NANOSTRUCTURES

Properties of Nanomaterials
Properties of Nanomaterials

Zero-Dimensional Nanomaterials

One-Dimensional Nanomaterials

Two-Dimensional Nanomaterials

Three-Dimensional Nanomaterials
 Zero-Dimensional Nanomaterials
These materials have diameters <100 nm, and are denoted by
Properties of Nanomaterials

nanoparticles, nanoclusters, or nanocrystals

Nanoparticle
The term nanoparticle is generally used to encompass all 0 D
nanosized building blocks (regardless of size and morphology),
or those that are amorphous and possess a relatively irregular
shape
Herein, we will define
nanoparticles as amorphous
or semicrystalline or single 0
D nanostructures crystal with
dimensions larger than 10
nm, and a relatively large
(≥15%) size dispersion.
 For the fabrication of nanoparticles, a small size is not the only
requirement.
Properties of Nanomaterials

For any practical application, the processing conditions need to

be controlled in such a way that resulting nanoparticles have the
following characteristics:

(i) identical size of all particles (also called monosized or

with uniform size distribution)
(ii) identical shape or morphology,
(iii) identical chemical composition and crystal structure (iv)
individually dispersed or monodispersed, i.e. no agglomeration.

If agglomeration does occur, nanoparticles should be readily

redispersible
Properties of Nanomaterials
 The first 0D nanoarchitecture: the fullerenes
Properties of Nanomaterials

“Nanotechnology revolution” was catalyzed by the mid-1980s

discovery of carbon nanoclusters known as fullerenes C60

The 1996 Nobel Prize in Chemistry was awarded to Richard

Smalley, Robert Curl, and Sir Harold Kroto for this discovery

To date, the most common applications for fullerenes include

MRI contrast agents (exploiting its container properties),
drug-delivery agents (through surface functionalization), and
light-activated antimicrobial Agents etc.
Properties of Nanomaterials

C60, containing alternating six- and five membered rings of sp2

hybridized carbon atoms. This is only one isomer for C60, out of
a staggering total of 1,812 possible structures
 For amorphous/semicrystalline nanostructures smaller in size
Properties of Nanomaterials

(i.e., 1–10 nm), with a narrow size distribution, the term

nanocluster is more appropriate.
 It is also important here to note the difference between
nanoparticles/nanoclusters and traditional colloids, which date
back to the early 1860s
Properties of Nanomaterials

Term colloid, which is used to describe solid/liquid and solid/gas

suspensions such as milk, paints, butter, smoke, and smog.

Although both types of materials have sizes within the

nanoregime, the leading difference is the control one has over
composition and morphology.

In order to stabilize metal nanostructures, a stabilizing agent

must be used to prevent agglomeration into a larger powder. This
is also the case for colloids, which generally employ
polydispersed organic polymers and other ionic species that may
adsorb to the colloid surface.
 Analogous to bulk materials, any nanomaterial that is crystalline should be
referred to as a nanocrystal. This term should be reserved for those
materials that are single crystalline; if a particle exhibits only regions of
crystallinity, it is better termed a nanoparticle or nanocluster depending
Properties of Nanomaterials

on its dimensions.

Transmission electron microscopy, especially in tandem with electron

diffraction is most useful in determining the crystallinity of any
nanostructure

A special case of nanocrystal that is comprised of a semiconductor is

known as a quantum dot.

Typically, the dimensions of these nanostructures lie in the range 1–30 nm,
based on its composition Quantum dots currently find applications as
sensors, lasers, and LEDs. In fact, new high-density disks (e.g., HD-DVD and
Blu-ray high-definition DVD formats) may only be read via blue lasers, which
are fabricated from quantum dots. Long-term applications for these
structures will likely include optical computing and high-efficiency solar
cells.
 TEM images of amorphous
Properties of Nanomaterials

nanoclusters (a), and nanocrystals,

(b). The inset of (a) shows selected
area electron diffraction (SAED);
the absence of a pattern indicates
an amorphous structure. The
scale bar is 20 nm. The high-
resolution TEM image inset in (b)
shows lattice spacings of an
individual nanocrystal.
 Quantum dot
when an electron is promoted from the valence to conduction bands, an
Properties of Nanomaterials

electron–hole pair known as an exciton is created in the bulk lattice. The

physical separation between the electron and hole is referred to as the
exciton Bohr radius (rB) that varies depending on the semiconductor
composition.

In a bulk semiconductor crystal, rB is significantly smaller than the overall size

of the crystal; hence, the exciton is free to migrate throughout the lattice

However, in a quantum dot, rB is of the same order of magnitude as the

diameter (D) of the nanocrystal, giving rise to quantum confinement of the
exciton. Empirically, this translates to the strongest exciton confinement when
D ≤ 2rB.
 Analogous to the “particle-in-a-box” model from introductory physical
chemistry, exciton quantum confinement results in discrete energy levels
rather than the continuous bands of a bulk semiconductor crystal. Since
Properties of Nanomaterials

the gap between adjacent energy levels is infinitesimally small for a bulk
semiconductor, the bandgap is considered as a fixed value. In contrast,
since the dimensions of a quantum dot are extremely small, the
addition/subtraction of a single atom will significantly change the
nanocrystal dimensions and bandgap.

Table lists the rB values for common semiconductor crystals whose bandgap
may be easily fine-tuned by simply changing the diameter
of the quantum dot, as long as the dimensions are smaller than rB.
 In the early 1980s, Efros described the size-dependent electronic properties
of quantum dots, first delineating that the bandgap, En, will increase from
the bulk value based on a 1/R2 confinement energy term (Eq. 1).
Properties of Nanomaterials

According to quantum confinement theory, electrons in the conduction

band and holes in the valence band are spatially confined by the potential
barrier of the surface. Due to confinement of both electrons and holes, the
lowest energy optical transition from the valence to conduction band will
increase in energy, effectively increasing the bandgap.

where Eg is the bandgap of the bulk semiconductor; h, Planck’s constant; R,

the radius of the quantum dot; and μ is mass of the exciton given by
memh/(me +mh). Here me and mh are masses of the electron and hole,
respectively
Properties of Nanomaterials

where ER is the Rydberg (spatial correlation) energy of bulk

semiconductor:

where ε0 is the permittivity of free space; ε, the dielectric constant of the bulk
semiconductor; and me is the mass of the electron. Hence, the absorption
energy of quantum dots will shift to higher frequency with decreasing
diameter of the dots, with a dependence of 1/R2.
 Synthesis of metallic and oxide nanoparticles
Reduction of metal complexes in dilute solutions is the general
Properties of Nanomaterials

method in the synthesis of metal colloidal dispersions, and a

variety of methods have been developed to initiate and control
the reduction reactions.
In the synthesis of metallic nanoparticles, or more specifically
speaking, metallic colloidal dispersion, various types of
precursors, reduction reagents, other chemicals, and methods
were used to promote or control the reduction reactions

Colloidal dispersion of rhodium by refluxing a solution of

rhodium chloride and PVA in a mixture of methanol and water
at 79°C. Here, methanol was used as a reduction reagent

Commonly oxide particles in colloidal dispersions are

synthesized by sol-gel processing.
 One-Dimensional Nanostructures
Nanotube, Nanofiber, Nanowire, and Nanorod
Properties of Nanomaterials

Referred to as 1D nanostructures, is reserved for those materials

that have nanoscale dimensions that are equivalent in all but one
direction.

