A333 Revision Notes (P1-P13)

A333
Nanotechnology
Revision Slides
A333 ESE
OFFICIAL (CLOSED) \ NON-SENSITIVE
Date 19 August 2022 (Friday)

Time 9am to 11am
(Report to your venue by 8:30am)
Coverage P1 to P13
Format CLOSED BOOK PAPER ESE
Section A: COMPULSORY Multiple Choice

Questions (10 marks)
Section B : COMPULSORY Fill in the Blanks (20

marks)
Section C: COMPULSORY Short answer questions

Working must be shown
(50 marks)
Total: 80 marks
A333 ESE: Announcements
• For this CLOSED BOOK PAPER ASSESSMENT, students

are NOT allowed to refer to any written materials, and notes
and resources stored in their notebook computer during the
exam.
• Students may use electronic calculator and electronic

dictionary during the exam.
• Students may have a blank piece of paper (no larger than A4

size) for rough working, but such paper will not be accepted
for submission at the end of the exam.
• Please bring your own pen and calculator (calculator in laptop

and mobile phones cannot be used)
A333 ESE: Announcements
• If formula is needed for calculation, it will be provided in the

question.
• Before the start of the exam, place all bags and laptops at the
front of the classroom.
• Write answers only in the box provided. Answers written

anywhere else in the script will not be accepted.
P1: Nanoscale and size
effect
What are nanomaterials?

∗ Nanomaterials have extremely small size which having at least one
dimension 100 nm or less.
∗ They can be classified based as shown below.
What is so special about nanoscale?

Surface effects
∗ SAV ratio = Total surface area / volume

∗ S.I. unit for SAV ratio is m−1
∗ Dimensions of the cube ↓  SAV ratio ↑ contact between material
and surrounding ↑ dissolution rate / reactivity ↑
What is so special about nanoscale?

Quantum effects
∗ Quantum effects – material’s properties change dramatically

at nanoscale (size dependent)  properties can be
manipulated by changing the size
Material Bulk Nano

Carbon nanotubes –
Charcoal – low electrical high electrical
Carbon
conductivity conductivity
Gold Gold in color Range of colors

Aluminium Non-reactive Highly reactive
P2: Surface property and
Mechanical Property
Contact Angle, Surface Energy and Wettability
• Total surface energy E (in Joules) belonging to a surface of surface

area S (in meter2) with surface free energy per unit area γ (in J/m2) is
given by:
E = γ ·S
Contact angle < 90° Contact angle > 90° Contact angle > 150°
Hydrophilic
___________surface  Hydrophobic surface
___________ Superhydrophobic
_____________ surface
Higher surface energy  Low surface energy  low surface energy
Photocatalytic nanomaterial
• Photocatalytic nanomaterials, are nano-sized particles which
catalyst in the presence of sunlight, which do not
work as a _______
change themselves or being consumed in a chemical reaction.
• UV light excites electrons and holes
in photocatalytic material (e.g.
titanium dioxide/titania (TiO2)).
• Electrons then react with oxygen in
the sample to form oxygen
superoxide anion (O2-)
O 2 + e - → O2 -
• Holes react with surface hydroxyl
groups to form hydroxyl radicals
(OH•).
H2O + h+ → OH• + H+
• The radical species then attack the
dirt/ microbe causing it to gradually
__________
break down and loosen.
Self-cleaning approach
Self-cleaning
Superhydrophobic Superhydrophilic
The requirements for a self- The requirements for a self-

cleaning superhydrophobic cleaning superhydrophilic surface
high static
surface are a very ____ is the need to spread
______ water that
water contact angle θ, and a very carries away dirt. Coatings based
low sliding angle, i.e. the on nano-sized TiO2, however,
minimum
_______ inclination angle have an additional property: they
necessary for a droplet to slide can chemically _____break down
off the surface, carrying away absorbed dirt in sunlight.
dirt.
Superior mechanical properties achievable by abalone

shell
Strong: Interlocks
function as physical
obstacles to the
relative movement
of aragonite
platelets
Tough: brittle aragonite platelets and ductile

adhesive layers. increased surface area and
interfaces between platelets and adhesive
layers  increased matrix-reinforcement
interface  increased crack deflection 
increased toughness
Stiff: Organic matrix acting as glue
adjacent between layers of aragonite where ,Em is the Young’s modulus of mineral platelets,
platelets. Gp is the shear modulus of protein matrix,
Φ is the volume concentration of mineral platelets, and
ρ is the aspect ratio (width over thickness) of the
mineral platelets.
P3: Optical property
How to synthesize silver nanoparticles?
Borohydride ions adsorbed on the

