PHYSICS OF NANOMATERIALS

Module -III
Growth Techniques in Nanomaterial
Recap of previous Modules
Module -I
1. Defination of Nano and Nanomaterial
2. Classification of Nanomaterials
3. Size effects
4. Significancy, Challenges and Applications of Nanomaterials

Module -II
1. Microstructure
2. Defects in nanomaterials
3. E'ect of nanodimension on material properties
 Growth Techniques in Nanomaterial
Or
Preparation methods for Nanomaterials
 Preparation methods for Nanomaterials

Mainly Two approches are there

1.Top down
2.Bottom up
 Top down
Bottom up
Top down

Nanoparticles
Nanowires/rods/tubes
Nanothinfilms
Bottom up
 Preparation methods for Nanomaterials

(Top down) (Bottom up) Non-

Lithographic Lithographic

Vacuum based Solution

process based process
 (Bottom up)
Non-Lithographic

Vacuum based Solution

process based process

1.Evaporation
1.Sol-Gel
2.Sputtering
3.Pulsed laser deposition 2.Electrodeposition
4.Molecular beam epitaxy
5.Chemical vapor deposition
 (Top down)
Lithographic

Photolithography Electron beam

lithography
 (Bottom up)
Non-Lithographic

Vacuum based process Solution based process

Vacuum: It is a region with a gaseous pressure much less than

atmospheric pressure

O2,H2, N2
etc Remove
 (Bottom up) Non-Lithographic
Vacuum based process
Adv
1.Clean process
2.Deposition of unwanted
material is low
3.High efficent devices
Dis adv
1. Costly
2. Complicated equipments
3. Limited to some materials
Solution based process
At atmosphere pressure
Adv
1. Simple process
2 Less cost
3. Long range of material
Dis adv
1.Not very clean process
2.Deposition of undesired
materials is high
3. not compatible with
modenn technology
For each technquie/method

1. Principle
2. Expt Set up
3.Working
4.Advantage and disadvantage
4.Which materials are prepared
General vacuum system
1. Vacuum chamber or
deposition chamber
or growth chamber

2. Vacuum pumps

3.Vacuum
measurement guages

4. Gas inlet
Vacuum chamber Substrate Heater
Substrate rotator
5.Substrate holder
6.Substrate heater
Crystal/Thick
7.Substrate rotator ness monitor
8.Crystal monitor
9. Shutter holder Substrate

Shutter

Variable material source

And power supply
Preparation of Nanomaterials by Evaporation
Priniciple

Material to be deposited (to be prepared in the form

of nanomaterial) is heated to using resistive heating
or electron bombardment and the evaporated
material ( atoms) depostied on the substrate in form
of nanomaterials (particles, wires, film) depending on
the conditions at the substarte. Wafer holder

Wafers

heating by means of energy produced by the

Atomic
passing of electric current through resistance flux

units. Source material

Vacuum Heater (resistance
or E-beam)

Vacuum system
Exhaust
 Evaporation
Thermal evaporation Electron beam evaporation

Resistive Heating Electron Bombardment

Wafer holder

Wafers

Atomic
flux

Vacuum Source material

Heater (resistance
or E-beam)

Vacuum system
Exhaust
 Thermal evaporation

Principle
Material to be prepared in the form of nanomaterial is
heated to using resistive heating elements and the
evaporated material ( atoms) depostied on the
substrate in form of nanomaterials (particles, wires,
film) depending on the conditions at the substarte.
Resistive heating elements

Tungsten (3000oC)
Molybdenum (2300oC)
Tantalum (3000oC)
Experimental arrangement Heater

Thickness
monitor

holder Substrate
Photos of source material for evaporation

18
Substrate holders
Working Video
1. Load the substrates and material to be deposited in to the vacuum chmaber

2. Create the high vacuum using pumps (10-6-10-8 mbar)

3. Resistive element (boat/spira wire) is heated by passing high current through it (I2R)

4. When the substance/material is heated adequately

It begins to evaporate, travel towards substrate and deposit on the substrate.

Wafer holder

Wafers

Atomic
flux

Vacuum Source material

Heater (resistance
or E-beam)

Vacuum system
Exhaust
Depending on the conditions at the substarte
(particles, wires, film)
4. Advantages

1.It is simple and cheap.

2.Excellent purity of films
3.Less substrate surface damage from impinging atoms as
the film is being formed.
 4. Disadvantages

1.Limited to low melting point metals.