The common thread among all of these structures is that their

diameters must be within the 1–100 nm range; typically, their
lengths are within the micron (or larger) regime.
 Carbon nanotubes
Properties of Nanomaterials

The most widely studied 1D nanomaterial is the carbon

nanotube (CNT).

These structures were first discovered by Iijima in 1991, and

consist of a graphitic sheet(s) rolled into a tubular array.

Based on the layers of graphene sheets that comprise the CNT,

the structures are designated as single-walled, double-walled,
or multiwalled nanotubes (SWNTs, DWNTs, or MWNTs
respectively)
Properties of Nanomaterials

TEM images of MWNTs, formed from the folding (a) 5-, (b) 2-
(i.e., DWNT), and (c) 7- stacked graphene sheets.
 The diameters of CNTs range from 1 nm (SWNTs) to >30 nm
(MWNTs), with aspect ratios (length:width) ranging from 100 to
Properties of Nanomaterials

greater than 1 × 106 .

Even though the diameters of CNTs are orders of magnitude

smaller than a human hair, their tensile strength is ca. 20 times
greater than steel – a property attributed to extremely strong
sp2 bonding between neighboring hexagonal units.

The electrical conductivity of SWNTs may vary from metallic

to semiconducting, depending on the way a graphene sheet
is folded

For metallic SWNTs, the electrical conductance may exceed

silver or copper by three orders of magnitude.
 metallic

semiconducting
Properties of Nanomaterials
 Since CNTs have a high electrical conductivity and contain
sharp tips, these nanomaterials are the best-known field
Properties of Nanomaterials

emitter.

In general, the smaller the radius of curvature of the tip, the

more concentrated the electric field will be, which corresponds
to increased field emission at low required voltages. This
property is currently being exploited for the design of flat-panel
field emission displays.

Though plasma and LCD displays are hot ticket items at

electronics stores, they both possess inherent disadvantages.
Plasma displays are extremely heavy, consume a significant
amount of energy, and are prone to “burn-in,” which
permanently degrades the screen. On the other hand, LCD
screens are expensive to produce and often lack the response
time required to view fast-paced sporting events/movies
without blur.
 Hence, as far as picture quality is concerned, traditional CRT
Properties of Nanomaterials

displays are still among the finest quality. The replacement of

this technology with CNTs is a logical step in the evolution of
display panels. Rather than a single electron gun, CNT-based
screens will contain a separate nanotube electron gun for each
individual pixel in the display – dramatically enhancing the
resolution and clarity of the picture. Further, in contrast to
current large flat-panel televisions, the overall weight
of CNT-based analogues will be significantly lower, and they
will consume far less power.
 A nanotube is a 1D structure that contains a hollow core,
Properties of Nanomaterials

whereas the other three nanoarchitectures are solid

throughout.

MnO2 nanotube arrays

 Nanorods
A nanorod is typically a crystalline 1D nanostructure, with an
Properties of Nanomaterials

overall length comparable to its width (i.e., both dimensions are

<100 nm). As their name implies, another feature of nanorods is
their rigid sidewall structures. The term “nanocrystal” is
probably more appropriate for these structures (or, more
explicitly: “rod-like nanocrystals”).

SEM pictures of
ZnO nanorods
on sapphire
substrate (A)
and SiO2
substrate (B)

Whereas nanowires, nanofibers, and nanotubes exhibit an

interwoven array, nanorods are completely linear in
morphology. As such, nanorods are capable of stacking onto
each other to yield interesting 2D and 3D arrays
 Nanofibers

The term nanofiber should be reserved for 1D nanostructures

Properties of Nanomaterials

that are amorphous (and usually nonconductive) such as

polymers and other nongraphitized carbonaceous structures

Polymeric nanofibers can be made using the electrospinning

process. Elecotrospun nanofibers, with fiber diameters of 0.25
microns have been used in industrial, consumer and defense
filtration applications for more than twenty years.
Nanofibers provide dramatic increases in filtration efficiency
 2Dimentional Nano Structured Materials
Properties of Nanomaterials

2D nanostructures have two dimensions outside of the

nanometric size range. In recent years, a synthesis 2D NSMs
have become a focal area in materials research, owing to their
many low dimensional characteristics different from the bulk
properties. In the quest of 2D NSMs, considerable research
attention has been focused over the past few years on the
development of 2D NSMs. 2D NSMs with certain geometries
exhibit unique shape-dependent characteristics and
subsequent utilization as building blocks for the key
components of nanodevices
Properties of Nanomaterials

SEM image of Bi2WO6 nanoplates

Properties of Nanomaterials

SEM and TEM images of ZnO nanodisks

 3 Dimentional Nano Structured Materials
Properties of Nanomaterials

It is of great interest to synthesize 3D NSMs with a controlled

structure and morphology. In addition, 3D nanostructures are an
important material due to its wide range of applications in the area
of catalysis, magnetic material and electrode material

for batteries. Moreover, the 3D NSMs have recently attracted

intensive research interests because the nanostructures have higher
surface area and supply enough absorption sites for all involved
molecules in a small space . On the other hand, such materials with
porosity in three dimensions could lead to a better transport of the
molecules

nanoballs (dendritic structures),

nanocoils, nanocones, nanopillers
and nanoflowers
Properties of Nanomaterials

3D urchin-like nanostructured AlN

Properties of Nanomaterials

SEM image of Ag dendrites formed on the surface of Al foil

Properties of Nanomaterials

Low-magnification SEM images of 3D crystalline

TiO2 nanostructures
 Nanopowder
Properties of Nanomaterials

Analogous to bulk materials, the agglomeration of

noncrystalline nanostructural subunits should best be
termed a nanopowder
 Many techniques have been developed in the
synthesis and formation of one-dimensional
nanostructured materials
Properties of Nanomaterials

These techniques can be generally grouped into four

(1) Spontaneous growth:

(a) Evaporation-condensation
(b) Vapor (or solution)–liquid–solid (VLS or SLS) growth

(2) Template-based synthesis:

(a) Electroplating
(b) Colloid dispersion, melt, or solution filling

(3) Electrospinning
(4) Lithography
 Spontaneous growth and template-based synthesis are
Properties of Nanomaterials

considered as a bottom-up approach, whereas lithography

is a top-down technique.