surface  repulsive  stabilise
silver nanoparticles and prevent
aggregation
Surface plasmon resonance:

light sets up a sinusoidally varying electric
field  electron cloud around the metal
atoms oscillates with the field EM wave
with the same frequency as the resonating
frequency of the particle is being absorbed
 light not absorbed will go through and
show the color
Why are the colours of metallic nanoparticles

different from that of their bulk counterparts?
• Effect of size: As particle size increases  peak plasmon resonance

shifts to longer wavelengths  absorb light of longer wavelength
• Effect of aggregation: conduction electrons near each particle surface
become delocalized and are shared amongst neighbouring particles 
absorption shifts to longer wavelength
• Particles destabilize  original extinction peak decrease in intensity
(due to the depletion of stable nanoparticles)  peak will broaden or a
secondary peak will form at longer wavelengths (due to the formation of
aggregates).
P4: Top-down approach
How to fabricate nanostructures from bulk

material?
Wet chemical etch Physical vapour
deposition
Chemical vapour
Dry chemical etch deposition
What are the various approaches to fabricate

nanostructures from bulk material?
Types of lithography
Initial “Pencil” doing
Type of
location of the
lithography 1
pattern writing
flood of light
Photolithography Mask
(photons)
Electron beam Beam of
Data File
lithography electrons
Physical
Nanoimprinting Mold
contact
Stamping Physical
Mold
lithography contact
Wmin can be
improved by
replacing the
medium with a
higher refractive
index (n).
Positive vs negative photoresist
Positive photoresist Negative photoresist

Photoresist is exposed to a radiation source Photoresist is exposed with UV light wherever the
wherever the underlying material is to be underlying material is not to be removed.
removed.
Exposure to the radiation source causes the Exposure to the radiation source causes the
photoresist to become easier to dissolve. photoresist to become more difficult to dissolve.
The exposed photoresist is then washed away Photoresist remains on the surface wherever it is
by the developer solution, leaving windows of exposed, and the developer solution removes
the bare underlying material. only the unexposed portions.
What are the various approaches to fabricate

nanostructures from bulk material?
Electron beam lithography Mechanical milling - repeated
deformation, rewelding,
fragmentation of premixed powders
P5: Bottom-up approach
How to fabricate nanostructures starting from

atoms/molecules?
Basic step Purpose/Function
Making molecules,
Building
particles, or layers – basic
block
building blocks of bottom
fabrication
up nanofabrication.
Putting together building

Self-
blocks into functioning
assembly
nanostructures.
Building Block Fabrication
Molecule
synthesis: Tail
group – gives
functionality; head
group –
determines what
molecule to attach
to Dendrimers
Colloidal chemistry: Shape/size of nanoparticles

controlled by the type of solvent used
Building Block Fabrication
Chemical vapour growth
Vapour condensation
• Metal nanoparticles: rapidly condense
supersaturated inert gas + atomic vapour
of metal
• Metal oxide nanoparticles: rapidly
condense supersaturated oxygen gas +
atomic vapour of metal
• Size of particles depends on temperature,
gas flow and the vapour production rate
Self-assembly
In water
In mixture of oil
and water
In oil
Micelles: aggregate of surfactants

(hydrophilic head and hydrophobic tail)
Self-assembled monolayer:
sulphur group attracted to gold
and the hydrophobic tails pack
together to push away water in
the solution
Dip pen nanolithography
P6: Nanomagnetism
What are the various types of magnetism?
Magnetic
Types of Magnetic field Magnetic field
susceptibility
magnetism applied removed
(χm)
Align in the
Diamagnetis opposite Does not retain
Small negative
m direction of the magnetisation
magnetic field
Align in the
Paramagneti same direction Does not retain
Positive
sm of the magnetic magnetisation
field
Align in the
Ferromagnet same direction Retains
Large positive
ism of the magnetic magnetisation
field
Superparamagnetism
• Ferromagnetic material reduces to

nanosize (3~50nm)  superparamagnet
• Properties of superparamagnet is
intermediate between ferromagnet and
paramagnet: high saturation but zero
coercivity and remanence (i.e. does not
retain magnetisation when electric field
is removed)
• Magnetisation can randomly flip
direction under the influence of
temperature.
• T < Blocking T: Behave like ferromagnet
• T > Blocking T: Behave like paramagnet
• Magnetic storage too small 
superparagnetism sets in  magnetic
moment flips randomly  stored data
can get corrupted and becomes
unreliable
What is giant magnetoresistance (GMR) effect?