2.Step coverage is more difficult to improve (or) complex

geometries can not be coated
3. More di&cult control of (lm composition (ex:ZnS, ZnSe)

4.Materials react with heated boat and

form alloy leads to impure films
5.Which materials are prepared

Mostly Thin films (2D nanomaterials)

Nanowires, Nanorods (1D )

Very rarely used for nanoparticles (0D)

 Electron beam evaporation

1. Principle
Material to be prepared in the form of nanomaterial is
heated to using Electron beam bombardment
(heating) and the evaporated material ( atoms)
depostied on the substrate in form of nanomaterials
(particles, wires, film) depending on the conditions at
the substarte.
 2. Experimental set up
Thickne
ss
monitor
holder Substrate

Evaporated material
Photos of source material for evaporation

No powder samples
Source material crucibles

Graphite, Alumina cruicbles

Working Video
Working
1.Load the substrates and material to be deposited in to the
vacuum chmaber.

2.Create the high vacuum using pumps (10-6-10-8 mbar).

3.Supply current to the filament, when the filament gets heated to

High temperatures thermoionic emission of electrons takes place
(beam electrons are emitted from filament).

4.Emitted electrons accelearted towards anode (crucible/material in

the cruicble) by high poterntial difference (5-10kV).
4.A magnetic field is often applied to bend the electron beam and
made it fall on the material to be evaporated.

5.Energetic impact of the electron beam raises the temperature of

the material,

6.When the substance/material is heated adequately It begins to

evaporate, travel towards substrate and deposit on the substrate.

7. Crucible is always cooled with cold water circulation.

 3. Advantages
1. Controlled deposition rates (very low to very high)
2. Excellent purity of films
3. Used for low and high melting point materials also

Disadvantages
1.It is costly
2. Incident electron beam can produce the x-rays
3. More di&cult control of (lm composition (ex:ZnS, ZnSe)
4.Which materials are prepared

Mostly Thin films (2D nanomaterials)

Nanowires, Nanorods (1D )

Very rarely used for nanoparticles (0D)

 1. Principle
Sputtering is a process whereby atoms are ejected from a solid target material
due to bombardment of the target by energetic partciles ( gas ions).
It is a momentum exchange between the ions and atoms in the target materials, due to
collisions.
Sputtering can be performed top-down and
bottom-up.
2. Expt Set
up

1.Vacuum system
2.High voltage source
3. Gas inlet(Argon)
Anode

Cathode
Expt Set up
Sputtering
Substrate

Target
material
Portable sputtering systems
Target holders
Substrates:on which we want to
grow nanowires/particles/nanofilms

Usually : Silicon wafers (substrates)

Glass substrates
Working Video 1111

2222

1.Load the substrates and target material to be deposited in to the

vacuum chmaber.

2.Create the high vacuum using pumps (10-6-10-8 mbar).

3. Allow Argon gas till 10-3-10-2 chamber pressure and maintain the
pressure constantly.
4.Switch on the high voltage and apply between the cathode
(target material) and anode (substrate holder).

5.Plasma is generated due to highly accelerated electron impact

with Ar atoms and Ar atoms becomes ionized (Ar+).

6. Ar+ ions and colloide with target material (since it is cathode) ,

atoms are ejected (Sputtered) from a solid target material and
deposit on the substrate as a thinfilm.
Advantages
1.High and low melting points materials are easily sputtered.
2.Sputter deposited films have a composition close to that of the
source(target) material (ZnSe,YBCO).
3.Sputtered films typically have a better adhesion on the
substrate than evaporated films.
4. Step covarage is more
Disadvantages
1.Sputtering rates are low compared to those that can
be attained in thermal evaporation
2.Substrate damage due to ion bombardment or UV
generated by plasma

3. Slightly expensive
5.Which materials are prepared

Mostly Thin films (2D nanomaterials)

Very rarely used for

Nanoparticles (0D)
Nanowires, Nanorods (1D )
Sputtering – additional methods

● Reactive sputtering
● RF sputtering
● Magnetron sputtering
● Collimated sputtering
● Hot sputtering
Molecular beam epitaxy

Most expensive
Mostly used in semiconductor industry
Most Complicated
 Molecular beam epitaxy
1.Principle
2. Expt Set up
3. Working
4.Advantages and disadvantages
5.Which materials are prepared
 Molecular beam epitaxy
Molecular: Any Material
‘Beam’ :
means the evaporated atoms do not interact
with each other or with other vacuum chamber
gases until they reach the wafer
Epitaxy

growth of film with a crystallographic

relationship between film and substrate
 Molecular beam epitaxy
Principle
1.Ultra pure elements are heated in separate quai-
effusion cells.
2.Molecular or atomic beams from effusion cell go
and fall on a surface of a heated crystalline
substrate under ultra high vacuum
Expt Set Up
Expt Set Up
Atomic beam
Working

Video
1,2,3,4

1.Load the substrates in load lock chamber and target materials to

be deposited in to effusion cells in the the main vacuum chmaber.