Spontaneous growth commonly results in the formation of

single crystal nanowires or nanorods along a preferential
crystal growth direction depending on the crystal structures
and surface properties of the nanowire
materials.

Template-based synthesis mostly produces polycrystalline

or
even amorphous products
 Evaporation (dissolution)-condensation growth

Evaporation-condensation process is also referred to as

Properties of Nanomaterials

a vapor–solid (VS) process

Nanowires and nanorods grown by evaporation-condensation

methods are commonly single crystals with fewer imperfections.
The formation of nanowires, nanorods or nanotubules through
evaporation (or dissolution)-condensation is due to the
anisotropic growth.
 In a VLS growth, the process can be simply described as
following
Properties of Nanomaterials

The growth species is evaporated first, and then diffuses and

dissolves into a liquid droplet. The surface of the liquid has a
large accommodation coefficient, and is therefore a preferred
site for deposition. Saturated growth species in the liquid
droplet will diffuse to and precipitate at the interface between
the substrate and the liquid. The precipitation will follow first
nucleation and then crystal growth.

Continued precipitation or growth will separate the substrate

and the liquid droplet, resulting in the growth of nanowires.
Properties of Nanomaterials

Schematic showing the principal steps of the vapor–

liquid–solid growth technique: (a) initial nucleation
and (b) continued growth
 Example the VLS growth

A thin layer of gold is sputtered on a silicon substrate and

Properties of Nanomaterials

annealed at an elevated temperature (above the eutectic point

of 385 C of the silicon–gold system), which is typically the same
as the growth temperature.

During the annealing, silicon and gold react and form a liquid
mixture, which forms a droplet on the silicon substrate surface.

When silicon species is evaporated from the source and

preferentially condensed at the surface of the liquid droplet, the
liquid droplet will become supersaturated with silicon.
Subsequently, the supersaturated silicon will diffuse from
the liquid–vapor interface to and precipitate at the solid–liquid
interface
 Control of the size of nanowires
Properties of Nanomaterials

The size of nanowires grown by VLS method is solely

determined by the size of the liquid catalyst droplets. To
grow thinner nanowires, one can simply reduce the size of
the liquid droplets. Typical method used to form
small liquid catalyst droplets is to coat a thin layer of catalyst
on the growth substrate and to anneal at elevated temperatures
Properties of Nanomaterials

Synthesis of 3D NSMs by physical processes In recent

years, with the progress of nanotechnology, there has
been increasing interest in the synthesis of 3D NSMs (for
instance spring-like nanocoils, ball-like nanodendritic
structures, and nanoflowers) because they are exhibit
newer and/or better physical/chemical properties.

Concerning the fabrication of these nanoarchitectures,

evaporation technique, sputtering technique, lithography
process, hot plasma, cold plasma, spray pyrolysis, inert
gas phase condensation technique,
 3D graphitic nanosheets using CVD in the presence of
methane gas
Properties of Nanomaterials

(A) SEM and (B) AFM images of the 3D graphitic nanosheets

 Metallic nanoparticles
Properties of Nanomaterials

Metallic nanoparticles possess unique optical,

electronic, chemical and magnetic properties that
are strikingly different from that of the individual
atoms as well as their bulk counterparts .

Various physical properties, such as, mechanical

strength, ductility, thermal stability, sintering ability,
diffusivity and the chemical reactivity of the particles
in the nanometer regime have also been found to be
dependent on particle size without a change in the
chemical composition of the particles.
 In a metal cluster, atoms at surfaces have fewer
neighbours than atoms in the bulk. As a result, the atoms in
Properties of Nanomaterials

the bulk are co-ordinatively saturated while the atoms on the

surface are co-ordinatively unsaturated.

Because of this lower coordination and unsatisfied bonds,

surface atoms are less stabilised than bulk atoms.

The smaller a particle, the larger the fraction of atoms at the

surface and the higher the average binding energy per atom.

One distinguishing characteristic of nanometer scale

structures is that unlike macroscopic materials, they typically
have a high percentage of their constituent atoms at the
surface.
 The volume of an object (Vα R3, where R is the
characteristic length) decreases more quickly than
Properties of Nanomaterials

its surface area (S αR2) as the size diminishes: S/V α

R-1, where R has atomic or molecular dimensions.

This scaling behavior leads, in the most extreme

case, to structures where nearly every atom in the
structure is interfacial and in some sense, it could
be assumed that nanostructures are “all surface”.
The term ‘surface’ has been used to indicate the
geometrical separation between two or more
phases of matter whereas the term ‘interface’
implies a region of finite thickness over which the
phase change occurs
 Another important aspect is the electronic structure of the
nanoparticles that depends critically on the size of the
Properties of Nanomaterials

particles.

In metals and semiconductors, the electronic wavefunctions of

conduction electrons are delocalised over the entire particle.

Electrons can, therefore, be described as ‘particles in a box’

and the densities of state and the energies of the particles
depend crucially on the size of the box which, at the onset,
leads to a smooth size dependence.
Properties of Nanomaterials

The HOMO– LUMO band gap of semiconductor particles and

therefore, their absorption and fluorescence wavelengths
become size dependent

Ionisation potentials and electron affinities are tuned

between the atomic values and the work function of the bulk
material by variation of the cluster size. These properties
relate to the availability of electrons for forming bonds or
getting involved in redox reactions and thus, the catalytic
activity and selectivity also become functions of size
 However, for small particles with dimension in the nanometer
regime, the electronic states are not continuous, but discrete,
due to confinement of the electron wavefunction.
Properties of Nanomaterials

The average spacing of successive quantum levels, δ, known as

the Kubo gap, is given by,
δ = 4EF /3N
where, EF is the Fermi energy of the bulk materials and N, the
nuclearity i. e., the number of atoms in the nanocluster.

Fermi energy of the bulk metal and n is the number of valence

electrons in the nanoparticle (usually taken as its nuclearity).
Thus, for a Ag nanoparticle of 3-nm diameter containing ~103
atoms, the value of d would be 5–10 meV. Since at room
temperature, kT @ 25 meV, the 3-nm particle would be metallic
(kT > d). At low temperatures, the level spacings especially in
small particles, may become comparable to kT, rendering them
nonmetallic
Properties of Nanomaterials

Named after the Japanese theoretical physicist, Roygo Kubo

introduced the concept in 1962.

The Kubo gap is the average spacing that exists between

consecutive energy levels and measured in the units of
millielectron volts (meV).

Since, the number of valence electrons in the nanoparticles

is measured as a function of nuclearity, the energy level
spacing varies inversely with the nuclearity of the particles
Properties of Nanomaterials

Evolution of the band gap and the density of states as

the number of atoms in a system increases
 In band theory, the breadth of a band is directly related to the
strength of interactions among nearest neighbours.
Properties of Nanomaterials

For atoms/molecules, this interaction is weak which

corresponds to a narrow band.