• Magnetoresistance (MR) : material
undergo a change in their electrical
resistance when subjected to an
external magnetic field
• GMR effect is exhibited by materials
made from alternating layers of
ferromagnetic and non-magnetic
metals; thickness of these layers in
nanometres (smaller than mean free
path)
• Anti-parallel: scatters both “up” and
“down” spin electrons  high
resistance
• Parallel: only scatters one of the “up”
and “down” spin electrons  low
resistance
• Spacer too thin  coupling between
magnetic layers (align with each other)
Application of GMR (Hard disk read-out head)

• Hard disk stores information in the form of
microscopically small areas magnetised in different
directions.
• Read-out head scans the disk  GMR effect convert very
small magnetic changes into differences in electrical
resistance  into changes in the current
• Different strengths of the current represent “1”s and “0”s.
• The smaller and more compact the hard disk, the smaller
and weaker the individual magnetic areas.
• GMR effect has enabled more sensitive data reading of
hard disks.
P7: Ferrofluids
• Ferrofluid: Ferromagnetic nanoparticles

(NP) suspended in carrier liquid 
behave like superparamagnet  can be
strongly magnetised in the presence of
a magnetic field but does not retain
magnetism in absence of magnetic field
• Magnetic particles must be very small
on the order of 10 nm so that thermal
energy of particles is large enough to
overcome magnetic interactions
between particles.
• NP are coated with surfactant 
surfactant’s VDW forces > magnetic
attraction between NP  prevent
agglomeration
• Magnetic field applied  surface
instability  if magnetic force > surface
tension + gravity spikes appear
 Viscosity (η ): resistance to flow

 Fluidity (ϕ ) : ease with which a fluid flows (= 1/η)
 ν = η /ρ where ν is the kinematic viscosity (in m2/s), η is the
dynamic viscosity (in Pa⋅s) and ρ is the density (in kg/m3).
 Diameter of NP decrease  total surface area increase 
interaction between NP and surrounding fluid increase 
viscosity increase
NR = inertial forces / viscous forces
= ρ vD /η
Reynolds number (NR) Type of flow
Very high (> 4000) Turbulent Nanofluids
Moderate (< 2300) Laminar - viscous
Very low (< 1) Stoke force
dominates
P8: STM and MFM
Scanning Tunneling Microscope

Imaging
Quantum tunnelling:
There is a finite probability
that the electron is able to
tunnel through the energy
barrier
Constant height mode:

 Tip’s height is fixed
 Sample-tip distance and
current varies • Tip features must be smaller
Constant current mode: than the surface features
 Sample-tip distance and • Tunneling current is highly
current is fixed sensitive to sample-tip
 Tip’s height is varies separation  Vibration isolation
unit necessary
Scanning Tunneling Microscope

Nano-manipulation
Lateral
manipulation
Vertical
manipulation
• Apply voltage  potential barrier dops  atom

can be transferred / attracted to the tip
• Reverse bia  atom gets transferred / released
back to the sample surface
Magnetic Force Microscope
• Flexible MFM cantilever probe oscillates near its natural

frequency and scans laterally across the sample surface in a
raster pattern
• Tip is coated with a ferromagnetic thin film
Type of force Sample-tip Oscillation
distance frequency
(increase /
decrease)
Repulsive Increase Increase
Attractive Decrease Decrease
P9: Optical tweezers
Rayleigh and Mie Regime
Rayleigh Mie
Size d << λ d >> λ
Model Electric dipole Ray optics
Physical Dielectric Transparent and
properties (polarisable) spherical
of particle
Ray Optics Model

• Light (as in photons) carries
momentum.
• Reflection / refraction  change in
momentum  impart force
• Gradient force: move the bead towards
the laser focus due to refraction of light
• Scattering force: move the bead in the
direction of light due to reflection
• Optical traps involve the balance of two
types of forces  particle will stay
slightly behind the focus
Electric Dipole Model

• Polarized light  EM radiation has an electric field vibrating in a
particular direction and a magnetic field vibrating in another direction
• Particle regarded as an electric dipole  can be polarised by EM
• Gradient force pulls the dipole towards the most intense region of the
light
• Scattering force: points in the direction of the incident light
• Stable trapping requires that the gradient force be greater than the
scattering force maximum
Fscattering
Applications of optical tweezers

