structure with two strands coiled around each other. When the
two strands are uncoiled, singular strands of nucleotides are left. These nucleotides consist of a
sugar (pentose ring), a phosphate (PO4) and a nitrogenous base. The order and architecture of these
components are essential for the proper structure of a nucleotide.

There are typically four nucleotides found in DNA: adenine (A), guanine (G), cytosine (C) and
thymine (T). A key property of the DNA structure is that the described nucleotides bind
specifically to another nucleotide when arranged in the two-strand double helix (A to T and C to
G). This specific bonding capability can be used to assemble nanophase materials and
nanostructures. For example, nucleotide functionalised nano-gold particles have been assembled
into complex 3D structures by attaching DNA strands to the gold via an enabler or linker. In a
separate work, DNA was used to assemble nanoparticles into macroscopic materials. This method
uses alkane dithiol as the linker molecule to connect the DNA template to the nanoparticle. The
thiol groups covalently attach themselves to the colloidal particles, leading to aggregate structures.

Figure 7: Schematic illustration of the formation process of the Fe3O4 nanoflakes by self assembly.
1.2.2 Top Down approach:

A microcrystalline material is fragmented to yield a nanocrystalline material.

Starting materials in these methods are in the solid state.
The top-down techniques do not usually lead to individual nanoparticles; however, they
can produce bulk nanostructured materials.
The Top Down processes can be easily scaled up.

Mechanical Alloying:
The mechanical alloying (MA)/milling process was originally developed by Benjamin of the
International Nickel Company for the production of oxide dispersion strengthened (ODS)
superalloys. It is now a widely used process for the fabrication of nanocrystalline powders.
Recently, nanocrystalline high-entropy solid solutions with high hardness have been synthesized
in multicomponent equiatomic alloys by MA. Mechanical alloying or milling is usually carried
out in high-energy mills such as vibratory mills (Spex 8000 mixer/mill), planetary mills (Fritsch
and Retsch) and attritor mills. The vibratory mill has one vial, containing the sample and grinding
balls and vibrates in all three directions. Because of the amplitude (about 50 mm) and speed (about
1200 rpm), the ball velocities are high (in the order of 5 m/s) and consequently the force of the
balls impact is unusually high. Another popular mill for conducting MA experiments is the
planetary ball mill. In this mill, the vials rotate around their own axes and at the same time around
the axis of a disc on which they are mounted. The centrifugal force produced by the vials rotating
around their own axes and that produced by the rotating support disk together act on the vial
contents, consisting of material to be ground and the grinding balls. Since the vials and the
supporting disc rotate in opposite directions, the centrifugal forces alternately act in opposite
directions. Due to this, the balls run down the inside wall of the vial. This is followed by the
material being ground and grinding balls being lifted off and travelling freely through the inner
chamber of the vial and colliding against the opposing inside wall. Grinding vials and balls are
available in eight different materialsagate, silicon nitride, sintered corundum, zirconia, chrome
steel, CrNi steel, tungsten carbide and plastic polyamide.

Figure 8: Schematic of the different stages during MA of a nominally ductile powder material: a)starting powder
b)flattened, layered composite particles c)homogeneous equiaxed particles.
The mechanism of nanocrystallization during high-energy ball milling was first proposed by H.J.
Fecht in 1983. He summarised the phenomenon of the development of nanocrystalline
microstructure into three stages;
Stage 1: Localization of deformation into shear bands with high dislocation density.
Stage 2: Dislocation, annihilation and recombination to form nanometre-scale subgrains, which
extend throughout the sample with further milling.
Stage 3: Transformation of subgrain boundary structure to randomly oriented highangle grain
boundaries. Superplastic deformation processes such as grain boundary sliding causes self-
organisation into a random nanocrystalline state.

Nanolithography

STM-based nanolithography: This has been exploited for local oxidation and passivation,
localized chemical vapour deposition, electrodeposition, mechanical contact of the tip with the
surface, and deformation of the surface by electrical pulses. Patterns with a minimal size from 10
20 nm to 1 nm in ultrahigh vacuum (UHV) have been demonstrated. Nanometre-sized holes can
be formed using low energy electrons from a scanning tunnelling microscope (STM) tip when a
pulsed electric voltage is applied in the presence of sufficient gas molecules between the substrate
and the tip. For example, holes that are 7 nm deep and 6 nm wide on highly ordered pyrolytic
graphite (HOPG) substrate were formed in nitrogen at a pressure of 25 bar by applying a 7 V pulse
to thetip for 130 mins, with the distance between the tip and the substrate being 0.61 nm.

Nanostructures can be created using field evaporation by applying bias pulses to the STM tip
sample tunnelling junction. For example, nanodots, nanolines, and nanocorrals of gold on a clean
stepped Si (111) surface were fabricated by applying a series of bias pulses (< 10 V and 30 s)
to an STM gold tip at UHV (a base pressure of 10-10 mbar). Nanodots with diameter as small as a
few nanometres can be realised. By decreasing the distance between adjacent nanodots, it was
possible to create continuous nanolines, a few nanometres wide and over a few hundred
nanometres long. A nanocoral of diameter about 40 nm, formed by many Au nanodots, each with
diameter of a few nanometres, was also created on the Si (111) surface.

AFM-based nanolithography: Direct contacting, writing or scratching is referred to as a

mechanical action of the AFM tip that is used as a sharply pointed tool in order to produce fine
grooves on sample surfaces. Although direct scratching creates grooves with high precision, low
quality results are often obtained due to tip wear during the process. An alternative approach is to
combine scratching on a soft resist polymer layer, such as PMMA or polycarbonate, as a mask for
the etching process and subsequent etching to transfer the pattern to the sample surface. This
method ensures reduced tip damage, but also precludes an accurate alignment to the structures
underneath. A two-layer mask has been investigated as a further improvement. For example, a
mask coating consisting of a thin layer of polycarbonate of 50100 m and a film of an easy-to-
deform and fusible metal such as indium or tin was used to create 50 nmwide structures. Figure
3.23 is a typical layout of the sample and process steps with AFM lithography.

Figure 9: Layout of the sample and the process steps with AFM lithography

1.3 CHARACTERIZATION TECHNIQUES:

The characterization of small structures or small-sized materials in the nanometric-scale usually

calls for sophisticated characterization tools. Characterization of nanomaterials and nanostructures
has been largely based on certain critical advancement of conventional characterization methods
developed for bulk materials. For example, X-ray diffraction (XRD) has been widely used for the
determination of crystalline character, crystallite size, crystal structures and lattice constants of
nanoparticles, nanowires and thin films. Scanning electron microscopy (SEM) and transmission
electron microscopy (TEM), together with electron diffraction, have been commonly used in the
characterization of nanoparticles to get an idea of the size, shape and defects present in these
materials. Fig. shows the various characterization techniques used to obtain information about
Microstructure, Chemistry, Defects and Structure of the nanomaterials.
Figure 10: Various Characterization Techniques and its Applications.
 2. NANOWIRES

A nanowire is a nanostructure, with the diameter of the order of a nanometer (109 meters). It can
also be defined as the ratio of the length to width being greater than 1000. Alternatively, nanowires
can be defined as structures that have a thickness or diameter constrained to tens of nanometers or
less and an unconstrained length. At these scales, quantum mechanical effects are important
which coined the term "quantum wires". Many different types of nanowires exist, including
superconducting (e.g. YBCO), metallic (e.g. Ni, Pt, Au), semiconducting (e.g. silicon nanowires
(SiNWs), InP, GaN) and insulating (e.g. SiO2, TiO2). Molecular nanowires are composed of
repeating molecular units either organic (e.g. DNA) or inorganic (e.g. Mo6S9xIx).