Additional atoms are added to the solid, stronger interactions

will occur resulting in a greater density of states near the Fermi
level.

Hence, the insulating properties of very small nanoclusters are

due to the small number of neighboring atoms which are
held together primarily by non-metallic interactions (e.g., van
der Waal forces).

As size of the nanocluster increases, the atomic s/p and d

orbitals from a larger number of constituent atoms will broaden
into bands forming an energy continuum
 Theoretical investigations of the electronic structure of metal
nanoparticles gold clusters with N = 6,……,147 also throw light
on the size-induced changes in the electronic structure.
Properties of Nanomaterials

The HOMO-LUMO gap decreases with particle size from 1.8 eV

for Au6 to 0.3 eV for Au147.

The Kubo gap has dramatic effect on the properties associated

with the material. It is possible to control the Kubo gap
which will, then, cause the system to become metallic or non-
metallic.
 Atoms have their well known atomic orbitals. Depending on
the extent of overlap in a solid they remain mostly
Properties of Nanomaterials

unperturbed, as in noble gases, or they combine to extended

band structures, as in metals or semiconductors. The core
orbitals are confined to a relatively small volume and remain
localised (atom-like). Each of N atoms contributes with its
atomic states to a band so that, although the width of a band
increases slightly when more atoms are added, the density of
states (DOS) within a band is basically proportional to the
number of atoms of an ensemble with an extended band-like
state.

The band width amounts typically to a few eV. Thus, the DOS is
on the order of N per eV, which is very large for a bulk amount
of matter (N # Avogadro’s number, NA) but low for small
clusters.
Properties of Nanomaterials

An important threshold is reached when the gap between the

highest occupied and the lowest unoccupied state (called the
Kubo gap d) equals thermal energy

When electrons get thermally excited across the Kubo gap, a

low temperature insulator becomes a semiconductor and at
higher temperatures a metal; and also magnetic properties of
small clusters can change dramatically. This non-metal-to-metal
transition can take place within a single incompletely filled
band, or when two bands begin to overlap because of band
broadening
Properties of Nanomaterials

Temperature dependence of the resistivity for

nanostructured Nb films with different grain
sizes (dXRD). The scale on the left refers to the
metallic films with dXRD 8 nm while the scale on
the right is for the insulating films with dXRD < 8 High resolution transmission electron
micrographs of the nanostructured Nb
nm. sample with dXRD ≈ 5 nm. The grains are
defined as
crystallographically ordered regions
Particle size dependence of the resistivity at 10 (delineated in the figure) while the
and 300 K, depicted, respectively, by open disordered inter-granular regions are ≈1
triangles and circles. nmwide.
 Nanocomposites
Properties of Nanomaterials

The creation, processing, characterization, and

utilization of materials, devices, and systems with
dimensions on the order of 0.1–100 nm, exhibiting
novel and significantly enhanced physical,
chemical, and biological properties, functions,
phenomena, and processes due to their nano-
scale size’’ .

Current interests in nanotechnology

encompass nano-biotechnology, nano-systems,
nano-electronics, and nano-structured materials,
of which nanocomposites are a significant parti
Properties of Nanomaterials

The expansion of length scales from meters (finished

woven composite parts), micrometers (fiber diameter),
sub-micrometers (fiber/matrix interphase) to nanome-
ters (nanotube diameter) presents tremendous
opportu-nities for innovative approaches in the
processing, characterization, and analysis/modeling of
this new gen-eration of composite materials.
Properties of Nanomaterials

Constituents have at least one dimension in

the nanometer scale.

 Nanoparticles (Three nano-scale dimensions)

 Nanofibers (Two nano-scale dimensions)
 Nanoclays (One nano-scale dimensions)
 Nanoparticle-reinforced composites
Properties of Nanomaterials

Particulate composites reinforced with micron-sized particles of various

materials are perhaps the most widely utilized composites in everyday
materials. Particles are typically added to enhance the matrix elastic
modulus and yield strength. By scaling the particle size down to the
nanometer scale, it has been shown that novel material properties can be
obtained

Micron-scale particles typically scatter light making otherwise

transparent matrix materials appear opaque. showed in their
study of SiO2/epoxy composites that decreasing the particle size
resulted in significantly improved transmittance of visible light.
 Nanoplatelet-reinforced composites
Clay and graphite. In their bulk state, both clay and
Properties of Nanomaterials

graphite exist as layered materials. In order to utilize these

materials most efficiently, the layers must be separated and
dispersed throughout the matrix phase.

The advantages of polymer-based clay nano-composites

include improved stiffness, strength, tough-ness, and thermal
stability as well as reduced gas permeability and coefficient of
thermal expansion

In addition to mechanical properties, the thermal sta-bility, fire

resistance and gas barrier properties of poly-mer/clay
nanocomposites can be enhanced through the addition of
nanometer-scale reinforcement.
Nanoclays
Properties of Nanomaterials
 Nanofiber-reinforced composites
Vapor grown carbon nanofibers (CNF) have been
Properties of Nanomaterials

used to reinforce a variety of polymers, including poly-

propylene, polycarbonate, nylon, and epoxy.
Carbon nanofibers are known to have wide-ranging
morphologies, from structures with a disordered bamboo-
like structure to highly graph-itized ‘‘cup stacked’’
structures

Carbon nanofibers typically have diameters on the order of 50–200 nm

Properties of Nanomaterials

Researchers utilized a variety of techniques to

achieve dispersion of carbon nanofibers in a poly(ethylene
terephthalate) (PET) matrix and subsequently melt-spun
fibers. The compressive strength and torsional moduli of the
nanocomposite fibers were considerably higher than that for
the unreinforced PET fiber
Properties of Nanomaterials Carbon nanotube-reinforced composites

The density of a SWCNT is about 1.33–1.40 g/cm3

, which is just one-half of the density of aluminum. The elastic
modulus of SWCNT is comparable to that of diamond
(1.2 TPa). The reported tensile strength of SWCNT is much
higher than that of high-strength steel (2 GPa). The
tremendous resilience of SWCNT in sustaining bending to
large angles and restraightening without damage is
distinctively different from the plastic defor-mation of metals
and brittle fracture of carbon fibers at much lower strain when
subjected to the same type of deformation.
Properties of Nanomaterials

The electric current carrying capability is estimated to be 1·10

9 amp/cm 2 , whereas copper wires burn out at about 1·10
6 amp/cm 2 . The thermal conductivity of SWCNT is predicted
to be 6000 W/ m K at room temperature; this is nearly double
the ther-mal conductivity of diamond of 3320 W/m K.
SWCNTs are stable up to 2800 C in vacuum and 750 C in air,
whereas metal wires in microchips melt at 600–1000 C.
SWCNTs have great potential in field emission applications
because they can activate phosphors at 1– 3 V if electrodes are
spaced 1lm apart. Traditional Mo tips require fields of 10–100
V/lm and have very limited lifetimes.
 The outstanding thermal and electric properties com-bined
Properties of Nanomaterials

with their high specific stiffness and strength, and

very large aspect ratios have stimulated the development
of nanotube-reinforced composites for both structural
And functional application
 Both SWCNTs and MWCNTs have been utilized for
Properties of Nanomaterials

reinforcing thermoset polymers (epoxy, polyimide, and

phenolic), as well as thermoplastic polymers (polypro-
pylene, polystyrene, poly methyl methacrylate (PMMA),
nylon 12 etc.

