Module 4: Synthesis of nanomaterials: The Top-Down Approach

In the present module, we are focussing on the synthesis of nanomaterials, preferably

by the top-down approach. There are two important synthetic approaches for nanomaterial
preparation. They are exactly two opposite approaches. The first approach is top-down
approach and next approach is the bottom-up approach. Now we can move on to the details.
First of all the top-down approach. What we are doing in the top-down approach? Here,
nanomaterials are synthesized by breaking down of bulk solids into nanosized particles. It is
based on the principle of dispersion. The starting material is in the solid state. A pictorial
representation of the top-down approach is here

Here, we begin the synthesis from a bulk material, it is transformed into fragments and finally
converted into nanoscale or nanostructured materials. Now the next approach, that is the
bottom-up approach. Here, nanomaterials are synthesized by assembling the atoms/molecules
together. The starting material is ether in gaseous or in liquid state. The picture clearly depicts
the bottom-up approach.

Here, we are beginning from small molecules or atoms, combine together to get clusters and
clusters are finally converted to nanoscale objects or nanosized materials. The two synthetic
approaches are pictorially represented here in the same diagram.
So, the two approaches are exactly opposite approaches; one begins from the bulk and other
begins from atoms or molecules. By these two approaches we get nanoparticles. A more
conceptually legible picture is here.

Both the approaches will ultimately give the nanomaterials. The present module is aimed to
discuss the top-down approach and we can move on to different top-down methods. The
different popular top-down methods are:

➢ RF Plasma method
➢ Thermolysis
➢ Mechanical grinding
➢ Laser ablation
➢ Nanolithography
▪ Electron Beam Lithography
▪ Photolithography
➢ Sputtering

Moving on to the first method that is;

R F plasma method (Radio Frequency plasma method)

 It is one of the oldest techniques, especially for the synthesis of metal nanoparticles. It
involves the vaporization of the bulk metal and its condensation on a suitable substrate. Metal
placed in a container in an evacuated chamber is heated using high voltage RF coils. Helium
gas is then injected into the system to form high temperature plasma. The pictorial
representation of the experimental set up that we used in R F Plasma method is here.

There is a collector rod. The entire system is connected to the vacuum pump. There are RF
coils. The entire chamber is evacuated. The helium can be injected to the system. RF coils
generate plasma and that plasma convert metal to metal nanoparticles, as per the theory
discussed. Now the metal vapours nucleate on He gas ions. The particles diffuse towards colder
collector rod to deposit as nanoparticles. The reactive nanoparticles are finally passivated by
introducing gases like oxygen.

Now the second method under top-down synthesis;

Thermolysis
‘Thermo’ means temperature and ‘lysis’ means fission. That is, we are breaking the
materials into components by the application of high temperature. Thermolysis is the
decomposition of solids at high temperature. It is commonly used for metal nanoparticles. The
solid should contain metal cations and molecular anions or metal organic compounds. Pictorial
representation of thermolysis is shown here.
 The material is placed in an evacuated quartz tube and heated to decompose. The
obtained nanoparticles are finally passivated by suitable gas.
The third method under top down-synthesis;
Mechanical Grinding
Mechanical grinding or attrition or ball-milling is a top-down procedure. It is a popular
method due to simplicity and relatively inexpensive nature. Used in the synthesis of different
types of nanomaterials.
This picture represents the process under mechanical grinding.

Milling is achieved using high energy shaker, planetary ball, or tumbler mills. During
mechanical grinding, the energy transferred to the powder from the balls depends mainly on:
1. Rotational speed
2. Size and number of the balls
3. The time of milling
4. The milling atmosphere
Nanoparticles are produced by the shear action during grinding.

