CONSTANTS

h = 6.63 x 10-26 g .cm2 . s-1

= 8.85 x10 -14 F/cm

1
 FORMULAS
PART 1
Bulk modulus

Stress

Strain
Energy absorbed/generated to deform/fracture

Young’s Modulus
E = stress/strain

Surface pressure of nanoparticle Surface free energy (activity)

2
Gibbs-Thomas Equation Average Latent Heat for nano

For free cluster (not nano) :

For nano:

Latent heat Hm is not a constant

- There exist a critical temp Tc where surface
melting is initiated
- At or above Tc, thickness of this liquid-like layer
increases
- Melting is a discontinuous process for bulk (first
order) but is continuous process for nano

3 melting hypotheses for nanoparticles Melting of film VS sphere

3
Melting/Solidification reversal Melting of pore-confined nanophase

Lotus Leaves Effect

When yws – ywl >0 melting pt lowered)

yws – ywl < 0 (melting pt increase)

DEPENDENT ON:

Eg. For water confined in mesoporous silica

- Completely filled pores → melting/freezing lower
with decreasing nanophase size
- Partially filled pores → freezing exhibit several
stages depending on pore filling ratio

4
 Hall-Petch Relation (HPR) Modified Hall-Petch Relation for nanometals to include
contributions from grain & grain boundary

Yield stress dependence of grain size (d) Yield stress

Flow stress dependence of grain size (d) Flow stress

Hardness (H) dependence of grain size (d) Hardness

Grain fraction for 2D squares

Grain fraction for 3D cubes

Grain fraction for 3D spheres : where spherical core-shell

is considered for each grain

Grain fraction for 3D

5
 PART 2
Ballistic transport: the unimpeded flow of electrons over
a relatively long distance in a material
- Where electric conductance is quantized (jumps
in discrete steps)

- mean free path of the electrons are longer than

geometric dimensions of the conductor.

Coulomb blockade: is the decrease in electrical Conductance G: measuring the ease with which an
conductance at small voltage bias of a small electronic electric current passes
device. It is used to describe quantization of electric 1
G=
charges where current-voltage graph appears to be a 𝑅
stepwise function
Charging energy (energy to Threshold voltage
tunnel)
For 1D wire, 1 mode:

For metallic (conducting) SWCNT:

Landauer Resistance
Condition for coulomb blockade: - Not ohmic resistance, just a probability of
transmission

&

6
Current flow in nanotube Energy (E)

or

For 1D 1
Kinetic energy = = KT
2

Energy - Capacitance

Mean free path

Mobility Beer-Lambert equation

- Change in intensity with distance travelled

Diffusion coefficient D

7
Reflective Index (n) EXCITON: a bound state of an electron and hole pair
- When wave is transmitted through medium, where E-H pairs can exist longer due to coulomb
frequency remains constant, but velocity attraction
decreases Effective reduced mass of exciton

Energy of exciton

Radius of exciton

Plasmon frequency Quantum Confinement Effects

Total Energy:

Plasmonic Core-shell

Energy of n level (or band level):

8
Magnetism (Definition: magnetism based on concepts of ATOMIC magnetic moment (orbiting)
magnetic dipole moments.)

Magnetic Dipole moment:

L is orbital angular momentum which is:

**derivation can be found in magnet notes slides 5

_______________________________________________
ATOMIC Magnetic moment (spinning electrons)

Overall magnetic moment of an atom:

Bohr magneton

Energy of a magnetic moment (E):

Magnetic Permeability = magnetic field / magnetizing Magnetic susceptibility Xm indicates degree of

field magnetization in response to an applied magnetic field

Relative permeability = FRACTION increase Relationship between Relative Permeability and

susceptibility:

Curie-Weiss Law – magnetic susceptibility X of a Curie Law – for primarily paramagnets, the magnetization
ferromagnet in the paramagnetic region above the Curie of the material is directly proportional to an applied
Point: magnetic field

9
Magnetostatic energy (Ems) Domain wall
Width (wall):

Exchange energy (Eex)

Energy / Area:

Magnetocrystalline anisotropy energy (Ea)

A = exchange parameter which is exchange energy/unit
volume
K = Anisotropy constant which is anisotropy energy
density