Researchers fabricated nanocomposites consisting of DWCNTs

with a high degree of dispersion The resulting composites
showed increase of strength, Young s modulus and strain to
failure at a nanotube con-tent of only 0.1 wt%. In addition, the
nanocomposites showed significantly enhanced fracture
toughness as compared to the unreinforced epoxy..
Properties of Nanomaterials

In the processing of nanocomposites, carbon nano-tubes need

to be separated from bundles and dispersed uniformly in a
polymer matrix for maximizing their contact surface area
with the matrix. Modification of nanotube surfaces, for
example, the creation of cova-lent chemical bonds between
nanotubes and the poly-mer matrix, enhances their
interactions and gives rise to higher interfacial shear strength
than van der Waals bonds.
 Critical issues in nanocomposites
There is a lack of understanding of the interfacial
Properties of Nanomaterials

bonding between the reinforcements and the matrix

material from both analytical and experimental
viewpoints
Dispersion
Uniform dispersion of nanoparticles, and nanotubes
against their agglomeration due to van der Waals bond-ing is
the first step in the processing of nanocomposites.
Beside the problems of agglomeration of nanoparticles,
exfoliation of clays and graphitic layers are essential.
SWCNTs tend to cluster into ropes and MWCNTs pro-duced
by chemical vapor deposition are often tangled
together like spaghettis. The separation of nanotubes
in a solvent or a matrix material is a prerequisite for
 Alignment
Properties of Nanomaterials

Because of their small sizes, it is exceedingly

difficult to align the nanotubes in a polymeric
matrix material in a manner accomplished in
traditional short fiber com posites. The lack of
control of their orientation dimin-ishes the
effectiveness of nanotube reinforcement in
composites, whether for structural or functional
performance.
 Volume and rate
Properties of Nanomaterials

High volume and high rate fabrication is fundamen-

tal to manufacturing of nanocomposites as a commer-
cially viable product. The lessons learned in the
fabrication of traditional fiber composites have clearly
demonstrated that the development of a science base
for manufacturing is indispensable. Efficiency in
manu-facturing is pivotal to the future development of
nanocomposites
 Cost effectiveness
Properties of Nanomaterials

Besides high volume andhigh rate production, the cost

of nanocomposites also hinges on that of the nano-
reinforcement material, particularly, nanotubes. It is
anticipated that as applications for nanotubes and their
composites increase the cost will be dramatically
reduced
Properties of Nanomaterials

Size dependent absorption spectra

Properties of Nanomaterials

UV-visible absorption spectroscopy probes electronic transitions

due to electronic excited states
 Some Applications
Properties of Nanomaterials

Detection of Impurities

UV absorption spectroscopy is one of the best methods for determination of

impurities in organic molecules. Additional peaks can be observed due to
impurities in the sample and it can be compared with that of standard raw
material. By also measuring the absorbance at specific wavelength, the impurities
can be detected.

Structure elucidation of organic compounds.

UV spectroscopy is useful in the structure elucidation of organic molecules.

It is rarely used as a primary method for structure determination

 Quantitative analysis
Properties of Nanomaterials

UV absorption spectroscopy can be used for the quantitative determination

of compounds that absorb UV radiation.

Qualitative analysis
UVabsorption spectroscopy can characterize those types of compounds
which absorbs UV radiation. Identification is done by comparing the
absorption spectrum with the spectra of known compounds.

Chemical kinetics
Kinetics of reaction can also be studied using UV spectroscopy. The
UV radiation is passed through the reaction cell and the absorbance
changes can be observed.

Band Gap determination

Particle size determination

Properties of Nanomaterials

Transition between two electronic energy levels should give

rise to a line in an absorption.

In practice, it may not be possible to distinguish individual

line.

Large molecules have large number of vibrational and

rotational levels. These energy levels may be close together.
UV-vis radiation may rise molecules at many slightly
different electronic energy levels to many slightly different
higher levels.

As a result sharp lines are replaced by narrow bands

 A convenient method of characterizing the size and size distribution of
semiconductor nano-particles is UV/Visible absorption spectroscopy
Properties of Nanomaterials

Semiconductor nano- crystallites are know to have an absorption edge, which is

shifted with respect to the bulk materials towards shorter wavelengths

Blue Shift
Nanosized semiconductor particles generally exhibit a threshold energy in the
optical absorption measurements, due to the size specific band gap structures,
which is reflected by the blue shifting of the absorption edge (from near-infrared
to visible) with decreasing particle size
Properties of Nanomaterials
Properties of Nanomaterials
 Blue shift provides an indirect way to evaluate, at least qualitatively, the
Properties of Nanomaterials

variation of particle core dimensions

Optical absorption spectra for d=2.8-, 4.1-, and 5.6-nm

CdSe quantum dots dispersed in chloroform
 UV-Vis absorption spectra for ZnO nanoparticles.
Properties of Nanomaterials
Properties of Nanomaterials
Properties of Nanomaterials

An exciton is a bound state of an electron and hole which are attracted to each other by
the electrostatic Coulomb force. It is an electrically neutral quasiparticle that exists in
insulators, semiconductors and some liquids. The exciton is regarded as an elementary
excitation of condensed matter that can transport energy without transporting net
electric charge

An exciton forms when a photon is absorbed by a semiconductor. This excites an electron

from the valence band into the conduction band. In turn, this leaves behind a localized
positively-charged hole. The electron in the conduction band is then attracted to this
localized hole by the Coulomb force. This attraction provides a stabilizing energy balance.
Consequently, the exciton has slightly less energy than the unbound electron and hole.
 Size distribution
Properties of Nanomaterials

If there is a very narrow size distribution, the first exciton peak will be
very sharp. This is because due to the
narrow size distribution, the differences in band gap between different
sized particles will be very small and hence most of the electrons will get
excited over a smaller range of wavelengths
Silver Nanoparticles
Properties of Nanomaterials
Properties of Nanomaterials

In metal nano particles such as in silver, the conduction band and

valence band lie very close to each other in which electrons move
freely. These free electrons give rise to a surface plasmon resonance
(SPR) absorption band occurring due to the collective oscillation of
electrons of silver nano particles in resonance with the light wave