Typical nanowires exhibit aspect ratios (length-to-width ratio) of 1000 or more. As such they are
often referred to as one-dimensional (1-D) materials. Nanowires have many interesting properties
that are not seen in bulk or 3-D (three-dimensional) materials. This is because electrons in
nanowires are quantum confined laterally and thus occupy energy levels that are different from the
traditional continuum of energy levels or bands found in bulk materials.

Figure 11: SEM image of Yittrium oxide nanowires

Recently, nanowires and nanorods of metallic and semiconducting materials have drawn a lot of
research interest because of their unique physical properties which are interesting from the view
point of different device applications. Nanowires have two quantum-confined dimensions and one
unconfined dimension. Therefore, the electrical conduction behaviour of nanowires is different
from that of their bulk counterpart. In nanowires, electronic conduction takes place both by bulk
conduction and through tunneling mechanism. However, due to their high density of electronic
state, diameter-dependent band gap, enhanced surface scattering of electrons and phonons,
increased excitation binding energy, high surface to volume ratio and large aspect ratio, nanowires
of metals and semiconductor exhibit unique electrical, magnetic, optical, thermoelectric and
chemical properties compared to their bulk parent counterparts. The interesting properties of
nanowires hold lot of promises for applications in the fields of electronics, optics, magnetic
medium, thermoelectronic, sensor devices etc. In view of the interest and immense importance that
has been attached to the different properties and applications of nanowires, herein we present a
review on the current state of nanowire research. The review aims at highlighting the properties of
nanowires and their probable applications in different fields. In addition to this the review also
covers in detail the synthesis of nanowires by using porous alumina oxide template.
 2.1 STRUCTURE RELATIONSHIPS OF NANOWIRES

Nanowires can be classified by their shapes such as

1. Classic nanowires
2. Quantum nanowires

Based on aspect ratio

1. Whiskers or fibers (very high L/D, >1000)

2. Nanowires (L/D > 20 )
3. Nanorods ( L/D < 20)

Figure 12: ZnO nanowhiskers and nanorods

 2.2 PROPERTIES OF NANOWIRES

Depending on what it's made from, a nanowire can have the properties of an insulator,
a semiconductor or a metal. Insulators won't carry an electric charge, while metals carry electric
charges very well. Semiconductors fall between the two, carrying a charge under the right
conditions. By arranging semiconductor wires in the proper configuration, engineers can create
transistors, which either acts as a switch or an amplifier.

Some interesting and counterintuitive properties nanowires possess are due to the small scale.
When you work with objects that are at the nanoscale or smaller, you begin to enter the realm of
quantum mechanics. Quantum mechanics can be confusing even to experts in the field, and very
often it defies classical physics (also known as Newtonian physics).

For example, normally an electron can't pass through an insulator. If the insulator is thin enough,
though, the electron can pass from one side of the insulator to the other. It's called electron
tunneling, but the name doesn't really give you an idea of how weird this process can be. The
electron passes from one side of the insulator to the other without actually penetrating the insulator
itself or occupying the space inside the insulator. You might say it teleports from one side to the
other. You can prevent electron tunneling by using thicker layers of insulator since electrons can
only travel across very small distances.

Another interesting property is that some nanowires are ballistic conductors. In normal conductors,
electrons collide with the atoms in the conductor material. This slows down the electrons as they
travel and creates heat as a by-product. In ballistic conductors, the electrons can travel through the
conductor without collisions. Nanowires could conduct electricity efficiently without the by-
product of intense heat.

At the nanoscale, elements can display very different properties than what we've come to expect.
For example, in bulk, gold has a melting point of more than 1,000 degrees Celsius. By reducing
bulk gold to the size of nanoparticles, you decrease its melting point, because when you reduce
any particle to the nanoscale, there's a significant increase in the surface-to-volume ratio. Also, at
the nanoscale, gold behaves like a semiconductor, but in bulk form it's a conductor.

Other elements behave strangely at the nanoscale as well. In bulk, aluminum isn't magnetic, but
very small clusters of aluminum atoms are magnetic. The elemental properties we're familiar with
in our everyday experience and the ways we expect them to behave may not apply when we reduce
those elements down to the size of a nanometer.

We're still learning about the different properties of various elements at the nanoscale. Some
elements, like silicon, don't change much at the nanoscale level. This makes them ideal for
transistors and other applications. Others are still mysterious, and may display properties that we
can't predict right now.

Physical properties of Nanowires

The unique physical properties of nanowires and nanotubes originate from either the small
dimensions of the objects, or structural modifications induced by the confined synthesis and
surface effects. These features make them very promising for applications in nanoelectronics and
nanosensors in particular. Their magnetic, electrical and optical properties differ from the bulk
counterparts.

The morphology of nanowires, including their geometry, size, and surface contour, is primarily
determined by the shape of the hosting channels. The production of templates with swift heavy-
ion beams in combination with track etching enables us to control several template parameters
such as well-defined channel shape and channel geometry, with the diameter adjustable between
a few nanometres up to micrometres, membrane thickness up to 100 m, and aspect ratios up to
1000. In addition, by varying the fabrication steps in a controlled manner, novel structures can be
synthesized, such as pores with conical geometry or channels with smooth or rough inner walls.
By exposing the samples to the ion beam under various tilting angles, nanochannel networks with
controlled density and interconnection degree are possible.

Implementation of nanowire cathodes in fields such as energy harvesting, sensing, or catalysis

requires a successful assembly of the nanostructures into 2-D and 3-D architectures. Fabrication
of 3-D nanowire superstructures by vapourliquidsolid processes has been reported; however,
revealing a limited tunability of the relevant parameters. Recently, Rauber et al. demonstrated the
fabrication of highly ordered Pt nanowire networks, consisting of well-defined interconnected
nanowires with controlled morphology. Ion irradiation of polymer foils at several incident angles
in consecutive steps, followed by chemical etching results in novel etched ion-track membranes
with nanochannel arrays tilted at various angles. Electrodeposition in the nanochannel network
results in highly ordered 3-D nanowire ensembles

