CH 586 : Structure and properties of Materials

C. Subramaniam
Department of Chemistry
Topic 1 - Materials at Extreme Dimensions
 Topic 2 - Materials at Extreme Temperatures
Pyotr Leonidovich Kapitsa
J. Georg Bednorz
K. Alexander Müller
Heike Kamerlingh Onnes
Lev Davidovich Landau
John Bardeen
Leon N. Cooper
J. Robert Schrieffer
Leo Esaki
Ivar Giaever
David M. Lee
Douglas D. Osheroff
Robert C. Richardson
Alexei A. Abrikosov
Vitaly L. Ginsburg
Anthony J. Leggett
Understanding structure-property-function correlation
CaCO3

SiO2

Huge variation in appearance and mechanical properties

WHY? 4
 Soft
Conducting

Hard,
insulating

Conducting

Huge variation in physical and chemical properties

WHY? 5
 Aim(s) and purposes(s) of this course

Understand and appreciate materials around you.

You just have to walk on the streets to find problems

in science
-Adapted from Sir C. V. Raman’s quote
 Fe3C –
orthorhombic

Why is carbon added to steel? How does quenching harden

steel and tempering soften it?
 Choice of material for applications
Single ply Cu wire
vs
Multiply Cu wire

Understanding and
designing structures of
Rupert’s glass drop materials Toughened glass

Designing materials for applications 8

 Rupert’s glass drop
https://youtu.be/k5MORochIDw 3:30 - 6:00 minutes

Notice the failure pattern!!!

ACS Nano 2020, 14, 12, 16723

 How do ...?

these work? these light up?

these attract? these repel? these differ?

10
 Message of this course
Tools to
understand
properties

Tools to
Properties of
understand
solids
structure

Structure of solids
11
Books (besides research articles)
1. Solid State Chemistry – A.R. West
2. Solid State Chemistry – L.E. Smart, E. A. Moore
3. Solid State Physics – C. Kittel
4. Electrical properties of materials – L. Solymar, D. Walsh
5. Transmission Electron Microscopy – C. Barry Carter

Suggested Reading
H2O – A biography of water – Philip Ball
The disappearing spoon – Sam Kean
Periodic Tales – Hugh Aldersey Williams
Fontana History of Chemistry – William Brock
Ground rules for this course
1. Quiz for 10 marks will on 29nd March, 2023. No re-quiz will be provided
(whatever be the reason).
2. Assignment for 10 marks: Deadline is 9 AM on 29nd March. Late
submissions will not be evaluated.
3. Last date of instruction :13th April, 2023
4. End-sem exam (25 marks) : as per academic schedule.
5. Those who take re-end-sem exam/make-up end-sem: Paper will be at
least 30% more difficult.
6. Whatsapp : will stop replying two days before the exam or quiz.
Topic 1 - Materials at Extreme Dimensions
Journey from Sand to Silicon

Chemistry in day-to-day life

 This is
Litho : Stone
Graphy : To write
LITHOGRAPHY
Wax statue

Wax covered
in clay

Clay cast

Casting of
metal/alloy Moulded
metal
 A word about clean-room
• Ambient air : 35,000,000 particles of dimensions > 0.5 micron
• Semiconductor processes : Clean rooms
• Class ‘n’ room : Air contains no more than n particles/ft3 that are
larger than 0.5 microns.
• Sources of contaminations :-
• Human, Chemicals, packaging, air etc
 Semi-conductor processes
Photo-resist
Exposure
Substrate

Development

Deposition

Lift-off
 Semi-conductor processes
Photo-resist
Exposure
Substrate

Development

Deposition

Lift-off
Single crystal growth : Czochralski process

Boule
Single crystal growth : Czochralski process
SiO2 + 2C → Si + 2CO
(98 -99%)

Components of Czochralski
process
1. Furnace (Graphite and RF)
2. Crystal pulling mechanism
3. Ambient control
4. Crucible (Quartz)

Pull-rate of crystal is critical

Purity of Si wafer is 99.9999% (6N)