Total energy of domain wall:

Not a formula but very important Single Domain (due to size effect): basically, the particle
is so small that it only has one domain. Domain wall
collapse

Energy (uniaxial anisotropy):

Tether= angle between easy axis and magnetization

vector (refer to below)

Critical diameter (below this d, domain wall is unstable)

➔ Formation of single domain

Self energy:

Bloch wall energy:

10
Anisotropy: Easy axis & hard axis direction of
magnetization Shape (Cube):

(take note that Dc here is the crit diameter also)

Shape (spherical):

(take note that Dc here is the crit diameter also)

Anisotropy energy
1) uniaxial

2) Triaxial

3) Cubic
Shape Anisotropy: shape can be used to increase
coercivity
- cylindrical shapes favor a coherent rotation of
the magnetization and thus large coercive fields. Where K = anisotropy constant, V = volume

11
Blocking Temperature: for a given particle size, there is a Super-paramagnetism: above Curie temperature,
temperature that marks the transition from a permanent Ferromagnetic/ferromagnetic materials undergo a
static moment to a fluctuating moment (spin flipping) transition to paramagnetic states.
➔ Superparamagnetism - Spins flip

- no hysteresis but very high Magnetization!

Superparamagnetic limit: limit on areal-density. This sets

a limit on the storage density of hard disk drives due to
the minimum size of particles that can be used.

Blocking temp estimated to be the lifetime of the

magnetization vector along a particular direction; Anisotropy constant for superparamagnetism
lifetime/residence time:

T0 in the eq above is natural lifetime (value at high

temperature limit)
Magnetic moment of the cluster:

Probability:

But usually, to be taken as a constant

Average magnetic moment per particle along the field
Frequency of flipping / Flipping rate: direction:

L(m) = Langevin Function

V0 = attempt frequency

12
Diameter at which magnetic moment becomes blocked Mean time between flips = Residence time = Neel
at a given temperature: relaxation time

K = magnetic anisotropy energy density

V = volume
Kb = Boltzmann constant
T = temperature

13
PART 1
19/20 paper
1a. What is Hall-Petch Strengthening? Describe the main mechanism leading to this strengthening effect.
Hall-Petch Strengthening describes an inverse relationship between grain size and yield strength.

Grain boundaries act as pinning sites, stopping dislocations from propagating. These dislocations will
accumulate at the grain boundary as they are unable to move past the boundary. Thus the grain boundaries
act as effective barriers to dislocation motion/activities.
Decreasing the grain size increases the number of grain boundaries, hence, increasing the amount of applied
stress needed to move a dislocation across a grain boundary. The higher the applied stress, the higher the
yield strength.
However, there is a limit to this mode of strengthening. As grain size reduces to 10nm, grain boundary
diffusion will occur. There will be too many grain boundaries and the grains become active. These grain
boundaries will move/rotate/slide like dislocations. This decreases yield stress.
(Strengthening during plastic deformation occurs with an increase in the dislocation density by dislocation
multiplication mechanisms and the interaction among them. It is common to strengthen metallic materials by
a variety of methods to make dislocation motion more difficult, including "solute/precipitates strengthening“,
where the solutes have to be dragged along by the moving dislocation (or broken away from) or introducing
obstacles to their motion.)
Work hardening/strain hardening
➔ Known phenon for metallic material
➔ Irregardless of nanopheon
➔ Particle dispersion also stop grain boundary
2c.i. What is surface tension?
(Surface tension is a result of the lattice strain in NPs. ) Surface tension is responsible for the shape of liquid
droplets, which is the tendency of liquid surfaces at rest to minimize surface area.
- Due to the cohesive forces, a molecule located away from the surface is pulled
equally in every direction by neighboring liquid molecules, resulting in a net force
of zero.
- The molecules at the surface do not have the same molecules on all sides of them
and therefore are pulled inward. This creates some internal pressure and forces
liquid surfaces to contract to the minimum area. There is a driving force for surface
reconstruction, in order to reduce the surface energy by saturating the dangling bonds, which results from the
missing nearest neighbours.

14
 - The spherical shape minimizes the necessary "wall tension" of the surface layer according to Laplace's

law.
Surface tension γ can be quantified as the force F acting per unit length l of the surface. F acts parallel to liquid

surface. Consider a film with 2 surfaces (top & bottom), total length is 2L therefore .