Magnetic properties of Nanowires

Magnetic nanowire arrays consisting of isolated needle-likemagnetic nanowires have recently
aroused considerableinterest from the viewpoint of perpendicular magneticrecording. The
nanowires that are introduced into the poresof alumina template by electro deposition are
potentiallycapable of producing bit densities in excess of 100 Gbit in2.When the magnetic field is
applied parallel to the longaxis of the magnetic nanowire, it exhibits a coercive field,which is
inversely proportional to the pore diameter. It has also been reportedthat the squareness of the
hysteresis loop can be increasedfrom 30% up to nearly 100% by decreasing the wire diameter,Dp.
Figures 1(a) and (b) show the variation of squareness ofthe hysteresis loop as a function of the
applied magneticfield (H) parallel and perpendicular to the wire axes fordifferent nanowire
diameters. A gradual increase of coercivityis observed with increasing aspect ratio (length
(l)/diameter (d)), but little change is observed when l/d >10. Moreover, now it has been
establishedthat depending on the geometry, different sites onthe surface will differ in local
coordination number,which may lead to the variation of moment with localenvironment. Here, it
is also important tonote that changes in the diameter of the nanowires mayinfluence the surface
energies of the different crystallographicplanes. It has been reported that in the case of bcc-Fe,
the order of surface free energy () for (110), (100)and (111) planes is 110 < 100 < 111, where
the values of110 and 100 are close to each other. However, it has beenfound that as the diameter
of the nanowire increases, thedifferences in the surface free energy between the
crystallographicplanes become more significant. Therefore, whennanowires are processed at low
temperatures, growth of(110) and (100) planes are nearly equal giving rise tooctagonal cross
section of the nanowires. At higher temperatures,growth of (110) plane predominates and square
shaped nanowires are formed. This change in morphologyis expected to cause a change in the
magnetization characteristicof the material. Therefore, it is apparent that onecan tune the magnetic
properties of the nanowires bysimply changing their diameter, which will change
coercivity,magnetization, remanance and squareness of thehysteresis loop.

Figure 13:The variation of squareness of hysteresis loops of Co nanowire arrays with applied magnetic field (H) parallel (||)
and perpendicular () to the wire axes: (a) nanowire diameter, 78 nm and (b) nanowire diameter, 18 nm.

It has been found that the total magnetic anisotropy ofthese nanowires is significantly influenced
by the magneticanisotropy, form of the nanowires and the demagnetizationfields between the
nanowires.

Electrical properties of Nanowires

Electron transport properties of nanowires are very importantfor electrical and electronic
applications as wellas for understanding the unique one-dimensional carriertransport mechanism.
It has been noticed that the wirediameter, wire surface condition, crystal structure and itsquality,
chemical composition, crystallographic orientationalong the wire axis etc are important
parameters, which influence the electron transport mechanism of nanowires.
It has been reported that quasi one-dimensional nanowiresexhibit both ballistic and diffusive type
electron transport mechanism, which depends upon the wirelength and diameter. Ballistic type
transport phenomena is associated with predominant carrier flow without scatteringwhich is due
to the fact that the carrier mean free pathis longer than that of the wire length.Ballistic type
transport mechanism is normally observedat the contact junction of nanowire and other
externalcircuits, where the conductanceis quantized into an integral multiple of 2e2/h, called
theuniversal conductance unit (e is the electronic charge andh the Planks constant)
In the case of ballistic type transport in metallic nanowires,the conductance quantization
phenomena takesplace because of the fact that the nanowire diameter becomescomparable to the
electron Fermi wavelength ofthat metal. As compared to theballistic transport mechanism, in
diffusive type conductionmechanism, the carrier mean free path is smaller thanthat of the wire
length. Therefore, various types of scatteringaffect the carriers and the carrier transport
mechanismof nanowires becomes quite similar to that of bulkcounterpart.
The clearest view of the electron transport mechanismof the metallic and semiconducting
nanowires can be easilyobtained by considering three parameters viz. wire diameter(d), carrier
mean free path (lc) and the de Broglie wavelengthof electron (e). Earlier studies have shown
thatwhen the wire diameter (d) is larger than the carrier meanfree path (lc) and the de Broglie
wavelength of electron(e) i.e. d >>lc and d >>e, the electron transport mechanismof nanowires
remains similar to that of bulk counterpart.However, if the wire diameter (d) becomes smalleror
comparable to that of the carrier mean free path (lc) andmuch larger than the de Broglie wavelength
of electron(e) i.e. d lc and d >>e, the electron transport mechanismof nanowires follows the
classical laws of physics.On the other hand, when the carrier mean free path (lc) andthe de Broglie
wave length of electron (e) both becomecomparable to the wire diameter i.e. d lc and d e,
thephenomena of quantum confinement occurs in nanowireswhich includes significant change in
the density of electronstates. Studies show that the electronic density of states(DOSs) of nanowires
is strongly diameter dependent.

Figure 14: Conductance, G (2e2/h) of silver nanowires with

However, it is found that the conductance of nanowiresstrongly depends on their crystalline
structure. For example,in the case of perfect crystalline Si nanowires havingfour atoms per unit
cell, generally three conductancechannels are found. One- or two-atomdefect, either by addition
or removal of one or two atomsmay disrupt the number of such conductance channel andmay cause
variation in the conductance. Variation inconductance due to the above reason is shown in figure
9,where conductance is plotted as a function of energy forperfect Si nanowires and single atom
addition defectnanowire.
Recently, electron transport mechanism of superlatticenanowires has acquired lot of interest
because of theirpotential applications in thermoelectronics (Lin and Dresselhaus 2003),
nanobarcodes (Wu et al 2002), nanolasers(Gudiksen et al 2002), one-dimensional waveguideand
resonant tunneling diodes (Bjork et al 2002a, b). Superlatticenanowires consist of periodic
modulation ofchemical composition and crystal structure in the form ofquantum dots along the
wire axes. The electron transportphenomena between those quantum dots are governed bythe
quantum tunneling mechanism in which specific regionsof the nanowires with a particular
composition act as thepotential barrier. As for example, in case of the InAsInPsuperlattice
nanowires the InP dots act as the potentialbarrier (Bjork et al 2002a, b). It is to be noted that
theinterfaces between the quantum dots have the capabilityof blocking the phonon conduction
along the wire axeswithout affecting the electrical conduction.

