NANO MATERIALS

Nano Science is the study of phenomena and manipulation of materials at atomic, molecular
and macromolecular scales where properties differ significantly from those ,when they are at
a large scale.
Nanotechnology is the design, characterization, production and application of structures,

devices and systems by controlling shape and size at nanometer scale.( 10 9 m).
The word nano comes from the Greek word "nano" meaning dwarf. The term nano is
the factor 10-9 or one billionth. (Ex. the diameter of one hydrogen atom is 0.1 nm. Five atoms
of carbon would occupy a space of about 1 nm wide, a human hire is approximately 80000
nm). These reduced dimensional systems have drastically different electronic, chemical,
mechanical and optical properties than the normal molecules. The properties depend on the
size of the nano particles constituting the material.
Though nanotechnology appeared before 1980’s it did not become an experimental
science as there were no experimental tools available to the scientists to handle materials at
the atomic level. The invention of Scanning tunneling microscope (STM) changed the
scenario. In these microscopy techniques, a cantilever arrangement is made to read the
surface successfully. The sensing arrangement resembles the way record players needle reads
a record.

Scanning Tunneling Microscope:

In Scanning tunneling microscopy, the cantilever carries a tiny charge. The electrons which
make the charge stay in the cantilever as though they are in potential well. The atoms in the
investigation tend to reduce the height of the wall at which time the electrons can tunnel
through the wall. An arrangement is provided in the STM to map the exact number of
electrons that tunnel through the walls as the cantilever scans the surface. Thus the surface
details are recorded. By modulating the voltage at the cantilever it is possible to exert pulling
and pushing forces on the atoms to place them suitably on the surface.

Nano materials: When matter is arranged by exercising control over lengths of 1 to 100
nano meters and the formulating structures exhibit characteristics that are specific to their
size and dimensions, the resulting materials are termed nano materials. We can divide nano
materials as inorganic nano materials and organic nano materials.

Application of nano technology/ nano materials:

 Sunscreens based around micro fine particles, which combined with nanoparticles of
zinc oxide absorb UV light while allowing visible light to pass through. These
sunscreens appear translucent but act as effective absorbers of UV light.
 Nano materials are used for very thin coatings, such as self cleaning windows. The film
made out of titanium dioxide nano particles speeds up the breakdown of dirt and bacteria
in the presence of water and sunlight, which is then washed off the glass more easily.
 Nanocomposites are used to make car bumbers that are claimed to be 60% lighter and
twice as resistant to scratches and bumps as usual.
 Nanoparticles may convert pollutants to less harmful chemicals in the environment
through enhanced chemical reactions. The nanoparticles of iron are used to remove
organic pollutants from soil and ground water.
 Nano-engineered membranes could enable more energy efficient water purification
through use of electro spinning technique to spin cellulose into thin ultra-thin fibers that
are less than 100 nm in diameter potentially creating a molecular sieve. Cellulose is a
significant waste product in the industrial manufacture of clothes. These biodegradable
electro spun cellulose mats could be used to absorb fertilizers and pesticides allowing a
more targeted approach and use of chemicals.
 Nano-sensors are used to detect chemicals in the environment, and monitor the state of
mechanical stresses within buildings.
 Nano particles in paint technology offer the possibility of thinner and therefore lighter
coatings which could reduce the weight of aircraft and so cut greenhouse gas emissions.
 Important applications of Nano technology
 Advanced drug deliver
 Chemical- mechanical polishing with nano particle slurries.
 Systems on a chip (thin film batteries, nano pixels sensors for lower
consumption)
 Carbon nano tube products
 Inkjets systems (nano particle pigments)
 High hardness cutting tools.
Synthesis of nano materials:
There are 2 methods followed in preparing nano materials
1. Top-down process: In top –down approach, the metal is reduced from bulk size to
nano scale.

In this method, the well known processes are,

a) Ball Milling –In this method the bulk material which is taken in powder form is reduced
further by grinding technique until nano scale is reached.
b) Lithographic process - It involves forming a thin film of material on a substrate, wherein
a precise control over its thickness and area is exercised.
Ex: Visible / UV / X – rays / electrons/ ions lithography / Micro electro mechanical system
(MEMS).
c) Machining – 3 dimension patterning.
 2. Bottom-up process: In Bottom –up approach, the matter in atomic or molecular level
get assembled to form tiny clusters which grow to reach nano size.