2c.ii. What is surface energy

Work done per unit area to disrupt the intermolecular bonds when a surface is created. Surface tension is just
abt the tension
The surface energy of a liquid may be measured by stretching a liquid membrane (which increases the surface

area and hence the surface energy).

The most common way to measure surface energy is through contact angle experiments.

15
2c.iii. what are the similarities and differences between them (if any)
Similarity Between Surface Tension and Surface Energy
Both surface tension and surface energy are expressions of how strongly molecules in a surface are attracted
to each other. We usually use surface tension when referring to liquids and surface energy when referring to
solids, but in reality they are the same thing.
Surface tension = surface energy per unit area
Surface tension = work done per unit area = surface energy
Difference Between Surface Tension and Surface Energy
Differ in what it measures
- Surface Tension measures the force applied parallel to a surface applied per unit length.
- Surface energy measures the energy required per unit area to create a new surface.

2d. What is a Wulff plot?

The Wulff plot is constructed by marking the points on the crystal in different directions that represent the
interfacial energy for a plane with that direction as the normal
To begin, a polar plot of surface energy as a function of orientation is made. This is known as the gamma plot
The second part is the Wulff construction itself in which the gamma plot is used to determine graphically
which crystal faces will be present. It can be determined graphically by drawing lines from the origin to every
point on the gamma plot. A plane perpendicular to the normal is drawn at each point where it intersects the
gamma plot. The inner envelope of these planes forms the equilibrium shape of the crystal.

Application: why material got diff shape → govern by Wulff law

16
 18/19 paper
1b. Describe growth of nanowires in VLS mode. (part 1 chap 3)
Vapor-Liquid-Solid (VLS): a method for growing 1D structures like nanowire
- Growth of a crystal through direct adsorption of a gas phase onto a solid surface is very slow.
Hence a new method VLS is proposed.
- Growth material is melted to form a eutectic liquid alloy with catalytic nanoparticles.
▪ The catalytic liquid alloy phase can rapidly adsorb vapor to supersaturation level.
Thus, crystal growth can occur from nucleated seeds at liquid-solid interface
Eg. Growth of Si nanowire
a. Au (metal catalyst) is heated on Si substrate above eutectic temperature
b. Form Au-Si liquid droplet
c. Feeding additional Si into the system in the form of vapor phase molecules such as SiCl4 or SiH4
d. These molecules will readily adsorb onto the liquid surface, hence
supplying more Si to the liquid droplet
e. Liquid droplet will become supersaturated with Si, which serves as a
driving force for crystallization (become solid) of the excess Si at the
liquid-solid interface
f. A continual supply of vapor phase Si will result in the growth of a
crystalline nanowire or microwire, with the liquid droplet remaining on
the tip of the wire via surface tension.

Eg. Growth of SiC nanorod (lecture 3 note)

17
Types of ZnO nanostructures growth with VLS but not possible by other techniques
- ZnO nanopropellers

18
1c.i. Give an explanation why geometry affects the melting point. (part 1 chap 1&2)
Diff geometry have diff curvature → diff radius → diff activity
N = total number of atoms in the cluster
n = number of atoms in 1D
A change in geometry affects the number of atoms confined in a cluster and ultimately changes the surface
tension. The number of atoms confined in a cluster falls dramatically which is evident by N/n ratio from 4 to

8/3 to 4/3. According to , melting temperature falls dramatically with a

decrease in number of atoms confined in a cluster
surface-to-volume ratio becomes substantial → decrease with the reduction in particle size from sphere to
nanofilm to wire

Where n is the total number of atoms in the

nanosolid, and N is the number of surface atoms.
The value of N/2n depends upon the shape and size of the nanomaterials.
- The value of N/2n = 2d/D for spherical nanosolids, where d is the diameter of an atom, and D is the
diameter of the spherical nanosolids.
- For nanowire: N/2n = 4d/3l where, l is the diameter of nanowire,
- and nanofilm = N/2n 2d/3h, and h is the width of the nanofilm.