Optical properties of Nanowires

Metallic nanowires exhibit interesting plasmon absorptioneffect. Research has shown that the
energy of thesurface plasmon band is sensitive to various factors suchas particle size, shape,
composition, surrounding mediaand inter particle interactions.The photoluminescence (PL)
spectroscopic studies onsemiconducting nanowires (InP, CdS, ZnO nanowires)have shown that
the PL energy peakand band gap increases with the decrease of the wire diameter.The above
phenomena confirm the effect ofquantum confinement in nanowires when the wire diameteris
reduced.
Fluorescence study of nanowires provides vivid informationabout the band gap, quantum
confinement effect,strain in nanowires, oxygen vacancies, electron effectivemasses and Fermi
energies. The number of sub bands ofthe nanowires can be measured with the help of magneto
optictechniques. The determination of the number ofsub bands in nanowires is very important for
determiningthe electron transport properties in them.It is to be noted that magnetic properties of
the nanowirescan also be determined by the above-mentioned techniques.
Nanowire arrays exhibit non-linear optical properties,which make them very attractive for
application as photonicmaterial. The sharp increase in the energy of the absorptionpeak with the
decrease of the wire diameter is attributedto quantum confinement effect and theoccurrence of the
blue shift. The extinction spectra ofsilver nanowires with different diameters revealed that for fixed
length (h) of the nanowireswhen the diameter (d) decreases, shifts towards theshorter wavelength
side because of the quantum confinementeffect.
Mechanical properties of Nanowires
Since its beginnings approximately two decades ago, nanowire (NW) related research has become
one of the hottest topics innanoscience and nanotechnology. The peculiar and fascinating
properties of NWs, as well as their unique performance in various applications, have driven
tremendous scientific interest. From a practical standpoint, the design, fabrication and application
of NW-based devicesand NW-strengthened compositesrely critically on the mechanical properties
of NWs, which often differ from their bulk counterparts due to their extremely small physical size
and high surface-to-volume ratio. From a scientific standpoint, NWs provide an ideal test-bed for
understanding the intrinsic and size-dependent mechanical properties of solid materials, allowing
for the validation of theoretical predictions. As a consequence, characterizing and understanding
the mechanical properties of NWs has become increasingly important in recent years.
Youngs modulus and fracture strength of Si NWs with diameters between 15 and 60 nm and
lengths between 1.5 and 4.3 m were observed. The NWs, grown by the VLS process, were
subjected to in situ tensile tests inside a SEM. The Youngs modulus of Si NWs was found to be
close to the bulk value (187 GPa for 111 orientation) when the diameters are larger than 30 nm.
However, the softening trend is obvious when the diameters of the NW are smaller than 30 nm;
the Youngs modulus of the NWs decreases with the decreasing diameters. Various experiments
also showed that fracture strain and strength of Si NWs increased as the NW diameter decreased.
The maximum strength was found to be over 12 GPa. The fracture strength also increased with the
decrease of the side surface area; the increase rate for the chemically synthesized Si NWs was
found to be much higher than that for the microfabricated Si thin films. Repeated loading and
unloading during tensile tests demonstrated that the NWs are linear elastic until fracture without
appreciable plasticity.
Similar observations were made with GaN nanowires, which show elongation on applying tensile
force. The force stretches the atomic bonds which causes elongation & necking. Breaking of bonds
occur from outside to inside of nanowire structure & this breaking stress was 80 Gpa.
 3. CARBON NANOTUBES

Since its discovery in 1991 by Sumio lijima. Carbon nanotubes have generated huge activity in
most areas of science and engineering due to their remarkable physicaland chemical properties.
No previousmaterials have displayed the combination ofsuperlative mechanical, thermal and
electronicproperties attributed to them. These propertiesmake nanotubes ideal, not only for a
widerange of applicationsbut as a test bed forfundamental science.Researchers have envisaged
takingadvantage of their conductivity and highaspect ratio to produce conductive plasticswith
exceedingly low percolation thresholds.Carbon nanotubes tend to have impressivemechanical
properties with Youngs modulus in the range 100-1000 GPa and strengths between 2.5 and 3.5
GPa. Nanotubes have diameter ranging from 1 to 100nm and lengths of up to millimeters. Their
densities can be aslow as ~1.3 g / cm3 and their Youngs moduli are superior to all carbon fibres
with valves greater than 1 TPa. The highest measured strength for a carbon nanotube was 63 GPa
and even the weakest of type of CNT has strength of several GPa. CNTs have received much
attention from scientific communities up to this date mainly because of their superior properties
such as having a wide band gap, high melting point, high tensile strength and high thermal
conductivity.

3.1 CLASSIFICATION:

Carbon nanotubes can be mainly classified, according to the number of walls of graphene layers
from which it is made of, as 1. Single Wall Carbon Nanotube (SWNT) and 2. Multi Walled Carbon
Nanotube (MWNT).

Single Walled Carbon Nanotube

Most single-walled nanotubes (SWNTs) have a diameter of close to 1 nanometer, and can be many
millions of times longer. The structure of a SWNT can be conceptualized by wrapping a one-atom-
thick layer of graphite called graphene into a seamless cylinder. The way the graphene sheet is
wrapped is represented by a pair of indices (n,m). The integers n and m denote the number of unit
vectors along two directions in the honeycomb crystal lattice of graphene. If m = 0, the nanotubes
are called zigzag nanotubes, and if n = m, the nanotubes are called armchair nanotubes. Otherwise,
they are called chiral.
 Figure 15: Various Single Walled Carbon Nanotubes.

SWNTs are an important variety of carbon nanotube because most of their properties change
significantly with the (n,m) values, and this dependence is non-monotonic. In particular, their band
gap can vary from zero to about 2 eV and their electrical conductivity can show metallic or
semiconducting behavior. Single-walled nanotubes are likely candidates for miniaturizing
electronics. The most basic building block of these systems is the electric wire, and SWNTs with
diameters of an order of a nanometer can be excellent conductors. One useful application of
SWNTs is in the development of the first intermolecular field-effect transistors (FET).

As of 2016 the retail price of as-produced 75% by weight SWNTs was $2 per gram, cheap enough
for widespread use. SWNTs are forecast to make a large impact in electronics applications by 2020
according to The Global Market for Carbon Nanotubes report.

Multi-walled Carbon Nanotube

Multi-walled nanotubes (MWNTs) consist of multiple rolled layers (concentric tubes) of graphene.
There are two models that can be used to describe the structures of multi-walled nanotubes. In the
Russian Doll model, sheets of graphite are arranged in concentric cylinders, e.g., a (0,8) single-
walled nanotube (SWNT) within a larger (0,17) single-walled nanotube. In the Parchment model,
a single sheet of graphite is rolled in around itself, resembling a scroll of parchment or a rolled
newspaper. The interlayer distance in multi-walled nanotubes is close to the distance between
graphene layers in graphite, approximately 3.4 . The Russian Doll structure is observed more
commonly. Its individual shells can be described as SWNTs, which can be metallic or
semiconducting. Because of statistical probability and restrictions on the relative diameters of the
individual tubes, one of the shells, and thus the whole MWNT, is usually a zero-gap metal.
 Figure 16: Multi Walled Carbon Nanotube.

Double-walled carbon nanotubes (DWNTs) form a special class of nanotubes because their
morphology and properties are similar to those of SWNTs but they are more resistant to chemicals.
This is especially important when it is necessary to graft chemical functions to the surface of the
nanotubes (functionalization) to add properties to the CNT. Covalent functionalization of SWNTs
will break some C=C double bonds, leaving "holes" in the structure on the nanotube, and thus
modifying both its mechanical and electrical properties. In the case of DWNTs, only the outer wall
is modified. DWNT synthesis on the gram-scale was first proposed in 2003 by the CCVD
technique, from the selective reduction of oxide solutions in methane and hydrogen.

The telescopic motion ability of inner shells and their unique mechanical properties will permit
the use of multi-walled nanotubes as main movable arms in coming nanomechanical devices.
Table gives a few important differences between SWNT and MWNT.

Differences between SWNT and MWNT:

Table 1: Differences between SWNT and MWNT.