 Single crystal growth : Czochralski process
Processes occuring :
At A : solidification and crystallization.
At B : Heat transport through crystal
At C : Heat radiated away
Isotherm S In ideal conditions, A = B

dm dT dT
L + Km Am = K s As
Isotherm M dt dxm dxs
dm dT
L = Ks As
L: Latent heat of fusion dt dxs
K : Thermal conductivity (of melt and solid)
dT/dx : Thermal gradient (in melt and solid) dx dT
A : Area of melt and solid  LAs  = Ks As
Assuming temperature gradient in melt is zero, dt dxs
dx dT
 = Ks L
dt dxs
 Single crystal growth : Czochralski process
Expression for maximum possible dx dT
pull-rate without resulting in thermal  = Ks L
gradient in melt
dt dxs

In ideal conditions, heat loss is entirely taken by Latent heat

Heat absorbed by system ~ Latent heat
dm dx
Heat input – Heat output = L = LA = as small as possible
dt dt
dx
Therefore, as A increases, decreases
dt
Larger area crystals have to be pulled at slower rates.
 Single crystal growth : Czochralski process
Seed crystal

Silicon melt

After 2000

1980-90
Single crystal growth : wafer dicing

• Dicing is carried out

with diamond-tip saw.
• Packaged in clean-
room environment.

Photoresist coating and baking

• Photoresist in form of solution (organic
solvent)
−0.5
 4  t  2
d = 
 3 
• Baking to remove the organic solvent.
 Photoresist material

Sourced : Microlithogrpahy fundamentals in semiconductor devices and fabrication technology

 Semi-conductor processes
Photo-resist
Exposure
Substrate

Development

Deposition

Lift-off
 Resolution of resists
Intended
exposure
Incident light
Refracted light
Scattered light Actual
Reflected light exposure

• Forward scattering : scattering by resist.

• Back scattering : scattering by substrate.
• This would lead to widening of area of exposure.
• Actual exposed area of resist > intended area of
exposure (always)
 Positive and negative resists

Undercut

Overcut

• Undercut and overcut of resists could also lead to loss

in resolution.
• Oriented deposition techniques can be used to
overcome undercut.
 Semi-conductor processes
Photo-resist
Exposure
Substrate

Development

Deposition

Lift-off
 Exposure techniques

~ nm ~ µm

Types of
exposure

Nano-
E-beam Optical/UV
imprint

Type of exposure is controlled by required resolution of

patterning
 Concept of resolution
Resolution : Ability to distinguish closely spaced points.

 Lens
d=
2n sin  . θ
d = radius of spot
λ = Wavelength of light Substrate
n = refractive index
 Concept of resolution
Resolution : Ability to distinguish closely spaced points.
 Lens
d=
2n sin  . θ
d = radius of spot
λ = Wavelength of light Substrate
n = refractive index

Numerical aperture = nsinθ =

light collecting ability of lens
 λ = 800 nm

λ = 200 nm

• Lower the wavelength, smaller

the spot size.
• Lower the wavelength, higher
the energy!!!
 Mask-based optical lithography
Process similar to photocopy
Light source

Light Wavelength Resolution

source
Mask Hg lamp 400 nm 200 nm
KrF laser 248 nm 110 nm
ArF laser 193 nm 50 nm
Photoresist
• Any wavelength from 400 nm to 190
Substrate nm (Deep-UV).
• Resolution up to 50 nm can be
achieved.
• Faster and repeatable
 Mask-based optical lithography

 z
R = 3  s + 
 2
s = Distance between mask
and photoresist
z = Photo resist thickness
λ = wavelength of light
 Types of mask-lithography
Contact exposure Proximity exposure

• Higher resolution • Lower resolution

• Lower lifetime of • Higher reproducibility.

H
mask

z
R = 3  
2
• Exposure time is few seconds to minutes.
• Much faster and efficient.
• Masks still have to be fabricated by e-beam lithography.
Generation of high energy electrons :
Thermionic emission
• Emission of electrons by heating materials.
• Materials must exhibit (a) high melting point, (b) low
work function.
• Produces a electron beam with distribution of energies.
• Materials such as W or LaB6 is used.

−

J = AT 2 exp k BT

J = Current density from

source.
T = Temperature
Φ = work function
A =Richardson’s
constant
Generation of high energy electrons : Field
emission
• Emission of electrons by voltage.

h
=
2m0 eV

• Sharp points are used to increase the strength of electric field.

• First anode extracts electrons and second anode accelerates them.
• Increasing the accelerating voltage reduces the wavelength of
electrons emitted.