Measure force exerted on bead
Calibration of trapping force
Displace trapped bead from the center
of bead with viscous force exerted by
fluid flow
Trap stiffness, k
Force exerted onto the bead =

Trap stiffness × displacement from
centre
Stokes’ law: F = 6πηrѵ At equilibrium:

where Trapping force = Viscous drag force
ѵ: velocity of fluid
η: viscosity of fluid
r: radius of the bead
Typical setup for optical tweezers
Standard Microscope with:

• High numerical aperture objective
lens
• Tightly focused light beam (i.e.
laser)
• Monochromatic continuous wave
(CW) Laser
• Wavelength in range of 750 – 1100
nm for biological samples
• Use heavy water (D2O) to avoid
heating of surrounding medium
P10: Nano-structured
liquid crystals
What are liquid crystals?
• Polymeric hydrocarbons
• Ordered at nanoscale, lack long-range order (between their solid and liquid
phases)
• Temperature sensitive
 Turn into solid if too cold
 Turn into liquid of too hot
Why do their colours change with temperature?
• Cholesteric liquid crystals: helical structure at nanoscale

• Pitch: Distance between layers with the same orientation
• Only light with wavelength equal to the pitch is reflected
• Temperature ↑  pitch ↓  wavelength of light reflected changes 
color changes
• Other factors that affect color: pressure, composition
Properties of LC molecules
• Heating: Heat is absorbed  energy ↑

 crystalline  smectic  nematic
isotropic
• Cooling: Heat is evolved  crystalline
phase is formed
LCD: LC rotate the plane of

polarized light and align parallel
to an applied electrical field 
application in various electronic
devices
P11: Carbon nanotubes
Types of Carbon Nanotubes

Can be thought of as rolled up
versions of graphene sheets
Armchair: Zigzag: Chiral:

• Chiral indices: (n, n) • Chiral indices: (n, 0) or • Chiral indices: (n, m)
• E.g. (3, 3) (0, m) • E.g. (2, 3)
• metallic • E.g. (2, 0), (0, 2) Semiconducting or
• Semiconducting or metallic
metallic
Metallic carbon nanotubes (n, m) are formed when n − m = 3i, where i is any
integer, …−2, −1, 0, 1, 2 ….
Properties of Carbon Nanotubes
• The band gap of semiconducting carbon nanotube is inversely related to

the diameter of the carbon nanotube.
• The diameter of the carbon nanotube, d, is given by:
a 2 2
d= n + nm + m
where a = 0.246 nm.
π
• Because of its nanoscale cross-section, electrons propagate only along
the tube’s axis. (one dimensional conductor)
• Undergoes ballistic conduction (Length of conductor < Mean free path)
 no scattering  negligible resistivity  negligible resistance 
negligible heat dissipation
• Strong covalent bonds between carbon atoms  minimal electromigration
Mean free path: Average length that an electron can travel freely before hitting
something
Single electron transistor (SET)
• Apply sufficient voltage at gate

electrode  energy levels lowered 
electron can tunnel through from source
to drain
• Control the voltage at the gate electrode
 control the current across source and
drain  acts as a switch
• If thermal energy at room temperature

(4.0 × 10−21 J) > U  electron can still
tunnel through without application of
voltage  cannot act as a switch.
P12: Quantum Dots
What is a Quantum Dot (QD)?

• Semiconductors
• Quantum confinement: Size of
semiconductor particles is reduced
to such an extent that charged
particles inside is severely
constrained in space (zero degree
of freedom in all three dimensions)
 Confines motion of conduction
band electrons and valence band
holes  density of states becomes
discrete
• Condition for quantum
confinement : Size of particles
must be reduced to Bohr exciton
radius (average distance between
an electron and hole in a material)
• Band gap increases as size of QD
decreases.
Bandgap energy for QD

• The bandgap energy for QD is given by:
where R is radius of QD, EBulkbg is semiconductor band gap, ħ

is the reduced Planck constant 1.0546×10 −34 J⋅s (=h/2π), ∈ is the
dielectric constant of the semiconductor and ∈0 is the dielectric
constant of free space (8.854x10-12 F/m), e is the charge of an
electron (1.6 x 10-19 C).
• µ is exciton reduced mass and is given by
where mh is effective mass of hole and me is effective mass of