SWNT MWNT

Single layer graphene Multiple graphene layer

Catalyst is required for synthesis Can be produced without catalyst

Bulk synthesis is difficult as it requires Bulk synthesis is easy

proper control over growth and atmospheric
conditions
Purity is poor Purity is high

A chance of defect is more during A chance of defect is less but once

functionalization occurred it is difficult to improve
 Less accumulation in body More accumulation in the body

Characterization and evaluation is easy It has very complex structure

It can be easily twisted & are more liable It cannot be easily twisted
 3.2 PROPERTIES

Physiochemical properties of CNTs

Carbon nanotubes are a huge cylindrical large molecules consisting of a hexagonal arrangement
of sp2 hybridized carbon atoms (C-C distance is about 1.4 ). The wall of CNTs is single or
multiple layers of graphene sheets, of which those formed by rolling up of single sheet are called
single-walled carbon nanotubes (SWCNTs) and those formed by rolling up of more than one sheets
are called multi-walled CNTs (MWCNTs). Both SWCNTs and MWCNTs are capped at both ends
of the tubes in a hemispherical arrangement of carbon networks called fullerenes warped up by the
graphene sheet. The interlayer separation of the graphene layers of MWCNTs is approximately
0.34 nm in average, each one forming an individual tube, with all the tubes having a larger outer
diameter (2.5 to 100 nm) than SWCNTs (0.6 to 2.4 nm). SWCNTs have a better defined wall,
whereas MWCNTs are more likely to have structural defects, resulting in a less stable
nanostructure, yet they continue to be featured in many publications due to ease of processing. As
for their use as drug carriers, there remain no conclusive advantages of SWCNTs relative to
MWCNTs; the defined smaller diameter may be suitable for their quality control while the defects
and less stable structure make their modification easier. CNTs vary significantly in length and
diameter depending on the chosen synthetic procedure. SWCNTs and MWCNTs have strong
tendency to bundle together in ropes as a consequence of attractive van der Waals forces. Bundles
contain many nanotubes and can be considerably longer and wider than the original ones from
which they are formed. This phenomenon could be of important toxicological significance. CNTs
exist in different forms depending upon the orientation of hexagons in the graphene sheet and
possess a very high aspect ratio and large surface areas. The available surface area is dependent
upon the length, diameter, and degree of bundling. Theoretically, discrete SWCNTs have special
surface areas of approximately 1300 m2/g, whereas MWCNTs generally have special surface areas
of a few hundred square meters per gram. The bundling of SWCNTs dramatically decreases the
special surface area of most samples of SWCNT to approximately 300m2/g or less, although this
is still a very high value. The markedly CNTs have various lengths from several hundreds of
nanometers to several micrometers and can be shortened chemically or physically for their
suitability for drug carriers by making their two ends open with useful wall defects for intratube
drug loading and chemical functionalization.

Electrical & structural properties of CNTs

Carbon nanotubes can be metallic or semiconducting depending on their structure. This is due to
the symmetry & unique electronic structure of graphene. For a given (n, m) nanotube, if n=m, the
nanotube is metallic, if n=m, is multiple of 3, then the nanotube is semiconducting with a very
small band gap, otherwise the nanotube is a moderate semiconductor. Thus all armchair (n=m)
nanotubes are metallic, and nanotubes (5, 0) (6, 4) (9, 1) etc. are semiconducting. Some nanotubes
have conductivities higher than that of copper, while others believe more like silicon.
Conductivity in MWNTs is quite complex. Some types of armchair-structured CNTs appear to
conduct better than other metallic CNTs. Furthermore, interwall reactions within MWNTs have
been found to redistribute the current over individual tubes non-uniformly. However, there is no
change in current across different parts of metallic single-walled CNTs. However, the behaviour
of ropes of semi-conducting SWNTs is different, in that the transport current changes abruptly at
various positions on the CNTs.

The conductivity and resistivity of ropes of SWNTs has been measured by placing electrodes at
different parts of the CNTs. The resistivity of the SWNT ropes was in the order of 104 ohm-cm
at 27C. This means that SWNT ropes are the most conductive carbon fibers known. The current
density that was possible to achieve was 107A/cm2, however in theory the SWNT ropes should be
able to sustain much higher stable current densities, as high as 1013 A/cm2.

It has been reported that individual SWNTs may contain defects. Fortuitously, these defects allow
the SWNTs to act as transistors. Likewise, joining CNTs together may form transistor-like
devices. A nanotube with a natural junction (where a straight metallic section is joined to a chiral
semiconducting section) behaves as a rectifying diode that is, a half-transistor in a single
molecule. It has also recently been reported that SWNTs can route electrical signals at high speeds
(up to 10 GHz) when used as interconnects on semi-conducting devices.

Mechanical properties of CNTs

The carbon atoms of a single (graphene) sheet of graphite form a planar honeycomb lattice, in
which each atom is connected via a strong chemical bond to three neighbouring atoms. Because
of these strong bonds, the basal-plane elastic modulus of graphite is one of the largest of any known
material. For this reason, CNTs are expected to be the ultimate high-strength fibers. SWNTs are
stiffer than steel, and are very resistant to damage from physical forces. Pressing on the tip of a
nanotube will cause it to bend, but without damage to the tip. When the force is removed, the tip
returns to its original state. This property makes CNTs very useful as probe tips for very high-
resolution scanning probe microscopy.

Quantifying these effects has been rather difficult, and an exact numerical value has not been
agreed upon. Using an atomic force microscope (AFM), the unanchored ends of a freestanding
nanotube can be pushed out of their equilibrium position and the force required to push the
nanotube can be measured. The current Youngs modulus value of SWNTs is about 1 Tera Pascal,
but this value has been disputed, and a value as high as 1.8 TPa has been reported. Other values
significantly higher than that have also been reported. The differences probably arise through
different experimental measurement techniques. Others have shown theoretically that the Youngs
modulus depends on the size and chirality of the SWNTs, ranging from 1.22 TPa to 1.26
TPa. They have calculated a value of 1.09 TPa for a generic nanotube. However, when working
with different MWNTs, others have noted that the modulus measurements of MWNTs using AFM
techniques do not strongly depend on the diameter. Instead, they argue that the modulus of the
MWNTs correlates to the amount of disorder in the nanotube walls. Not surprisingly, when
MWNTs break, the outermost layers break first.