Mechanical grinding-Advantages
➢ Low installation cost
➢ Low cost of grinding medium
➢ Suitability for both batch and continuous operation
➢ Capable of both open and closed-circuit grinding
➢ Can be used on materials of practically any degree of hardness
Laser Ablation

We will have a better control on particle size by laser ablation method. Laser ablation
synthesis involves nanoparticle generation using a powerful laser beam that hits the target
material. Here, material is removed from the surface of a sample by laser irradiation. The
irradiated laser beam is absorbed on the sample surface, leading to rapid increase in
temperature. This results in vaporizing the target material into the laser plume. This vaporized
material may condense to form particles or clusters. The condensed particles can be deposited
onto a substrate or collected using a filtering mechanism. Laser ablation instrumentation is
shown.

A laser ablation device typically consists of two parts:

1.Pulsed laser, and

2.Ablation chamber
Advantages of Laser ablation technique

➢ It can be considered as a green technique, as there is no need for stabilizing agents or

other chemicals
➢ It can be performed using both a pulsed wave and continuous wave laser
➢ Low heat transfer to surrounding
➢ Wide range of nanomaterials can be produced
Another top-down approach is;

Nanolithography

The word nanolithography consists of three parts: "nano" meaning dwarf, "lith"
meaning stone, and "graphy" meaning to write, or "tiny writing onto stone". In general, we start
with a bulk solid and nanosized patterns are developed on it by removing unwanted parts from
the material. In lithography, we use a mask containing a pattern to be written on a substrate and
through the mask the substrate is irradiated using a suitable radiation. The substrate will be
covered with a resist which facilitate the interaction of the beam with the substrate.
Nanolithography- Different types

Based on the tool we used to ‘chisel’ the object to nano level, there are several types
of lithography. Some of them are:

➢ Electron beam lithography

➢ Photolithography
➢ Nanoimprint lithography and so on

Out of these methods, the present discussion focusses on electron beam lithography and
photo lithography.

Electron beam lithography (EBL)

Electron beam lithography is a technique used to draw patterns over a substrate by used
focused electron beam. EBL is used to fabricate two dimensional photonic crystals, quantum
wells, quantum wires and quantum dots. Basically, electron beam is used to etch away the
unwanted parts of the material. The surface of the substrate is covered with an electron-
sensitive film, also termed as resist. On exposure to the electron beam, the solubility of the
resist changes and it can be selectively removed. Depends on the resist, either the exposed part
or the unexposed part becomes more soluble. The resist can be simply removed by immersing
it in a solvent (Chemical development). Nanosystems are created and then subsequently
transferred to a substrate. Various steps in EBL are shown
Photolithography

It uses light to produce minutely patterned thin films of materials over a substrate. The
desired geometrical pattern is created on a photomask. This pattern is transferred from the
photomask onto a light sensitive material (photoresist) on a substrate. Further chemical
treatments are done to engrave the exposed pattern on the substrate.

Steps in Photolithography

Sputtering

Sputtering is a process used to produce nanomaterials via bombarding solid surfaces

with high-energy particles (plasma or gas). It is an effective method for producing thin films
of nanomaterials. In the sputtering deposition process, energetic gaseous ions bombard the
target surface, causing the physical ejection of small atom clusters. The sputtering process can
be performed in different ways (utilizing magnetron, radio-frequency diode, and DC diode
sputtering). It is performed in an evacuated chamber, to which the sputtering gas is introduced.
A high voltage is applied to the cathode and free electrons collide with the gas to produce gas
ions. The positive ions strongly accelerate in the electric field and hit the cathode target,
resulting in the ejection of atoms. The pictorial representation is shown
Top-Down Approach: Advantages

Here are the advantages of the top-down synthesis;

➢ Large scale production is possible

➢ Deposition over a large substrate is possible by this approach
➢ Generally chemical purification is not required

Top-Down Approach: Disadvantages

Here are the disadvantages of the top-down synthesis;

➢ Size distribution is broad (10-1000 nm)

➢ Varied particle shape or geometry
➢ Defects or imperfections may get introduced
➢ Expensive techniques