electron.
QLED
• Larger QD  smaller bandgap 

emit light of lower energy (longer
wavelength)  redder spectrum
• Smaller QD  larger bandgap 
emit light of higher energy (shorter
wavelength)  bluer spectrum
• Different spectrum of light may be
emitted by tuning the size of QD
• The spectrum of photon emission is
narrow and of higher intensity
(brighter) for the QLED compared to
conventional LEDs.
QD Solar Cell
• Semiconductor absorb photons of Solar cell efficiency:
certain wavelength  free electrons
which forms the electric current Reflectivity:
• E > bandgap energy  extra energy Optimal refractive index:

expended as heat
Optimal thickness:
• E < bandgap energy  pass through
without being absorbed
• Low reflectivity desired  more light
absorbed  higher efficiency
• Lower refractivity  lower reflectivity
• QD solar cell  band gap of the
quantum dot can be “tuned” and
changed by varying its size  absorb
light from a wide range of solar
spectrum  higher efficiency
P13: Biomimicry
How does nature work?

Nanosized setae  increased surface area 
increased contact  increased van der Waals
attraction  increased adhesive strength
Hydrophilic nano-bumps attract water  rolls

down waxy area when enough is collected 
waxy area is hydrophobic  repel water into
beetle’s mouth
Ordered pattern of scales which are about 200

nm apart.
Wavelength of visible light is greater than the
spacing  scattering or reflection 
constructive interference  different colours
and increase in reflectance
Applications of Biomicry
Spacesuits for astronauts that help them stick to the
walls of a spacecraft
Indent wax surface using a micro/nano-fabricated
probe nano-tip  Mold it with a polymer 
Separate the polymer from the wax by peeling.
A device that can harvest water in dry lands

Coat hydrophobic surface with a matrix of silica
nanoparticles Coat nanoparticles with
photosensitive material Expose to UV  longer
and more intense exposure, more hydrophilic.
Fabrics with colours that never fade, pigment free
(environmentally friendly)
Combine 61 polyester and nylon fibres in alternating
layers  control thickness of each layer ranging
from 70 to 100 nmproduce four basic colours (red,
green, blue and violet) process reveals a rainbow
of colours according to the intensity and angle of
light due to the unique structure of the fibre.
Good Luck for your ESE!

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A333

Date 19 August 2022 (Friday)

Section A: COMPULSORY Multiple Choice

Section B : COMPULSORY Fill in the Blanks (20

Section C: COMPULSORY Short answer questions

• For this CLOSED BOOK PAPER ASSESSMENT, students

• Students may use electronic calculator and electronic

• Students may have a blank piece of paper (no larger than A4

• Please bring your own pen and calculator (calculator in laptop

• If formula is needed for calculation, it will be provided in the

• Write answers only in the box provided. Answers written

What are nanomaterials?

What is so special about nanoscale?

∗ SAV ratio = Total surface area / volume

What is so special about nanoscale?

∗ Quantum effects – material’s properties change dramatically

Material Bulk Nano

Gold Gold in color Range of colors

Contact Angle, Surface Energy and Wettability

• Total surface energy E (in Joules) belonging to a surface of surface

The requirements for a self- The requirements for a self-

Superior mechanical properties achievable by abalone

Tough: brittle aragonite platelets and ductile

How to synthesize silver nanoparticles?

Borohydride ions adsorbed on the

Surface plasmon resonance:

Why are the colours of metallic nanoparticles

• Effect of size: As particle size increases  peak plasmon resonance

How to fabricate nanostructures from bulk

What are the various approaches to fabricate

Positive vs negative photoresist

Positive photoresist Negative photoresist

What are the various approaches to fabricate

How to fabricate nanostructures starting from

Basic step Purpose/Function

Putting together building

Building Block Fabrication

Colloidal chemistry: Shape/size of nanoparticles

Building Block Fabrication

Chemical vapour growth

Micelles: aggregate of surfactants

What are the various types of magnetism?

• Ferromagnetic material reduces to

What is giant magnetoresistance (GMR) effect?

Application of GMR (Hard disk read-out head)

• Ferrofluid: Ferromagnetic nanoparticles

 Viscosity (η ): resistance to flow

Scanning Tunneling Microscope

Constant height mode:

Scanning Tunneling Microscope

• Apply voltage  potential barrier dops  atom

Magnetic Force Microscope

• Flexible MFM cantilever probe oscillates near its natural

Rayleigh and Mie Regime

Ray Optics Model

Electric Dipole Model

Applications of optical tweezers

Force exerted onto the bead =

Stokes’ law: F = 6πηrѵ At equilibrium:

Typical setup for optical tweezers

Standard Microscope with:

What are liquid crystals?

Why do their colours change with temperature?