Optical properties of CNTs

Carbon nanotubes have useful absorption, photoluminescence (fluorescence), and Raman
spectroscopy properties. Spectroscopic methods offer the possibility of quick and non-destructive
characterization of relatively large amounts of carbon nanotubes. There is a strong demand for
such characterization from the industrial point of view: numerous parameters of the nanotube
synthesis can be changed, intentionally or unintentionally, to alter the nanotube quality. As shown
below, optical absorption, photoluminescence and Raman spectroscopies allow quick and reliable
characterization of this "nanotube quality" in terms of non-tubular carbon content, structure
(chirality) of the produced nanotubes, and structural defects. Those features determine nearly any
other properties such as optical, mechanical, and electrical properties.
Carbon nanotubes are unique "one-dimensional systems" which can be envisioned as rolled single
sheets of graphite (or more precisely graphene). This rolling can be done at different angles and
curvatures resulting in different nanotube properties. The diameter typically varies in the range
0.440 nm (i.e. "only" ~100 times), but the length can vary ~10,000 times, reaching 55.5 cm. The
nanotube aspect ratio, or the length-to-diameter ratio, can be as high as 132,000,000:1, which is
unequalled by any other material. Consequently, all the properties of the carbon nanotubes relative
to those of typical semiconductors are extremely anisotropic (directionally dependent) and
tunable.
Whereas mechanical, electrical and electrochemical (supercapacitor) properties of the carbon
nanotubes are well established and have immediate applications, the practical use of optical
properties is yet unclear. The aforementioned tunability of properties is potentially useful
in optics and photonics. In particular, light-emitting diodes (LEDs) and photo-detectors based on
a single nanotube have been produced in the lab. Their unique feature is not the efficiency, which
is yet relatively low, but the narrow selectivity in the wavelength of emission and detection of light
and the possibility of its fine tuning through the nanotube structure. In addition, bolometer and
optoelectronic memory devices have been realised on ensembles of single-walled carbon
nanotubes.
Crystallographic defects also affect the tube's electrical properties. A common result is lowered
conductivity through the defective region of the tube. A defect in armchair-type tubes (which can
conduct electricity) can cause the surrounding region to become semiconducting, and single
monatomic vacancies induce magnetic properties.

3.3 APPLICATIONS
Many potential applications have been proposed for carbon nanotubes, including conductive and
high-strength composites; energy storage and energy conversion devices; sensors; field emission
displays and radiation sources; hydrogen storage media; and nanometer-sized semiconductor
devices, probes, and interconnects. Some of these applications are now realized in products. Others
are demonstrated in early to advanced devices, and one, hydrogen storage, is clouded by
controversy. Nanotube cost, polydispersity in nanotube type, and limitations in processing and
assembly methods are important barriers for some applications of single-walled nanotubes.

Carbon Nanotube Composites: The first realized major commercial application of MWNTs is
their use as electrically conducting components in polymer composites. Depending on the polymer
matrix, conductivities of 0.01 to 0.1 S/cm can be obtained for 5% loading; much lower conductivity
levels suffice for dissipating electrostatic charge. The low loading levels and the nanofiber
morphology of the MWNTs allow electronic conductivity to be achieved while avoiding or
minimizing degradation of other performance aspects, such as mechanical properties and the low
melt flow viscosity needed for thin-wall molding applications. In commercial automotive gas lines
and filters, the nanotube filler dissipates charge buildup that can lead to explosions and better
maintains barrier properties against fuel diffusion than do plastics filled with carbon black. Plastic
semiconductor chip carriers and reading heads made from nanotube composites avoid
contamination associated with carbon black sloughing. Similar materials are also used for
conductive plastic automotive parts, such as mirror housings that are electrostatically painted on
the assembly line, thereby avoiding separate painting and associated color mismatch. The
smoothness of the surface finish provides an advantage over other conductive fillers.

Electrochemical Devices: Because of the high electrochemically accessible surface area of porous
nanotube arrays, combined with their high electronic conductivity and useful mechanical
properties, these materials are attractive as electrodes for devices that use electrochemical double-
layer charge injection. Examples include supercapacitors, which have giant capacitances in
comparison with those of ordinary dielectric based capacitors, and electromechanical actuators
that may eventually be used in robots. Like ordinary capacitors, carbon nanotube supercapacitors
and electromechanical actuators typically comprise two electrodes separated by an electronically
insulating material, which is ionically conducting in electrochemical devices. The capacitance for
an ordinary planar sheet capacitor inversely depends on the interelectrode separation. In contrast,
the capacitance for an electrochemical device depends on the separation between the charge on the
electrode and the countercharge in the electrolyte. Because this separation is about a nanometer
for nanotubes in electrodes, as compared with the micrometer or larger separations in ordinary
dielectric capacitors, very large capacitances result from the high nanotube surface area accessible
to the electrolyte. These capacitances (typically between 15 and 200 F/g, depending on the surface
area of the nanotube array) result in large amounts of charge injection when only a few volts are
applied. This charge injection is used for energy storage in nanotube supercapacitors and to provide
electrode expansions and contractions that can do mechanical work in electromechanical actuators.

Hydrogen Storage: Nanotubes have been long heralded as potentially useful for hydrogen storage
(for example, for fuel cells that power electric vehicles or laptop computers). However,
experimental reports of high storage capacities are so controversial that it is impossible to assess
the applications potential. Numerous claims of high hydrogen storage levels have been shown to
be incorrect; other reports of room temperature capacities above 6.5 weight % (a U.S. Department
of Energy benchmark) await confirmation. Given the high research activity in this area, it is hoped
that this controversy will soon be resolved.

Field Emission Devices: Industrial and academic research activity on electronic devices has
focused principally on using SWNTs and MWNTs as field emission electron sources for flat panel
displays, lamps, gas discharge tubes providing surge protection, and x-ray and microwave
generators. A potential applied between a carbon nanotube coated surface and an anode produces
high local fields, as a result of the small radius of the nanofiber tip and the length of the nanofiber.
These local fields cause electrons to tunnel from the nanotube tip into the vacuum.

Nanometer-Sized Electronic Devices: Electronic circuits cannot continue to shrink by orders of

magnitude and provide corresponding increases in computational power, unless radically different
device materials, architectures, and assembly processes are developed. Dramatic recent advances
have fueled speculation that nanotubes will be useful for downsizing circuit dimensions. For
example, current-induced electromigration causes conventional metal wire interconnects to fail
when the wire diameter becomes too small. The covalently bonded structure of carbon nanotubes
militates against similar breakdown of nanotube wires, and because of ballistic transport, the
intrinsic resistance of the nanotube should essentially vanish. Experimental results show that
metallic SWNTs can carry up to 109 A/cm2 , whereas the maximum current densities for normal
metals are 105 A/cm2. Unfortunately, the ballistic current carrying capability is less useful for
presently envisioned applications because of necessarily large contact resistances. An electronic
circuit involving electrical leads to and from a SWNT will have a resistance of at least h/4e2 or 6.5
kilohms, where h is Plancks constant and e is the charge of an electron. Contacting all layers in a
MWNT could reduce this contact resistance, but it cannot be totally eliminated.

Sensors and Probes: Possible chemical sensor applications of nonmetallic nanotubes are
interesting, because nanotube electronic transport and thermopower (voltages between junctions
caused by interjunction temperature differences) are very sensitive to substances that affect the
amount of injected charge. The main advantages are the minute size of the nanotube sensing
element and the correspondingly small amount of material required for a response. Major
challenges remain, however, in making devices that differentiate between absorbed species in
complex mixtures and provide rapid forward and reverse responses.

4. FULLERENES

A fullerene is a molecule of carbon in the form of a hollow sphere, ellipsoid, tube, and many
other shapes. Spherical fullerenes, also referred to as Buckminsterfullerenes or buckyballs,
resemble the balls used in association football. Cylindrical fullerenes are also called carbon
nanotubes (buckytubes). Fullerenes are similar in structure to graphite, which is composed of
stacked graphene sheets of linked hexagonal rings. Unless they are cylindrical, they must also
contain pentagonal (or sometimes heptagonal) rings.