19
 17/18 paper

i) Nanostructured metals = based on the two-phase model:

Taking the peak=0.35, region 1: x<0.35(bulk),

dislocations control mechanical properties, as grain size decreases, HPR thus increase in mechanical strength
peaking at x = 0.35, beyond that there is a fall in the mechanical strength. This is due to an increase in activity
of the grain boundaries as grain boundaries are no longer effective barriers to dislocation activities, leading to
a fall in mechanical strength.

20
 16/17 paper
2d. What are core-shell clusters? What are the types of core-shell structures available?
Core–shell type nanoparticles are a type of biphasic materials which have an inner core structure and an outer
shell made of different components. Solid-like core and liquid-liquid outer shell.
Types of core-shell structures:
1. Single core-shell
2. Multi core single shell
3. Single core multi shell
4. Multi core-shell
5. Reverse core-shell
Examples of nanoconfinement (one
nanophase confine in another
material/matrix:
1. Pore channels in compounds
(nanopores)
2. Mesoporous materials
3. Sol-gel derived glass
4. Controlled pore glass (pores in glass)

15/16 paper
1a. Describe one example each for 0D, 1D & 3D nanomaterials that exhibit different behavior as compared
to those of their bulk counterparts, due to the size effects in nanometer scales
Chpt II/III
0D : QDs | 1D : NWs | 3D : Nanopores

21
1b. Formulate a relationship for cohesive energy of metal clusters as a
function of cluster size in the nanometer range. Sketch the
dependence of cohesive energy on the number of atoms in a metal
cluster, such as Mg cluster.
The cohesive energy of a solid is the energy required to break the solid
into isolated atomic species.
The number of bulk atoms increase with the cluster radius R3, that of
surface atoms with R2, while edge atoms vary linearly with R and the
number of corner atoms is a constant. The cohesive energy or binding
energy per atom is constant, therefore given approximately:

Cohesive energy proportional to N-1/3, Cohesive energy inversely

proportional to the cube root of size of cluster.

1c. In certain nanomaterials such as nanoparticles, the distinction

between first and second order phase transition can be blurred or may completely disappear. Can you
suggest a structural model and explain the phenomenon.
According to the solid core-liquid-shell model, the surface is already liquid with thickness given as t0, the
measured average latent heat per atom decreases according to the volume fraction of the solid core:

First-order phase transitions are those that involve a latent heat. During such a transition, a system either absorbs or
releases a fixed (and typically large) amount of energy. During this process, the temperature of the system will stay
constant as heat is added.

Second class of phase transitions are the continuous phase transitions. These have no associated latent heat.

Once latent heat reaches zero, the phase transition becomes a continuous process. This is due to the increment in the
liquid layer as the particle size decreases. As size decreases, the lattice strain increases thus making the surface layer
disorderly and amorphous. With an increasing thickness of the liquid like region, the latent heat slowly decreases till
zero. Melting of the solid crystalline phase is where the latent heat stems from. → melting in core

Macroscopic systems exhibit a continuous behavior. A nanosystem in contrast can be of quantum in some behavior. The
distinction between first and second order phase transitions and that between component and phase become blur.
Phase transitions are phenomena that are related to cooperative behavior of a large number of particles. When
different phase-like regimes co-existing in equilibrium, it reminds much more of chemical components or of isomers
rather than of phases, and the Gibbs phase rule loses its meaning.

22
2a. You are assigned to develop a superhydrophobic surface on solid substrates. What are the desirable
features for a superhydrophobic surface. Describe a technique to make the superhydrophobic surface.
“As a rule, a superhydrophobic surface shows a water contact angle (CA) higher than 150° and a sliding angle
(SA) less than 5°.” Superhydrophobic Surfaces: Insights from Theory and Experiment, Sumit Parvate, Prakhar Dixit, and Sujay Chattopadhyay. The Journal of
Physical Chemistry B 2020 124 (8), 1323-1360 DOI: 10.1021/acs.jpcb.9b08567

For a superhydrophobic surface, Cassie state is ideal such that when there is wetting, there would be small
contact area or large contact angle.
By varying the orientation of the NWs, the contact angle and contact surface between the liquid phase and the
NWs can be altered. By changing the orientation such that the contact area is reduced, the surface becomes
more hydrophobic such that the liquid phase slides off the surface at a low sliding angle.