2.Create the high vacuum using pumps (10-6-10-8 mbar) in load

lock chamber and create the ultra high vacuum (10-11 mbar) in
main chamber

3.Now move the substrates from load lock chamber to main

vacuum chamber.
4.Heat the source (which we want to deposit/evaporate)
material in the effusion cells and made it evaporate.

5.Now allow the evaporant from effusion cells in a

controlled manner on to the heated substrate.

6.After the desired thickness is achived (This can be

monitired using REED) close the shutter of the effusion cell.

7.Move the substrate the holder to load lock chamber,

unload the substrate the holder from the load lock takeout
the coated substrate.
Advantages
1.High purity,defect free and epitaxial films
2.Control of thickness at atomic layer level
3.Complex materials can be deposited
(GaAs,PbTiO3 etc)
4.Can be used for both high and low melting point
materials also
Disadvantages
1. Very expensive
2. Low deposition rate(~ 10 nm/min)
Which materials are prepared

Nanowires, rods, nanothinfilms but not nanoparticles

Plasma Arc Discharge/ Evaporation
1.Principle
2.Expt Set up
3.Working
4.Advantages and disadvantages
5.Which materials are prepared
Plasma

Plasma is described as a fourth state

of matter consist of electrons, ions
and atoms.
 Electric Discharge

Lightning is a sudden electrostatic discharge during an

electrical storm between electrically charged regions of
a clouds
Electric arc Video 11111
An electric arc is the form of electric discharge with the
highest current density. The maximum current through an arc
is limited only by the external circuit, not by the arc itself
Plasma Arc Discharge/ Evaporation
1. Principle
1.Electrical Arc produced between the anode and
cathode due to potential difference

2.Anode (material which we want to deposit) get heated

up, melt and vaporizes. Generated vapor deposited on
the cathode ( substrate on whcih we want to coat) and
chamber walls
 Expt Set up

1. Vacuum system
2. Electrodes
3. Voltage source
4. Extra gas inlet
Expt Set up
Working Videos 222_1,2,3
1. Load the source materials as a anode:
(which material we want to evaporate) and
cathode (on which we want to coat the
material).
2. The inter elect rode distance during t he
stationary period of discharge d ≤ few mm.
3. Create the high vaccum (10-4-10-6 mbar)
4.The pressure of the inert gas (helium) l l
in the discharge chamber is P =5OO Torr..
5. Apply voltage between electrodes

6.Electrical Arc produced between the anode and cathode due

to potential difference

7.Anode (material which we want to deposit) get heated up,

melt and vaporizes. Generated vapor deposited on the cathode
( substrate on whcih we want to coat) and chamber walls
SEM images of MWNT’s produced by arc
discharge (Kunsan National Univ)
Advantages
1. Easy and less cost (expensive)

Disadvantages
1.Only limited materials
2.It is difficult to deposit on the substrates like Silicon
Glass substrates.
Which materials are prepared

Mostly used for

Carbon nanotubes

Nanotubes, wires, rods, nanoparticles but not thinfilms

Chemical Vapor Deposition (CVD)

1.Principle
2.Expt Set up
3.Working
4.Advantages and disadvantages
5.Which materials are prepared
Chemical Vapor Deposition (CVD)

Thinfilm

Vapors (gases) Using

Solid materials
Gas Precursors
Chemical Vapor Deposition
● CVD => Chemical Vapor Deposition
● PE-CVD => Plasma Enhanced CVD
● MO-CVD => Metal Organic CVD
● Atmospheric pressure CVD (AP-CVD)
● Low-pressure CVD (LP-CVD)
● Ultrahigh vacuum CVD (UHV-CVD)
● Aerosol assisted CVD (AA-CVD)
● Direct liquid injection CVD (DLICVD)
1. Principle
Chemical vapour deposition (CVD) is a process where one or more
vapour phase precursors (material which we want to deposit)
decompose on a heated substrate (on whichwe want to
coat/deposit) and deposit in the form of a film.

(Or)
Thin film deposition take place due to a chemical reaction
between vapour phase precursors and hot substrate
2. Expt Set up

Substrate
 Working : CVD process steps
Video 1 2 3
Gas stream

1 7
2 6

3 4 5
Wafer
Susceptor

1.Transport of reactants to the deposition region.