Figure 17: Buckminsterfullerene and Carbon Nanotube.

The first fullerene molecule to be discovered, and the family's namesake, buckminsterfullerene
(C60), was manufactured in 1985 by Richard Smalley, Robert Curl, James Heath, Sean O'Brien,
and Harold Kroto at Rice University. The name was homage to Buckminster Fuller, whose
geodesic domes it resembles. The structure was also identified some five years earlier by Sumio
Iijima, from an electron microscope image, where it formed the core of a "bucky onion".
Fullerenes have since been found to occur in nature. More recently, fullerenes have been
detected in outer space. According to astronomer Letizia Stanghellini, "Its possible that
buckyballs from outer space provided seeds for life on Earth."

The discovery of fullerenes greatly expanded the number of known carbon allotropes, which had
previously been limited to graphite, graphene, diamond, and amorphous carbon such as soot and
charcoal. Buckyballs and buckytubes have been the subject of intense research, both for their
chemistry and for their technological applications, especially in materials science, electronics,
and nanotechnology.
 4.1 BUCKMINSTERFULLERENE

Buckminsterfullerene (or bucky-ball) is a spherical fullerene molecule with the formula C60. It
has a cage-like fused-ring structure (truncated icosahedron) which resembles a soccer ball
(football), made of twenty hexagons and twelve pentagons, with a carbon atom at each vertex of
each polygon and a bond along each polygon edge.

It was first generated in 1985 by Harold Kroto, James R. Heath, Sean O'Brien, Robert Curl, and
Richard Smalley at Rice University. Kroto, Curl and Smalley were awarded the 1996 Nobel
Prize in Chemistry for their roles in the discovery of buckminsterfullerene and the related class
of molecules, the fullerenes. The name is a reference to Buckminster Fuller, as C60 resembles
his trademark geodesic domes. Buckminsterfullerene is the most common naturally occurring
fullerene molecule, as it can be found in small quantities in soot. Solid and gaseous forms of the
molecule have been detected in deep space.

Chemical formula- C60

Molar mass- 720.66 gmol1

Appearance- Dark needle-like crystals

Density- 1.65 g/cm3

Melting point- 600C

Solubility in water- insoluble in water

 4.2 SYNTHESIS OF BUCKMINSTERFULLERENE

In 1989 physicists Wolfgang Krtschmer, Konstantinos Fostiropoulos, and Donald R. Huffman

observed unusual optical absorptions in thin films of carbon dust (soot). The soot had been
generated by an arc-process between two graphite electrodes in a helium atmosphere where the
electrode material evaporates and condenses forming soot in the quenching atmosphere. Among
other features, the IR spectra of the soot showed four discrete bands in close agreement to those
proposed for C60.

Another paper on the characterization and verification of the molecular structure followed on in
the same year (1990) from their thin film experiments, and detailed also the extraction of an
evaporable as well as benzene soluble material from the arc-generated soot. This extract had
TEM and X-ray crystal analysis consistent with arrays of spherical C60 molecules,
approximately 1.0 nm in van der Waals diameter as well as the expected molecular mass of 720
u for C60 (and 840 u for C70) in their mass spectra. The method was simple and efficient to
prepare the material in gram amounts per day (1990) which has boosted the fullerene research
and is even today applied for the industrial production of fullerenes.

Alternatively, soot is produced by laser ablation of graphite or pyrolysis of aromatic

hydrocarbons. Fullerenes are extracted from the soot using a multistep procedure. First, the soot
is dissolved in appropriate organic solvents. This step yields a solution containing up to 75% of
C60, as well as other fullerenes. These fractions are separated using chromatography. Generally,
the fullerenes are dissolved in hydrocarbon or halogenated hydrocarbon and separated using
alumina columns.

Figure 18: High-vacuum electrolysis of a C60-fullerene derivative. Slow diffusion into the anode (right side) yields the
characteristic purple color of pure C60.
Producer
The world's first computer controlled fullerene production plant is now operational at the MER
corporation US based company , who pioneered the first commercial production of fullerene and
fullerene products.

The lab scale producer of fullerene is:

Fullerene Sigma Aldrich- 16794 rupess/1gm

4.3 PROPERTIES

Molecular Properties
The structure of a buckminsterfullerene is a truncated icosahedron with 60 vertices and 32 faces
(20 hexagons and 12 pentagons where no pentagons share a vertex) with a carbon atom at the
vertices of each polygon and a bond along each polygon edge. The van der Waals diameter of a
C60 molecule is about 1.01 nanometers (nm). The nucleus to nucleus diameter of a C60
molecule is about 0.71 nm. The C60 molecule has two bond lengths. The 6:6 ring bonds
(between two hexagons) can be considered "double bonds" and are shorter than the 6:5 bonds
(between a hexagon and a pentagon). Its average bond length is 0.14 nm. Each carbon atom in
the structure is bonded covalently with 3 others.

Figure 19: Close view of Buckminsterfullerene.

The C60 molecule is extremely stable, withstanding high temperatures and high pressures. The
exposed surface of the structure can selectively react with other species while maintaining the
spherical geometry. Atoms and small molecules can be trapped within the molecule without
reacting.

C60 undergoes six reversible, one-electron reductions to C660, but oxidation is irreversible.
The first reduction needs 1.0 V (Fc/Fc+), showing that C60 is a moderately effective electron
acceptor. C60 tends to avoid having double bonds in the pentagonal rings, which makes electron
delocalization poor, and results in C60 not being "superaromatic". C60 behaves very much like
an electron deficient alkene and readily reacts with electron rich species.

A carbon atom in the C60 molecule can be substituted by a nitrogen or boron atom yielding a
C59N or C59B respectively.
Chemical properties-
The carbon atoms within a Fullerene molecule are sp2 and sp3 hybridized, of which the sp2
carbons are responsible for the considerably angle strain presented within the molecule. C60and
C70 exhibit the capacity to be reversibly reduced with upto six electrons. This high electron
affinity results from the presence of triply-degenerate low-lying LUMOs (lowest unoccupied
molecular orbital). Oxidation of the molecule has also been observed; nevertheless, oxidation is
irreversible. C60 has a localized pi-electron system, which prevents themolecule from displaying
superaromaticity properties.

Physical Properties-
Fullerenes are extremely strong molecules, able to resist great pressuresthey will bounce back
to their original shape after being subject to over 3,000 atmospheres. Theoretical calculations
suggest that a single C60 molecule has an effective bulk modulus of 668 GPa when compressed
to 75% its size. This property makes fullerenes become harder than steel and diamond, whose
bulk moduli are 160 GPa and 442 Gpa, respectively. An interesting experiment shows that
Fullerenes can withstand collisions of up to 15,000 mph against stainless steel, merely bouncing
back and keeping their shapes. This experiment resembles the high stability of the molecule.

Optical Properties-
Delocalized pi electrons in Fullerenes are known to provide exceptionally large nonlinear optical
responses. Fullerenes have shown particular promises in optical limiting and intensity-dependent
refractive index. Additionally, the transfer of electrons from enclosed atom(s) to the Fullerene
enhances the third-order nonlinear optical effect by orders of magnitude compared to empty cage
Fullerenes.