2b. Verify the validity of of Wulff’s construction for a non-hexagonal crystal

23
2c. Nanostructured metallic materials (grain size in nanometer) are known to be much stronger than their
microstructured counterparts (grain size in micrometer). Proposed a structural model and explain the
phenomenon.
The two-phase model for nano metal.
A polycrystalline nanometal can be regarded as a 2 phase material with grain boundary phase & grain phase.
This model can be used to describe dependence of hardness, yielding strength and flow stress on grain size
from micro to nano.
Yield strength can be described by hall-petch relationship →

Flow stress can be described by

Hardness →
14/15 paper
1a. What is the commonly defined upper threshold of feature size of a nanomaterials? Explain why it is
defined the common upper threshold, by giving 3 examples of size dependent behavior of nanomaterials.
100nm. Below this critical size, the properties of the nanomaterial start to differ from the bulk the; melting
point, color (bandgap), ionization potential, catalytic activity/selectivity, mechanical, electrical, optical, and
magnetic properties, are different from those of the bulk.

1c. Lattice shrinkage in nano clusters.

As particle size decreases, lattice strain increases as
there is a reduced coordination of surface atoms
due to a change in surface to volume ratio
(increase).

24
1d. The melting point of metal nanoparticles is known to be strongly dependent on the particles size in
nanometer range. Derive a relationship between the melting point and the particles size for metal
nanoparticles. Explain why the melting point is dependent on particles size in the way you have described.

I found another equation (PT1 CHAP 2 SLIDE 22) refer to below image

Melting enthalpy (latent heat) is not a constant, it is diminishing as particle become smaller.
Nanoparticles have a core-shell model where solid-like and liquid-like phases can co-exist. Hence, the measure
average latent heat per atom will decrease according to radius of the solid → diminishing. Melting occurs from
the surface in a continuous process unlike in bulk materials (discontinuous process, first order phase
transition). This phenomenon only occurs for nanomaterials hence size dependent. (this part can refer to chap
2 slide 26)

25
1d. Dependence of curie temperature on particle size

Curie temperature is the maximum temperature a

material can reach before losing its magnetic
properties. Curie temperature for transformation is
not a constant when particle size decreases.
Explain using core-shell structure → same as melting

For ZrO2 → curie temperature decreases with

decreasing particle size

2a. Define Wulff’s law. Describe a technique that you would choose to growth ZnO nanocrystals. Explain
how Wulff’s law can be applied to the technique that you choose to control the morphology of ZnO
nanocrystals.

26
 2b. Dependence of mechanical strength on grain size in nanometer range for( i) metal and (ii) ceramic

Nanometal Nanoceramic
1. Giant Strength/Hardness No dislocations in ceramic
Dislocation Control Boundaries are defects after sintering
With decreasing grain size Crack/defect size comparable to grain size
• Vol/number of grain boundaries increase Reducing diameter will also reduce crack size
• More boundaries than grains • When grain size become too small,
• Dislocations confined in smaller space boundaries become active and
• Dislocations stopped by boundaries (act ceramic weaker
as effective barriers)
• Yield stress increases
Grain Boundary control
Upon a threshold: when grain size become too small
• Too many grain boundaries
• Small grains become active and
move/rotate/slide like dislocations
• This decreases yield stress

2. Colossal Strain Hardening

3. Super-plasticity
Grain boundary diffusion & bulk-crystal diffusion
27
PART 2
19/20 paper
1b.i. What is coulomb blockade? Can this phenomenon be observed at room temperature? Explain.
Coulomb blockade is the decrease in electrical conductance at small voltage bias of a small electronic device.
It is used to describe quantization of electric charges where current-voltage graph appears to look like a
staircase (as a stepwise function?). Typically observed in metal/semiconductor nanocrystals.
When a device is as small as a quantum dot (0D), electrons inside the device will create a strong Coulomb
repulsion preventing other electrons to flow. This device will no longer obeys Ohm’s law.
Eg. Simplest device exhibiting coulomb blockage: single electron transistor
The conductance of this device may not be constant under a low bias voltage hence there exist a threshold
voltage where below this threshold, no current flows.