Classically, the electric field of an incoming wave induces a polarization

of the electrons with respect to much heavier ionic core of silver
nanoparticles. As a result a net charge difference occurs which in turn
acts as a restoring force. This creates a dipolar oscillation of all the
electrons with the same phase.
 When the frequency of the electromagnetic field becomes resonant with
the coherent electron motion, a strong absorption takes place, which is
the origin of the observed colour. Here the colour of the prepared silver
Properties of Nanomaterials

nanoparticles is dark reddish brown. This absorption strongly depends

on the particle size, dielectric medium and chemical surroundings

Small spherical nano particles (< 20nm) exhibit a single surface plasmon
band . The UV/Vis absorption spectra of the silver nano particles dispersed
in chloroform
 UV-vis absorption spectra of 9, 22, 48, and 99
nm gold nanoparticles in water
Properties of Nanomaterials

Figure shows the absorption spectra of four different size gold

nanoparticles. The plasmon absorption is clearly visible and its maximum
red-shifts with increasing particle diameter 517, 521, 533, and 575 nm for
the 9, 22, 48, and 99 nm particles).
 Absorption spectra of cadmium telluride
semiconductor nanocrystals including Bulk
Properties of Nanomaterials

Size(nm) Ab. Peak Gr. time

0.8 6 700 nm 8 min

Absorbance (arb. unit)

5.2 679 nm 4 min
4.7 665 nm 3 min
4.2 643 nm 2 min
0.6
2 531 nm 5 sec
Bulk

0.4

0.2

0.0
400 600 800 1000
Wavelength (nm)
 Phonons in Nanostructures
Properties of Nanomaterials
 Phonons are the principal carriers of thermal energy
Properties of Nanomaterials

in semiconductors and insulators, and they serve a

vital role in dissipating heat produced by scattered
electrons in semiconductor devices

Phonons are present in any material. They are the

driving forces for quite a number of phenomena
mentioning only the thermal expansion, heat
conductivity, temperature dependence of mechanical,
electric properties, phase transitions. They also enhance
the diffusion. They occur in bulk crystals, surface,
interfaces, multilayers, crystals with topological defects
and impurities.
 What are Phonons?
Properties of Nanomaterials

Just as light is a wave motion that is considered as composed of

particles called photons, we can think of the normal modes of vibration
in a solid as being particle-like. Quantum of lattice vibration is called
the phonon.
Phonon dispersion

The problem of lattice dynamics (LD) is to find the normal modes of vibration
of a crystal. In other words, LD seeks to calculate the energies (or frequencies
) of the phonons as a function of their wave vector's q . The relationship
between energy and q is called phonon dispersion .
Unlike static lattice model , which deals with average positions of atoms in a
crystal, lattice dynamics extends the concept of crystal lattice to an array of
atoms with finite masses that are capable of motion. This motion is not random
but is a superposition of vibrations of atoms around their equilibrium sites due to
the interaction with neighbor atoms.

A collective vibration of atoms in the crystal forms a wave of allowed

wavelength and amplitude.
 Two possible modes of vibrations of atoms in the crystal
Properties of Nanomaterials

Longitudinal

Transverse

In case of longitudinal mode the displacement of atoms from

their equilibrium position coincides with the propagation
direction of the wave

In the case of transverse mode, atoms move perpendicular to

the propagation of the wave.
 ACOUSTIC AND OPTICAL VIBRATIONS
Properties of Nanomaterials
 The difference between acoustical and optical branches
arises because of the more options of vibrations for atoms in
Properties of Nanomaterials

the unit cell. For example, atoms A and B of diatomic cell

can move together in phase (acoustical branch) or out of
phase (optical branch).
 ACOUSTIC AND OPTICAL BRANCHES
In a simple mono atomic solid with only one atom per primitive
cell , one can have only three acoustic phonon branches
Properties of Nanomaterials

corresponding to the three degrees of freedom of atomic motion.

On the other hand, for monoatomic solids with two atoms per
primitive cell such as diamond, magnesium, or diatomic
compounds such as GaAs, one also has three optic phonon
branches in addition to the three acoustic phonons

In compounds with a greater number of atoms and complex

crystal structures, the number of optic phonons is more than
three.

If the crystal unit cell contains N atoms, then 3N degrees of

freedom result in 3 acoustic phonons and 3N − 3 optical
phonons.
Properties of Nanomaterials

These phonons can propagate in the lattice of a single crystal as

a wave and exhibit dispersion depending on their wavelength
or equivalently their wavevector

Phonon propagation is interrupted when a grain boundary is

encountered in a polycrystalline material.

In an isolated grain the phonon can get reflected from the

boundaries and remain confined within the grain.
 However, from the point of view of phonons, a well-
crystallized
Properties of Nanomaterials

polycrystalline sample with several micrometer grain size can

be treated as a bulk/infinite crystal for all practical purposes

The consequences of phonon confinement are noticeable in

the vibrational spectra only when the grain size is smaller
than typically 20 lattice parameters.

The atomic vibrational frequencies in crystalline solids

range from zero to about 100 THz.
Properties of Nanomaterials

Acoustic phonons have frequencies from zero to

about a few hundred wave numbers

Optic phonons have higher frequencies

Hence the vibrational spectra could be probed using

infrared absorption/reflectivity or using Raman
spectroscopy
 One-dimensional lattice
Properties of Nanomaterials

The simplest model to study vibrations in periodic solid is known as

one dimensional monoatomic chain, which consists of a chain of
atoms of mass ‘m’ , equilibrium distance ‘a’ and harmonic interaction
between atoms.

Un =displacement of atom n from its equilibrium position

Un-1=displacement of atom n-1 from its equilibrium position

Un+1=displacement of atom n+1 from its equilibrium position

 One might think about the atoms in the lattice as interconnected by elastic
springs. Therefore, the force exerted on n-th atom in the lattice is given by
Properties of Nanomaterials

where C is the interatomic force (elastic) constant and

u n+1 – un relative displacement
Applying Newton’s second law (F = ma) to the motion of the n-th atom
we obtain

(1)

Note that we neglected here by the interaction of the n-th atom with
all but its nearest neighbors In order to solve the above equation,
travelling plans waves of amplitude A, frequency ‘ ω’ and wave number
‘q, are assumed

(2)
i. e

where xn is the equilibrium position of the n-th atom so that xn=na

 Now substituting Eq.(2) into Eq.(1) and canceling the common
quantities (the amplitude and the
time-dependent factor)
Properties of Nanomaterials

we obtain

This equation can be further simplified by canceling the common

factor eiqna , which leads to

We find therefore the dispersion relation for the frequency

which is the relationship between the frequency of vibrations and
the wavevector q.
Properties of Nanomaterials
 Diatomic 1D lattice
Now we consider a one-dimensional lattice with two non-equivalent
Properties of Nanomaterials

atoms in a unit cell

We can treat the motion of this lattice in a similar fashion as for monoatomic
lattice. However, in this case because we have two different kinds of atoms, we
should write two equations of motion:

Solution in the form of traveling mode for the two atoms leads to
 Depending on sign in this formula there are two different
solutions corresponding to two different dispersion curves, as
Properties of Nanomaterials

is shown in Figure
Properties of Nanomaterials

Phonons interaction are altered due to dimensional confinement in nanostructures

These effects show some similarities to those for an electron confined in a

quantum well.

