TOPDOWN APPROACH

There are plenty of methods to synthesis nano materials. These methods are
grouped into two categories namely Top-Down and Bottom-Up techniques. The
techniques are classified based on the phase of the starting material. In the Top-
down class of techniques, the starting material is in solid state. Top-down
approach refers to a subtractive process in which a bulk starting material is
divided into smaller ones of nanosize. Depending on the requirement we have to
select an appropriate method for preparation of nano materials.
Top-Down techniques are
1) Mechanical grinding (Ball Milling)
2) Lithography
3) Etching
4) Erosion
5) Ion implantation
6) Sputtering
BALL MILLING
A ball mill is a device used to grind and blend materials for use in
mineral dressing processes, paints, pyrotechnics, ceramics and selective laser
sintering. It is a physical method of synthesis of nanoparticles and is an example
of top down approach of producing nanomaterials.

The ball mill consists of a hollow cylindrical shell which rotates about its axis.
The axis of the shell may be either horizontal or inclined at a small angle to the
horizontal. It is partially filled with the balls which may be made of chrome
steel, stainless steel, ceramic or rubber. These balls form the grinding media of
the ball mill. The inner surface of the cylindrical shell is generally lined (ie,
coated) with an abrasion resistant material e.g.. rubber or manganese steel.
Rubber is preferred for this purpose due to less wear in mills lined with rubber.
The length and diameter of the ball mill are nearly equal.
Principle:
A ball mill works on the principle of impact and friction. The size reduction
is carried out by impact as the balls drop from near the top of grinding halls the
shell. In this process, the solid particles in between the balls and ground are
reduced in size by impact. A number of materials can be used as grinding media
in a ball mill.
eg. ceramic balls, flint pebbles and stainless steel balls.

The grinding works on the principle of critical speed which is the speed after
which the steel balls start rotating along the direction of the cylindrical device,
thus causing no further grinding. High quality ball mills can grind mixture
particles to as small as 5 nm which enormously increases the surface area and
the reaction rates.The key properties of grinding media are its size, density,
hardness and composition.

Types of Ball Mill:

There are two kinds of ball mill (i) grate type, and (ii) overfall type, according
to different ways of discharging material. Some of the common ball mills are as
follows:

1. Vibrating ball mill

2.. High energy ball mill

3. Low energy tumbling ball mill

4. planetary ball mill

Advantages of a Ball Mill:

1. The cost of installation and grinding medium is low hence inexpensive

process.
2.Ball milling is suitable for both batch and continuous operation
3. Ball milling is suitable for both open and closed circuit grinding
4. Material of any hardness can be grounded
5. Small particles with narrow size distribution (2 to 20 nm) can be produced.

Drawbacks of Ball Milling:

1.Low surface, highly polydisperse size distribution and partially amorphous

state of the powder.
2. Shape of the nanomaterial is irregular.
3.Contamination of product may occur as a result of wear and tear.

Applications:

A ball mill can be used for the synthesis of nanostructured metaloxides

for gas detection.
It can also be used for grinding materials such as ores, chemicals,
ceramic raw materials and paints etc.
 Ball mills are used in pyrotechnics and the manufacture of black powder.

ETCHING
1. The process of removing a surface layer from a metal or plastic surface
through chemical erosion is known as chemical etching.
2. This process involves one or more chemical reactions that consume the
original reactants and produce new species.
3. The chemical used for etching is called an etchant.
4. In this process, the wafer to be etched can be immersed in a bath of
etchant.
5. Generally, etchants such as HCl, HN𝑂3 , 𝐻3S𝑂4 and 𝐻3P𝑂4 are used for
etching semiconductor oxide thin films.
6. ICP-RIE (Inductively Coupled Plasma - Reactive Ion Etching) is a dry
etching method that combines both chemical and physical etching to allow
isotropic and anisotropic material removal.
7. Wet Etching is an etching process that utilizes liquid chemicals or etchants
to remove materials from the sample. Wet etching is generally isotropic,
i.e., it proceeds in all directions at the same rate.

NANOLITHOGRAPHY
1. Lithography is the transfer of a required pattern from a master
slide/plate/mask to another medium.
2. Nanolithography is one of widely used top down techniques for the
preparation of nanostructured materials and patterns.
3. Nanolithography techniques is based on depositing, masking, etching or
writing the desired patterns with dimensions of the order of nanometers on a
solid material surface.
4. Using this technique, a pattern or design can be transferred at once on the
surface of a device by exposure with a radiation.
5. Depending on the exposure radiation sources, like photons, X-rays,
electrons and ions, the technique is classified as photolithography, X-ray
lithography, electron-beam lithography and ion beam lithography,
respectively.

(1) surface is coated with metal, (2) coating of photo resist on the substrate,
(3) mask placed over upper layer, (4) exposed UV radiation,
(5) resist development and stripping, and (6) etching to get final
pattern
There are many types of nanolithography namely
 Electron Beam Lithography
 Ion Beam Lithography
 Neutral beam lithography
 Nano Sphere Lithography
 Scanning Probe Lithography
 Dip Pen Lithography
  Optical Scanning Probe Lithography
 Thermo-Mechanical Lithography
 Electrical Scanning Probe Lithography
 Soft Lithography

EROSION

The electrospark erosion method was used for the synthesis of the
MoS2@ZnO nanoheterostructures . In our case, a 38% aqueous solution of
hydrogen peroxide was employed. MoS2@ZnO nanoheterostructures were
synthesized by electrospark erosion of zinc in the hydrogen peroxide and
simultaneous addition of MoS2 nanostructured powder in the reaction zone.
The reactor represents a porcelain vessel very resistant to electric current pulses.
185 g of zinc granules were placed into the reactor and then 200 mL of
hydrogen peroxide solution were poured. Two zinc electrodes were immersed in
the hydrogen peroxide solution until the complete electric contact with the zinc
granules. After this procedure, electric current pulses were applied to the
electrodes from the power supply within 30 s for each experiment. The
experimental conditions were the following: the electrode separation distance
was 10 cm, the voltage was 500 V, the current was 150 A. After the experiment,
the prepared suspension was separated into two fractions by decantation. Both
fractions were then maintained at 80 °C in a drying oven for 1 h.
Applications:
To obtain nanoscale particles of conductive materials (metals, alloys and
semiconductors), a method of synthesis based on the electrospark erosion of raw
materials in a liquid dielectric using the Electrical Discharge Machine (EDM)
ION IMPLANTATION

Ion implantation is used to modify existing surfaces of materials. In this

method, electrostatically charged high energy (10-100 Kev) ions are directed
towards the surface, where they arrive with kinetic energies several orders of
magnitude higher than the binding energy of the host material, and become
implanted in a surface layer that may be tens of nanometers thick.
APPLICATIONS:
 Ion implantation has been used in the semiconductor and mechanical
industries.
 Nitrogen or other ions can also be implanted into steel materials can
prevent crack propagation and corrosion.
 The use of ion implantation in the surface modification of textiles has
also been investigated in recent years.

SPUTTERING:
 Sputtering is a physical process in which atoms in a solid-state (target)
are released and pass into the gas phase by bombardment with energetic
ions (mainly noble gas ions).
 The principle of Sputtering is to use the energy of a plasma (partially
ionized gas) on the surface of a target (cathode), to pull the atoms of the
material one by one and deposit them on the substrate.
APPLICATIONS:
 1. In optical applications by depositing a thin layer on glass for
protection.
 2.In the semiconductor industry for depositing thin films of different
constituents on silicon wafers.