Using the tunnel diode as an example, current (electrons) flow through under
an applied bias voltage. This tunnel junction behaves like a resistor where it
obeys Ohm’s law (current is proportional to voltage).
Since tunnel diode has an insulating layer between 2 conducting electrodes, if
this thin layer is replaced with a quantum dot, the tunnel junction behaves
like a capacitor.
Current flowing through the tunnel junction is such that only electron tunnels though the tunnel barrier one at
a time. The tunnel junction will be charged with one elementary charge, resulting in a voltage build up. if the
capacitance is very small, voltage build up can be large enough to prevent another electron from tunneling
(coulomb repulsion). Current is suppressed at low bias voltages and resistance of this device is no longer a
constant.
➔ Meaning to say is applied voltage is lesser than the voltage builds up by the electron inside the
junction, the next electron from outside cannot jump in, hence no current flows.

28
Coulomb blockage can only be observed at low temperatures.
The temperature must be low enough such that the energy required to charge the junction with one
elementary charge (charging energy) is larger than the thermal energy of the charge carriers.

& Energy at room temperature (E = KT = 26meV) is too high to observe coulomb

blockade.
Condition for coulomb blockade:
1. Charging energy is greater than thermal energy
2. Very low temperature/energy
3. Size of quantum dot is ~ 1-3 nm
4. High resistance with low capacitance (high charging energy)
5a. What is the particle in a box model for carrier confinement and how does it predict the change in
semiconductor band gap with particle size?

Conductors: CB & VB overlap Semiconductor: CB & VB has a small Insulator: CB & VB are far apart
but distinct gap
Femi level EF is the highest level where electrons are present
Reducing particle size allows for discrete band gap → loss of overlapping bands
Particle in a box model
Particle in a box model explains a particle free to move in a small space surrounded by impenetrable barriers.
This model is of a one-dimensional system in which a single particle of mass m is confined in a box of length L,
which it cannot escape. The energy of the particle is quantized as a result of the need to fulfill the boundary
conditions imposed on the system. However, the lowest amount of energy of the particle is at n=1, which
implies that the lowest amount of energy of the particle is never zero. In QDs, the electron and hole are
confined such that they move freely within the dot but cannot go out, just like the particle in a box.
Size dependent semiconductor band gap
Size quantization arises because the size of a nanoparticle is comparable to the de Broglie wavelength of its
charge carriers (i.e. electrons and holes). Due to the spatial confinement of the charge carriers, the edge of the
valance and conduction bands split into discrete, quantized, electronic levels. These electronic levels are like
those in atoms and molecules.
Energy gap become size dependent and increases with decreasing radius. This is called quantum confinement
effect and is thereby observed when the QD material size is close to the exciton Bohr radius. Electron hole
pairs are now much closer together and the Coulombic interaction between them can no longer be neglected
giving an overall higher kinetic energy.
This increase in bandgap can be observed experimentally by the blue-shift in the absorption spectrum or
sometimes even visually by the colour of the samples. A larger bandgap means that more energy is required to
excite an electron from the valance band to the conduction band and hence light of a higher frequency and
lower wavelength would be absorbed.

29
5b. You synthesize some semiconductor nanocrystals and find that 10nm particles emit at a wavelength of
500nm, however nanoparticle of 6nm in size emit at 350 nm. What is the bulk bandgap of semiconductor?

5c. metal nanoparticles do not have band gaps but still appear colored. What is the reason for this?
Surface plasmon resonance where electrons oscillate in phase. Collective oscillation led to a large absorption
and scattering cross-section. For small particles < 15nm , absorption dominates and absorption cross section is
large (narrower resonance peak and blue shift). For bigger particles >15nm, the scattering cross section
dominates (broaden and red shift in spectrum). Strong optical absorption means light is near fully absorbed.

Bandgap
When decreasing the size of the nanoparticles the energy states
will become discrete, so that the energy gap will increase. With a
decrease in their size, the band gap increases, and a “blue shift”
is observed upon absorption and photoluminescence.