= ħ2 (k2 x + ky 2 )/2 me* + n22 ħ2/ 2m Lz 2

( n = 1, 2,3,…)

kz = n/Lz

The dimensional confinement of phonons also results in similar restrictions in the

phonon wave vector, qz = n/Lz
 Scaling- induced phonon confinement effect
in GaAs Nanoparticles
Properties of Nanomaterials

Raman spectra of confined LO phonon in GaAs nanoparticles. The bulk

spectrum is also shown for comparison.

Note the asymmetric broadening of the line shape and also the shift of the
peak towards the low-frequency side
 Scaling- induced phonon confinement effect in
Nanowire structures
Properties of Nanomaterials

Raman spectra of 3 Ge NW samples (D=5, 10, 20nm) and

bulk Ge measured at 500uW laser power with 514.523 nm
wavelength.
Properties of Nanomaterials

Experimental Raman spectra four Si nanowire samples (each is a different

ensemble of Si nanowires with a different core diameter distribution, as
measured by TEM)
 Raman spectra develop marked asymmetry towards the low frequency
Properties of Nanomaterials

side and exhibit marginal shift in the peak position also towards the same side.

As the optical phonon dispersion curves in most solids have negative dispersion,

That is, phonon frequency decreases as a function of wavenumber, the increased

intensity in the wing of the Raman spectra on the low-frequency side basically arises
from the contribution from the phonon branch away from the zone center

Raman red shift is the consequence of the combination of the effects of size-
induced phonon confinement and surface relaxation. The structural defects
may also contribute to the Raman red shifts
 The dependence of the peak shift and the line
broadening on the particle size is shown in
Properties of Nanomaterials

Figure for the longitudinal optic phonon in

GaAs.

Both peak shift and the line width increase as the

particle size reduces.

However, the changes are marginal if the particle

size is larger than 10 nm.
 Other methods of observing the dispersion
relation of lattice vibrations
Properties of Nanomaterials

•Neutron Inelastic Scattering

•Electron Energy Loss Spectroscopy (EELS)
•Inelastic Atom Scattering
 Carbon Nanotubes
&
Inorganic nanowires
• Carbon, a group IV element, has two crystalline forms:
diamond and graphite. Carbon nanotubes (CNTs) are
allotropes of carbon.
• These cylindrical carbon molecules have novel properties that
make them potentially useful in many applications in
nanotechnology, electronics, optics and other fields of
materials science, as well as potential uses in architectural
fields.
• They exhibit extraordinary strength and unique electrical
properties, and are efficient conductors of heat.
• CNTs are members of the fullerene structural family, which
also includes the spherical buckyballs. The ends of a CNT
might be capped with a hemisphere of the buckyball structure.
 Who found first nanotube?

1970: Morinobu Endo- First carbon filaments of nanometer

dimensions, as part of his PhD studies at the University of
Orleans in France. He grew carbon fibers about 7 nm in
diameter using a vapor-growth technique. Filaments were not
recognized as nanotubes and were not studied.

1991: Sumio Iijima- NEC Laboratory in Tsukuba-- used high-

resolution transmission electron microscopy to observe carbon
nanotubes.
 Graphite
Hexagonal graphite:
I. Graphite has a structure containing layers of atoms
arranged at the corners of contiguous hexagons.
II. (not to be confused with hexagonal close packed).
III. 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).
IV. The lattice constant a = 246.6 pm
V. C=669 pm
Graphite
 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 are Carbon nanotubes?
•Carbon nanotubes
(CNTs) are allotropes of
carbon which are cylindrical
carbon molecules have
interesting properties that
make them potentially
useful in many applications.
 Carbon nanotube
CNT: Rolling-up a graphene sheet to form a tube

Schematic STM image

of a CNT of CNT

Institute of Optics, University of Rochester 8

 Properties
• 132,000,000:1 Length-To-
Diameter Ratio
• Diameter of 3 to 9 nm
• Lengths in the millimeter
range
• Efficient electrical
conductors
• Can act as both thermal
conductors and thermal http://brent.kearneys.ca/wp-content/uploads/2006/05/carbon_nanotube.jpg

insulators
Single-Wall Nanotube (SWNT)

Armchair Zig-Zag
 Multi-Walled Nanotubes
(MWNT)

• Multiple rolled layers of

graphene sheets
• More resistant to
chemical changes than
SWNTs

http://www.siemens.com/innovation/en/about_fande/corp_technology/par
tnerships_experts/uc_berkeley.htm
 How CNTs are made?
– Chemical Vapor Decomposition (CVD)
- Natural, incidental, and controlled flame environments
• Arc discharge
– CNTs Can be found in the carbon soot of graphite
electrodes during an arc discharge involving high
current. This process yields CNTs with lengths up to 50
microns.
• Laser Ablation
– In the laser ablation process, a pulsed laser vaporizes a
graphite target in a high-temperature reactor while an inert
gas is inserted into the reactor. Nanotubes develop on the
cooler surfaces of the reactor as the vaporized carbon
condenses.

–All these techniques rely on vaporizing carbon and

condensing some fraction into extended nanostructures.
–Morphosynthetic control provides routes to tune the
details of these self assembled nanostructures.
 Chemical Vapor Deposition
(CVD)
• This method is used to synthesize CNTs in
quantities in excess of few milligrams.
• In this hydrocarbon gas (Methane, CO, etc) is
decomposed at elevated temperatures (650 – 900
⁰C). Energy source transfers energy to carbon
molecule. After energy transfer, the carbon
molecule binds to the substrate, i.e. carbon
atoms are condensed onto a cooled substrate that
may contain various catalysts (Fe).
• Yield is usually about 30%
• One of the most common methods of carbon
nanotube synthesis
 Chemical Vapor Deposition
Advantages
• Open ended tubes are formed
• Allows continuous fabrication
• Easy to increase scale to
industrial production
• Large length
• Simple to perform
• Pure product
• Due to open ended tubes, can
be used as templating agents
 ARC DISCHARE METHOD
• High temperature is obtained by shorting two
carbon nanorods together, which causes a
plasma discharge.
• Such plasmas easily achieve temperatures in
excess of where carbon vaporizes at 4500 K.
• Low potential differences & moderately high
currents are needed to produce this arc.
 Important points
• Arc method & CVD produce MWNT.
• To encourage SWNT formation , it is necessary to
add a metal catalyst (Co, Fe, Ni) to the carbon source.
• These metal catalyst particles block the end-cap of
each carbon hemisphere and SWNT growth.
• The growth directions of nanotubes can be controlled
by van der waal forces, electric fields & patterning of
metal catalysts onto different substrates.
 Laser Ablation
• Discovered in 1995 at Rice
University
• Vaporizes graphite at 1200 ⁰C
• Helium or argon gas
• A hot vapor plume forms and
expands and cools rapidly
• Carbon molecules condense to
form large clusters
• Similar to arc discharge
• Yield of up to 70%
 Types of Laser Ablation
• Pulsed • Continuous
– Much higher light – Much lower light
intensity (100 kW/cm2) intensity (12 kW/cm2)