In this method, the well known processes are,

a) Arc discharge deposition method:
b) CVD – nano films,
c) PVD – multilayer’s, nano tubes nano filaments
d) sol-gel methods

Top-down process/ approach:

Ball Milling:
This method is called top –down approach method. In this method the bulk material which is
taken in powder form is reduced further by grinding technique until nano scale is reached.
The ball mill consists of a hollow cylindrical chamber that can rotate about its own axis.
There are hard and heavy balls made of tungsten carbide/steel inside the chamber. Larger
balls are used for milling to produce smaller particle size. The chamber is mounted such that
its axis is slightly inclined to the horizontal to enable the material inside to slide and
accumulate around in one region.

The given material is crushed into small grain size and fed into the chamber. As the
cylindrical chamber is rotated around its own axis, the balls get carried upwards. But under
gravity, they drop down and hit the sample with high speed. This happens repeatedly and the
material will be powdered to get reduced to nano size particles .Sometimes to rotate the balls
Argon flow also allowed. Milling carried out at room temperature for up to 20-200 hours and
Annealing the powder at a temp. of 14000C for 6 hrs. This method is employed while
producing metallic and ceramic nano materials.

Advantages:

1. This method is suitable for large scale production at low cost.

2. It can be used to grind material irrespective of hardness.

Bottom-up process/ approach:
Arc Discharge method:

The set-up used in arc discharge method consists of a vacuum chamber in which two graphite
rods are mounted on two supports. There is a gap of about 1-2 mm between the two tips.

The chamber is evacuated by using a vacuum pump, and methane gas at certain pressure
introduced into the chamber. The two rods are maintained at a suitable dc potential difference
(70 amperes at 18 V dc) to enable the discharge. On the application of the voltage, the arc
discharge starts. Carbon evaporates from the anode. Some part of the evaporated carbon,
deposits on the cathode tip layer by layer. This is called hard deposit and the rest condenses
on other parts of cathode (called cathode soot) and on the walls of the chamber (called
chamber soot). Both the cathode soot and chamber soot yield carbon nano tubes whereas the
hard deposit does not yield any. Purification of soot should be done by oxidation,
centrifugation, filtration and acid treatment.
Carbon nano tubes:
A carbon nano tube is a sheet of carbon atoms joined in a pattern of hexagons and rolled into
a cylinder.

The nano tube’s conducting properties depend upon how the two ends of the sheet meet
along. Linear carbon hexagon arrangement of atoms along the meeting line makes the entire
tube conducting like a metal. With Spiral carbon hexagon arrangement the tube behaves like
a semiconductor.

If there is only one layer of graphite sheet, then it is called single wall nano tube (SWNT). If
there are a number of such co-axial tubes then each unit is called multi walled nano tube
(MWNT).
Properties/ characteristics of carbon nano tubes:

1. These are 100 times stronger than steel and weight is about one sixth of that of steel.
2. They are nonreactive and can withstand high temperatures.
3. Fundamental gap (for metallic) = 0 eV,
For semiconductor = 0.5eV
4. Electrical resistivity =10-4 ohm-cm
5. Thermal conductivity at room temp. = 200 W/ m K

6. Young’s modulus =1 T Pa (SWNT)

= 1.28 T Pa (MWNT)

7. Tensile strength = 30 G Pa
8. Carbon nano tubes are stable in Argon environment
9. These are very strong against strong acid and high temp. because of perfect conjugate
system.
10. Good filler matrix material (Carbon reinforced composites)

Shapes of Carbon nano tubes:

There are 3 types of Structures are Possible in terms of roll up vector,

1. Arm Chair structure.

2. Zig zag structure

3. Chiral structure.
T signifies the axis about which the sheets rolled. If T is rolled parallel to c-c bonds then it
will give arm chair structure and if the sheet is rolled with T at a certain angle to C-C bonds
we will get zig –zag and chiral structures.

Application of Carbon nano tubes

1. Field Emission for flat panel displays: When a small electric field is applied to the axis
of the nano tube, electrons are emitted. The same effect can be observed by applying a small
voltage between two parallel metal electrodes and spreading a paste of CNT on the electrode.