2.Transport of reactants from the main gas stream through
the boundary layer to the wafer surface.
3. Adsorption of reactants on the wafer surface.
4. Surface reactions, including: chemical decomposition or reaction,
surface migration to attachment sites .
5. Desorption of byproducts.
6.Transport of byproducts through boundary layer.
7.Transport of byproducts away from the deposition region. 17
.
 Types of CVD reactions
• Thermal decomposition(pyrolysis)

SiH4(g) → Si(s) + 2H2(g)

Ni(CO)4(g)  Ni(s) + 4CO(g) (180oC)
CH4(g)  C (graphene/carbon nanotube)+ 2H2(g)

• Reduction (using H )
2

WF6(g) + 3H2(g)  W(s) + 6HF(g)

SiCl4(g) + 2H2(g)  Si(s) + 4HCl (g) (1200oC)

Oxidation (using O2)

•
: SiH4(g) + O2(g) ---> SiO2(s) + 2H2(g)
2AlCl3(g) + 3H2(g) + 3CO2(g)  Al2O3 + 3CO (g)+ 6HCl (g)
(1000oC) 18
Flow chart
Working :
Advantages:
High growth rates possible
Can deposit materials which are hard to evaporate Good
reproducibility
Can grow epitaxial

Disadvantages
High temperatures(>600OC)
Complex processes
Toxic and corrosive gasses
Which materials are prepared

Mostly used for

Nanowires, nanotubes

Nanotubes, wires, rods, thinfilms but not nanoparticles

● Atmospheric pressure CVD (AP-CVD)

● Low-pressure CVD (LP-CVD)

●

●
Chemical Vapor Deposition (CVD)
6. Plasma arc discharge
Electro Deposition/Electroplating

1.Principle
2.Expt Set up
3.Working
4.Advantages and disadvantages
5.Which materials are prepared
 Electrodeposition

=
+
Electricity and Liquids Thinfilm
Substrate
(chemicals) Using
Solid materials Gas Precursors
Liquid solutions
1. Principle
Electrodeposition is the application of a metal coating to a
metallic or other conducting surface by an electrochemical
process

Electrochemical reactions are

responsible for
Film growth
2. Expt Set up

1.Cathode: on which we want to deposit

It can be any conducting substrate
2.Anode: Material which we want to deposit in
the form of thin film
3.Electrolyte: Solution containing Anode
material
4.DC power supply
Electro Deposition/Electroplating

at anode M(s) → Mz+(aq) + ze-

at cathode Mz+(aq) + ze-→ M(s)

Working

1.The Substrate on which coating/plating is going to

takes place is made it as cathode
2.Material which is to be deposited/plated on the
cathode is made as a anode.

3.Choose An aqueous solution containing the

required anode metal in an oxidised form, either as an
aquated cation or as a complex ion.
4. Now immerse the both electrodes in the
electrolyte solution glass beaker and connect to
the battery
5. Switch on the battery Video 1 2 3 4
6. During electrolysis metal is deposited on to the
cathode and metal from the anode dissolves in the
aqueous solution

at anode M(s) → Mz+(aq) + ze-

at cathode Mz+(aq) + ze-→ M(s)
Example -1

Copper Cathode is reduced Nickel Anode is oxidized

(accepts electrons) (gives us electrons)

Nick Raymond

Ni2+ ions within solution become attracted to Copper cathode

Example -2
Example -3
Example -4
Electrodeposition
1.Electrolytic deposition (ELD) : Thin films (Metal
salt solutions)
2.Electrophoretic deposition (EPD): Thick films
(Suspension of cermic particles)
Advantages:
Good control of thickness
Uniform deposition
Low cost for equipment and starting material
Deposition on complicated shapes

Disadvantages

Typically restricted to electrically conductive substrate materials

Limited materials
Additional high temperature annealing steps are required and
unsuitable for polymer substrates
Which materials are prepare d

Only
thinfilms

Not for Nanotubes, wires, rods, nanoparticles

6. Plasma arc discharge
 Sol-gel

1.Principle
2.Expt Set up
3.Working
4.Advantages and disadvantages
5.Which materials are prepared

Solution based method

Sol
A sol is a colloidal suspension of very small solid particles in a continuous liquid medium.

Gel
A gel is a semi-rigid mass that forms when the solvent from the sol begins to evaporate and
the particles or ions left behind begin to join together in a continuous network
Sol-gel
 Sol-gel
Principle: Sol-Gel synthesis of nanomaterials
(particles, 4lms, 4bers and wires) are mainly depend on the
hydrolysis and condensation of metal alkoxides and
metal chlorides.