30
5c. The development of white light emitting diode has saved much of the world’s energy but a
semiconductor laser could save even more. Compare and contrast these 2 devices.
White light emitting diode
LED emits light as a consequence of charge carrier
recombination across P-N junction
- the forward biased P-N junction emits
light when electrons and holes recombine
at the junction.
- GaAsP (Gallium Arsenide Phosphide) and
GaP (Gallium Phosphide) emit energy in
the form of light
Light produced incoherent
Low concentration of charge carriers
Light produced in many colors
Power to light conversion efficiency ~ 20%
Junction area is wider → light pass through a wider area
Light Amplification by Stimulated Emission of
Radiation (LASER)
Emits light as a result of photons striking the atoms
and compels them to release the similar photon.
- electrical energy is supplied to the
electron at the lower energy level, it will
jump from valence band to conduction
band absorbing the additional energy
supplied to it → absorption
- electrons at higher energy is unstable
hence releases energy in the form of light
(emit photon) → spontaneous emission
- Photon strikes atom and it will strike
electrons at higher energy state. Electrons
will move to lower energy state and
release a photon in addition with the
incident photon → simulated emission
- GaAs
Laser requires population inversion
Light produced is coherent
High concentration of charge carriers → sufficient
energy to cut object in contact
Monochromatic light
Power to light conversion efficiency ~ 70%
Extremely narrow junction area → light pass through
extremely small area
31
MLE5211
2c. What is a Metal Oxide Varistor (MOV)? Explain the working principles of the MOV and its corresponding
microstructure and electronic band-structure. Give two examples of compounds that are used to make
MOVs.
MOV is a voltage suppression device where its resistance changes
with applied voltages → non ohmic response. They can pass large
currents while preventing voltage from rising too much above
breakdown voltage.
At low voltage → ohmic response
At high voltage (applied voltage > varistor voltage )→ power law
Electronic properties MO.

Microstructure: Brick structure with a range of grain sizes & shape

Materials : ZnO (bandgap = 3.2eV) doped with Bi or

oxides such as Co & Fe | SiC |TiO2 | SrTiO3

32
3a. A polycrystalline ferromagnetic material is placed in a magnetic field which is increased to saturation, as
in the diagram below. The schematics show the magnetic domain structure (the applied field is to the right).
Explain what is happening from U to Y and Y to Z.

Change of magnetic moment with changing B field of multi

domain magnetic material (alignment of domains lead to
magnetization)
From U to Y, it is categorized as domain wall motion, where we
see the domain that has the smallest angle with H becomes bigger
whilst the other domain becomes smaller.
➔ Domains oriented favorably along the field direction will
grow at the expense of the unfavorably oriented domains
From Y to Z, it is categorized as domain wall rotation. The
misoriented spins in the domain wall will turn to match the
magnetic field, H, direction.
Take note that the 2 processes can also occur simultaneously as the field increases.
Also, rotation of spin is opposed by the increase in anisotropy energy
3b. The field is reduced to zero. Sketch the resulting magnetization curve. What is the magnetization at H=0
called?
Remanence magnetisation, Mr. Refer to the image below.

3c. You now reverse the applied magnetic field until the magnetization becomes zero. What is this field
strength called?
Coercivity. -Hc.
3d. Now complete the hysteresis loop to negative saturation and back to positive again.

33
3e. You now synthesize the same material in nanoparticle form and
find the hysteresis loop gets wider. Explain this phenomenon.
When size decreases, coercivity increases. The coercivity will keep
increasing and reach its peak at the critical diameter.
For multi-domains, when it reaches its coercivity point, domain wall can
move hence the spins in the different domain will cancel out each
other.
However, when particle size decreases to nanometre, domain wall
becomes unstable hence cannot exist. Formation of single domains make magnetization reversal difficult as it
is hard for the domains to rotate to demagnetize in the given magnetic field. Hence, coercivity increases.

3f. You manage to synthesize the nanoparticles even smaller, 10 run in diameter, and find that at room
temperature they are no longer ferromagnetic. What is this phenomenon called?
It has transitioned into super-paramagnetism state. it is not paramagnetism because it occurred at room
temperature. → below curie temperature

3g. Sketch the form of the hysteresis loop in this case.

3h. What is an application for such a nanocrystalline material?