2. They can be used in field effect transistor,

3. CNTs are used in batteries to store Li + ions and to store hydrogen atoms.

4. as super capacitors
 Quantum Computation
Quantum Structures:
When the reduction from the bulk material (in 3–dimensions) is in one direction, it results in
a structure in 2- dimensions and is called Film.

If the reduction is in two directions, the resulting structure in 1- dimensions and is called
quantum wire.

If the reduction is in all the three directions, the material reduces to a point which is known as
quantum dot or nano particle or cluster.

As we can expect, the charge carriers were able to move in all the three directions in a 3D
material will be confined to plane in a film and to only one direction in a quantum wire but in
0 –D they will be confined to a small space. The film, wire and dot which are of dimensions
less than the bulk material must always possess certain thickness less than the mean free path
of electron along the absent direction. The thickness will be in nano meter range and material
exhibits mesoscopic properties along these directions.
Quantum Wires and Quantum Dots

What are Low-Dimensional Structures?

When one or more of the dimensions of a solid are reduced sufficiently, its
physicochemical characteristics notably depart from those of the bulk solid. With
reduction in size, novel electrical, mechanical, chemical, magnetic, and optical
properties can be introduced. The resulting structure is then called a low-dimensional
structure (or system). The confinement of particles, usually electrons or holes, to a low
- dimensional structure leads to a dramatic change in their behaviour and to the
manifestation of size effects that usually fall into the category of quantum-size
effects.
The low dimensional materials exhibit new physicochemical properties not
shown by the corresponding large-scale structures of the same composition.
Nanostructures constitute a bridge between molecules and bulk materials. Suitable
control of the properties and responses of nanostructures can lead to new devices and
technologies.

Classification of Low-dimensional Materials

Low-dimensional structures are usually classified according to the number of reduced
dimensions they have. More precisely, the dimensionality refers to the number of degrees of
freedom in the particle momentum. Accordingly, depending on the dimensionality, the
following classification is made:
Three-dimensional (3D) structure or bulk structure: No quantization of the particle
motion occurs, i.e., the particle is free.
Two-dimensional (2D) structure or quantum well: Quantization of the particle motion
occurs in one direction, while the particle is free to move in the other two directions.
One-dimensional (1D) structure or quantum wire: Quantization occurs in two directions,
leading to free movement along only one direction.
Zero-dimensional (0D) structure or quantum dot (sometimes called “quantum box”):
Quantization occurs in all three directions.
 Table 1. Nanostructures and their typical nano scale dimensions

Tradition has determined that reduced-dimensionality structures are labeled by the

remaining degrees of freedom in the particle motion, rather than by the number of
directions with confinement.

Physical behaviour at the nanoscale is accurately predicted by quantum

mechanics, as represented by the Schrödinger equation, which therefore provides a
quantitative understanding of the properties of low-dimensional structures.

INTRODUCTION to QUANTUM WIRES and QUANTUM DOTS

The most significant nanostructures required to design nano electronic devices are Quantum
Wells, Quantum Wires and Quantum Dots. They are the basic building blocks of nano
electronic devices. In nano electronics also we are going to control the transfer of electrons.
But how to confine them?, how to activate them?, how to fix the threshold level for
conductance?. All these questions will be answered when we understand the physics of these
three quantum structures.

Before discussing about the three types of fundamental nanostructures, let us

discuss the analogy of these structures for a basic understanding:

Quantum Wire
How to prepare Quantum Wire?
A standard quantum well layer can be patterned with photolithography or perhaps electron-
beam lithography, and etched to leave a free standing strip of quantum well material; the
latter may or may not be filled in with an overgrowth of the barrier material (in this case,
Ga(1-x)AlxAs ). Any charge carriers are still confined along the hetero structure growth (z-)
axis, as they were in the quantum well, but in addition (provided the strip is narrow enough)
they are now confined along an additional direction, either the x- or the y-axis, depending on
the lithography.

The following Fig. shows an expanded view of a single quantum wire, where clearly the
electron (or hole) is free to move in only one direction, in this case along the y-axis.

Quantum Dot

Quantum dots can again be formed by further lithography and etching, e.g. if a
quantum well sample is etched to leave pillars rather than wires, then a charge carrier
can become confined in all three dimensions, as shown in Fig.