Solution properties-
Fullerenes are sparingly soluble in aromatic solvents such as toluene and carbon disulfide, but
insoluble in water. Solutions of pure C60 have a deep purple color which leaves a brown residue
upon evaporation. The reason for this color change is the relatively narrow energy width of the
band of molecular levels responsible for green light absorption by individual C60 molecules.
Thus individual molecules transmit some blue and red light resulting in a purple color. Upon
drying, intermolecular interaction results in the overlap and broadening of the energy bands,
thereby eliminating the blue light transmittance and causing the purple to brown color change.
 Figure 20: Solution of Pure C60 having purple color.

Band Structure and Superconductivity

In 1991, Haddon et al. found that intercalation of alkali-metal atoms in solid C60 leads to
metallic behavior. In 1991, it was revealed that potassium-doped C60 becomes superconducting
at 18 K. This was the highest transition temperature for a molecular superconductor. Since then,
superconductivity has been reported in fullerene doped with various other alkali metals. It has
been shown that the superconducting transition temperature in alkaline-metal-doped fullerene
increases with the unit-cell volume V. As caesium forms the largest alkali ion, caesium-doped
fullerene is an important material in this family. Recently, superconductivity at 38 K has been
reported in bulk Cs3C60, but only under applied pressure. The highest superconducting transition
temperature of 33 K at ambient pressure is reported for Cs2RbC60.
 4.3 APPLICATIONS

Solar Cells
The high electron affinity and superior ability to transport charge make Fullerenes the best
acceptor component currently available. First, they have an energetically deep-lying LUMO,
which endows the molecule with a very high electron affinity relative to the numerous potential
organic donors. The LUMO of C60 also allows the molecule to be reversibly reduced with up to
six electrons, thus illustrating its ability to stabilize negative charge. Importantly, a number of
conjugated polymerfullerene blends are known to exhibit ultrafast photoinduced charge
transfer, with a back transfer that is orders of magnitude slower. The state of the art in the field
of organic photovoltaic is currently the Bulk Heterojunction (BHJ) solar cells based on Fullerene
derivate phenyl- C61_butryric acid methyl ester (PCBM), whit reproducible efficiencies
approaching 5 %.

Conventional silicon solar cells exceed 20% efficiency. Therefore, we can ask ourselves, why is
it so important to think of organic solar cells? First, the cost of production of organic light-
converting devices compared to the corresponding inorganic analogues is lower by more than
two orders of magnitude. And second, an important merit of organic solar cells is their
flexibility. They can be rolled up, cut, and spread over any surface. Particularly, such plastic can
be used for covering both the inner and outer walls of buildings; cells of any color and texture
can be manufactured. For example, a cell phone can be painted with this material, thus walking
in a sunny day will be enough to charge the devices battery. American military departments
actively support projects associated with organic solar cells because these materials demonstrate
high capabilities to be used in new armaments and attendant systems.

Finally, great expectations are also associated with the use of organic cells in the advertising and
packaging business. These involve autonomous luminous banners, large liquid crystal line
displays and packaging for food.

Fullerene Strengthening/Hardening of Metals-

Fullerenes offer unique opportunities to harden metals and alloys without seriously
compromising their ambient temperature ductility. This is due to the unique characteristics of
fullerenes, namely their small size and high reactivity, which enable the dispersion strengthening
of metallic matrices with carbide particles that result from in-situ interactions between fullerenes
and metals. In a comparison of the hardness of a popular aerospace intermetallic compound Ti-
24.5AI-17Nb, with and without fullerene additives, a 30% hardness enhancement was measured
for the material with fullerene additives.

Optical Application of Fullerene-

Optical limiting refers to a decrease in transmittance of a material with increased incident light
intensity. The phenomenon of optical limiting has a significant potential for applications in eye
and sensor protection from intense sources of light. Based on the optical limiting properties of
fullerenes, one can make an optical limiter, which allows all light below an activation threshold
to pass and maintains the transmitted light at a constant level below the damage threshold for the
eye or the sensor.

Fullerenes as Molecular Wires-

Recent experiments have documented electron transport through single molecules. Under certain
experimental conditions molecular conduction through a single molecule rather than through an
ensemble of molecules is guarantee. This phenomenon is possible due the high electron affinity
of Fullerenes. If a molecular computer is ever to be built, then it will need molecular wires in
order to connect to its various components. Figure shows a computer created scenario of a
possible use of Fullerenes in the manufacture of molecular conductors. When a source of UV
light is applied to the system in figure, the Fullerene molecules get excited and electrons move
from the Porphyrin wire towards the Fullerenes. These electrons leave holes in the Porphyrin
through which electrical current can flow from one electrode to the other.

Figure 21: Fullerenes on a Porphyrin wire.

Fullerene in Medicine-
Interest of scientists in water-soluble fullerene compounds is directly related to their biological
activity. Dendrimer 4p containing 18 carboxyl groups is the more promising today. The synthesis
and the use of this compound in medicine were patented in the U.S. (C-sixty Corporation); at
present, this drug undergoes clinical trials as a promising medication for treatment of AIDS.
Fullerene derivatives can be used in the photodynamic cancer therapy as antibacterial agents and
medications of neuroprotective action. Because of their ability to enclose atoms, Fullerenes
promise to be of great use as drug carriers. Additionally, noble gases have been encapsulated in
Fullerenes, which have no desire to bond with the surrounding carbon atoms but can be used in
applications such as magnetic resonance imaging (MRI). Researchers at Rice University have
designed C60 and other fullerenes molecules with an atom of gadolinium inside and with
chemical appendages that make them water-soluble. In typical MRI contrast agents, the metal
gadolinium is lined to a non-fullerene molecule, which is normally excreted quickly from the
body. Fullerenes encapsulated with gadolinium might allow the contrast agent to remain in the
body longer, allowing doctors to perform slower studies.

Figure 22: Schematic of a Fullerene encapsulating another particle.

5. REFERENCES:
1. Rao, Chintamani Nagesa Ramachandra, Achim Mller, and Anthony K.
Cheetham, eds. The chemistry of nanomaterials: synthesis, properties and
applications. John Wiley & Sons, 2006.
2. Murty, B. S., et al. Textbook of nanoscience and nanotechnology. Springer
Science & Business Media, 2013.
3. W. J. Anton, R. W. Stephen, I. S. David , Biological Applications of
Fullerenes. New York City, NY: Elsevier Science, 1996.
4. M. S. Dresselhaus, G. Dresselhaus, P. C. Eklund, Science of Fullerenes and
Carbon Nanotubes. Boston, MA: Academic Press, 1996.
5. Liu, Xiaodi, et al. "Ionic liquid-assisted solvothermal synthesis of oriented
self-assembled Fe 3 O 4 nanoparticles into monodisperse
nanoflakes." CrystEngComm 15.17 (2013): 3284-3287.
6. Baughman, Ray H., Anvar A. Zakhidov, and Walt A. De Heer. "Carbon
nanotubes--the route toward applications." science 297.5582 (2002): 787-792.