Hydrolysis and condensation reactions lead to the

formation of colloids (Sol).
2. Expt Set up

No special set up
1.Glass beakers
2.Precursor solutions
3.Heating arrangement
4.Spin coater,Dip coater,Spray
coater
Working
Step 1-2: Take the required solution precursors and
allow them to undergo condensation reaction, which
results in the formation of Sol.
Step 3: Take the prepared sol solution and deposit in
the form of thinfilm by spin coating, dip coating and
spray coating.

Video 1 2 3

Spin coat (Thin film) Dip coat (Thin film) Spray (Thin film)
Step 4: Take sol and draw the fibers
Step 1

Step 2

Step 3

Step 4
Step 5: Convert sol into gel

Dehydration
Slow dry
Rapid dry

Xerogel
Aerogel

Sinter/calcination
Dense
ceramic
Unifrom particles
Advantages
Simple process and low cost
Can coat onto large area or complex shape objects

Multicomponent systems

Large range of materials can be deposited

Disadvantages
1. Not a clean process
2. Not compatiable with latest device fabrication technology
Which materials are prepared

We can prepare nanoparticles,

nanofibers, wires, rods and thinfilms
Above structures are
prepared by top down
process only
PHYSICS OF NANOMATERIALS

Module -III
Growth Techniques in Nanomaterial

Lecture 25
6. Plasma arc discharge
Above structures are
prepared by top down
process only
6. Plasma arc discharge
Photography
 Lithography
Principle: It is a printed method that uses
chemical processes to create at image
using light/electron beams/ion beams and
photo resistive material.

Light: Photo lithography

Electrons: Electron beam lithography
Photoresist
A photoresist is a light-sensitive material (PMMA)

Positive Negative
 Photo lithography
Principle: It is a printed method that uses
chemical processes to create at image
using light (UV light) and photo resistive
material
 PMMA
Working Video 1

5) Develop 6) Etch 7) Strip

Working

Light
Working steps

Step1: Take required substrate on which you want to form

specail structure/features

Step 2: Coat the photoresist material on to the above

substrate using spin coating

Step 3: Now expose the light through selected mask pattern

Step 4: Now immerse the above substrate (light reacted) in

the developer solution

Reaction takes depending on the photoresist

Step 5 Now immerse the above developed substrate inthe
etching solution (removing material wherever we required)

Step 6 Finally, strip off the leftover phtotresist

Step 7 we can find the required pattern on the substrate

Can we prepare features from 1-
100 nm using light ???

Big No

Why
Small feature requires

Smaller size pattern on the mask

When the mask pattern size euql or smaller

than wavelength of the light used ?????

Diffraction
Diffraction limits the resolution = 50 nm

In photolithography
If you want resolution <50 nm

We need to use e-beam

E-beam lithography
 E-beam lithography
Principle: It is a printed method that uses
chemical processes to create at image
using electron beam and photo resistive
material
Working
Working steps

Step1: Take required substrate on which you want to form

specail structure/features

Step 2: Coat the photoresist material on to the above

substrate using spin coating

Step 3: Now expose the e-beam using CAD-Mask

(E-beam move according to the CAD design on the substarte)

Step 4: Now immerse the above substrate (e-beam reacted)

in the developer solution

Reaction takes depending on the photoresist

Step 5 Now immerse the above developed substrate inthe
etching solution (removing material wherever we required)
Or
Step 5 Deposit the metal deposition

Step 6 Finally, strip off/lift off the leftover phtotresist

Step 7 we can find the required pattern on the substrate

Advantages of lithography
1.Once the master template has been made, no special equipment
is required.

2.Soft lithographic methods are capable of producing nanostructures

in a wide range of nanostructures in a wide range of materials and
can print or mold on curved as well as planar surfaces
Advantages and Disadvantages of
Topdown and Bottom up approaches
Top down Bottom up
1. More defects 1.Less defects

2.Introduces internal stress 2.Homogeneous chemical

composition and no internal stress
3.Contamination is more
3.Less contamination
4.Diffraction limited
4.No limitation

5.E-beam lithography is 5.Not very expensive

Expensive
6.Need less time to
6.Need more time to Prepare nanomaterials (few min)
Prepare nanomaterials(few
hours)
 Advantages and Disadvantages of
Topdown and Bottom up approaches
Top down Top down
7. Capable of producing 7. Difficult to produce
nanostructures in a wide range of nanostructures in a wide range of
nanostructures in a wide range of nanostructures in a wide range of
materials with specified design materials with specified design