http://www.goalfinder.com/product.asp?productid=112
 Laser Ablation
Advantages
• Good diameter control
• Few defects
• Pure product

Disadvantages
• Expensive because of lasers
and high powered
http://www.gsiglasers.com/MarketSectors.aspx?page=
equipment 56
 Ball Milling
• Powder graphite is
placed in a stainless
steel container
• Argon gas is used
• Process occurs at room
temperature
http://www.rsphysse.anu.edu.au/nanotube/

• Powder is then annealed

 Applications
Electrical
• Field emission in vacuum
electronics
• Application in electrodes, capacitors
Energy storage
• Lithium batteries
• Hydrogen storage
Biological
• sensors
• AFM tips
• DNA sequencing
 Electrical Application: FED
Field Emission Display ( FED)
- Uses electron beam to produce color
images (FED)
- Traditionally cathode ray tubes are used
but recently more focus on using carbon
nanotubes
- NASA is researching this technology to
use in space exploration
 Energy Storage: Lithium batteries
• Nanotubes have the highest reversible
capacity of any carbon material for use in
Lithium ion batteries

• Nanotubes have intrinsic characteristics

desired in material used as electrodes in
batteries and capacitors

• Nanotubes are outstanding materials for

super capacitor electrodes

• They also have a number of properties

including high surface area and thermal
conductivity that make them useful as
electrode catalyst supports in Polymer
Electrolyte Membrane (PEM) fuel cells
 Energy storage: Hydrogen storage
• Single-walled carbon
Nanotubes can store hydrogen
• Nano tube technology will
meet the challenge of storing
hydrogen and releasing them
adequately in hydrogen fuel
car in future
• Physisorption and
chemisorption mechanisms
used for hydrogen storage in
carbon nanotubes
 Biological applications: sensing
• Many spherical Nano-particles have been
fabricated for biological applications.
• Nanotubes offer some advantages relative to
Nano-particles by the following aspects:
1. Larger inner volumes – can be filled with chemical or biological
species.
2. Open mouths of Nano tubes make the inner surface accessible.
3. Distinct inner and outer surface can be modified separately.
Biological applications: AFM tips
Carbon nanotubes as AFM probe tips:
1. Small diameter – maximum resolution

Resolution of ~ 12nm is achieved

 Biological applications: DNA
sequencing
• Nanotubes fit into the
grove of the DNA
strand
• Apply voltage across
CNT, different DNA
base-pairs give rise to
different current
signals
• With multiple CNT, it
is possible to do
parallel fast DNA Top view and side view of the
sequencing assembled CNT-DNA system
Paper battery
• The battery is made up of
cellulose paper embedded with
aligned carbon nanotube
electrode and electrolyte;
• Could easily be mistaken for a
sheet of black paper

• Functions as both a lithium-ion

battery and a supercapacitor

• Lightweight, thin, flexible

• Can function at a wide range of

temperatures
Nanotube speakers
• Thin carbon nanotube
films can act as
speakers
• New generation of
cheap, flat speakers
• Transparent, flexible,
stretchable, and magnet
free
Nanotube thermocell
• uses multiwalled
carbon nanotubes as
electrodes
• 3 times efficient than
conventional
• Converts waste heat
from industrial plants,
pipelines into
electricity
Nanotube Catalysts
• Carbon nanotubes doped
with Nitrogen
• Reduce oxygen more
effectively than platinum
catalysts
• Not susceptible to carbon
monoxide poisoning,
known to deactive
platinum catalysts
 Inorganic nanowires
• A nanowire is a nanostructure, with the
diameter of the order of a nanometer
(10−9 meters).
• Nanowires are microscopic wires that have a
width measured in nanometers. Typically
their width ranges from forty to fifty
nanometers, but their length is not so
limited. Since they can be lengthened by
simply attaching more wires end to end or
just by growing them longer, they can be as
long as desired.
• At these scales, quantum mechanical effects
are important — which coined the term
"quantum wires".
 What Are Nanowires Made of?

• Nanowires are metal just like other, regular

wires. The only real difference in concept is
their size. They also vary in complexity and
uses. While they can do many of the same
things, they have many other capabilities
beyond those of regular wire.
 Types of nanowires
• Superconducting (e.g., YBCO[1]),
• Metallic (e.g., Ni, Pt, Au),
• Semiconducting (e.g., Si, InP,GaN, etc.),
• Insulating (e.g., SiO2, TiO2).
• Molecular nanowires are composed of
repeating molecular units either organic
(e.g. DNA) or inorganic (e.g. Mo6S9-xIx).
 Synthesis of nanowires
• There are two basic approaches to synthesizing nanowires:
top-down and bottom-up.
• A top-down approach reduces a large piece of material to
small pieces, by various means.
• A bottom-up approach synthesizes the nanowire by
combining constituent atoms. Most synthesis techniques use a
bottom-up approach.
• Nanowire production uses several common laboratory
techniques, including suspension, electrochemical deposition,
vapor deposition, and VLS growth. Ion track
technology enables growing homogeneous and segmented
nanowires down to 8 nm diameter.
 Most common method
Colloid-templating strategy
• It uses a colloid-templating strategy that involves layer-by-
layer assembly of polyelectrolytes & inorganic nanoparticles
on submicrometre- and micrometre-sized polystyrene (PS)
latex particles.

Other methods
• Laser Ablation
• Carbo-thermal reduction
• Solution based methods
 Au/TiO2 core sheath nanowire

• By using nanowire-templating technique based on layer-by-

layer approach & calcining (heating in air to drive off volatile
templating agents), ordered Au/TiO2 core sheath nanowires are
fabricated.
• A template-grown gold nanowire array is used as a positive
template
• Then a cationic polyelectrolyte & an inorganic precursor are
assembled on gold nanowires by layer-by-layer technique.
• Calcination then converts the inorganic precursor to titanium
dioxide.