Nano-medicine (read more)
3i. Estimate the anisotropy constant for this material.
Anisotropy constant = K

given diameter and rtp

34
3j. You wish to use these nanoparticles in a hard disc at an operating temperature of 50 °C.What diameter
nanoparticles are required?
use this equation, and the K from the previous question

3k. What bit density would you achieve (in Gbits/sq. inch)? You may assume one nanoparticle represents
one bit.
Use one d-block to find area (assume square). Take one sq.inch / area = that will be the bits. But remember to
change to Gbits.

4d. Metal nanorods have two quite different absorption peaks. What is the reason for this phenomenon?
Spintronics (spin electronics) uses electron spin instead of charge. What is meant by a spin diffusion length?
(b) Explain with the aid of a sketch the phenomenon of spin accumulation at a junction of a ferromagnet
and a normal metal.
( c) Exchange bias occurs when a ferromagnetic layer (F) is coupled with an antiferromagnetic layer (AF).
Sketch the resulting hysteresis loop.
(d) This is used in a giant magnetoresistance (GMR) read head to pin one of the layers. Draw a schematic of
a GMR magnetic tunnel junction and explain why the AF layer increases the sensitivity of the head.
( e) A magnetic tunnel junction is also used in solid state memories. Describe the working principle of a solid
state memory.
(f) A newer, lower power, memory device uses the spin properties of the electrons to switch the device.
What is this kind of memory called and how does it work?
6. The development of the white light emitting diode has saved much of the world's energy but a
semiconductor laser could save even more. Compare and contrast these two devices.

35
 18/19 paper
2.a.i. Sketch the density of state of 2D nanomaterials. Explain the relationship between 2D DOS and the
energy

0D

2D → step wise function

- Once the electrons achieve enough energy, they can "jump" into the next available discrete sub
band, however once in that sub band they have a constant plateau of energy. Hence the staircase
shape.

Density of state (DOS) & Energy

- Density of state is the possible number of state an electron when excited can occupy per unit
volume
- When electrons are trapped within a metal, we can imagine that metal is a finite potential well.
Electrons will have a potential energy of zero inside the well (metal) but the potential energy
jumps to a high value at the edge of the metal
0D – eg. Quantum dots 1D – eg. Nanowire
In 1D materials, DOS is defined as the number of
electronic/quantum states per unit energy per unit
length
When considering DOS for 0D structure (quantum
Eg. An electrically conducting wire in which quantum
dot), no free motion is possible as there is no k-
transport effects are important
space to be filled with electrons and all available
states exist only at discrete energyies, we describe
the DOS with delt function

Eg. A semiconductor crystal that confines electrons,

holes or electron-pairs to zero dimensions

36
 2D
In 2D materials, DOS is defined as the number of
electronic/quantum state per unit energy per unit
area
Eg. A potential well that confines particles in one
dimension, forcing them to occupy a planar region
3D – eg. Nanopores
In 3D materials, DOS is defined as the number of
electronic/quantum states per unit energy per unit
volume
In 3D, particles move freely in all directions with zero
confinement

3a. You synthesize some nanoparticles 5 run in diameter from a ferromagnetic material but find they are
superparamagnetic at room temperature. Sketch the variation of magnetization vs. applied magnetic field
(include both positive and negative directions of applied field). Mark the points of saturation magnetization
Ms and anisotropy field Ha.

Focus on the blue line. Reminder that superparamagnetism only

has one line

37
3b. You find the nanoparticles become ferromagnetic on cooling to -100 °C. Again sketch the variation of
magnetization vs. applied magnetic field and mark the saturation magnetization Ms and anisotropy field Ha.

Focus on the pinkish red line. The part that cuts the x-axis
is coercivity. The part that cuts the y-axis is the magnetic
remanence.

3c. Estimate the anisotropy constant for this material.

given

3d. You wish to use these nanoparticles in a hard disc at an operating temperature of 50 °C. What diameter
nanoparticles are required?
use this equation, and the K from the previous question

3e. What bit density would you achieve (in Gbits/sq inch)? You may assume one nanoparticle represents
one bit.
4a. For perpendicular magnetic recording it is useful to make the bits elongated in the vertical direction.
Why does this increase the achievable bit density?
4b. Why is spintronics a nanotechnology?
4c. Giant magnetoresistance (GMR) and tunnelling magnetoresistance (TMR) are two nanoscale phenomena
used in magnetic recording devices. Explain the principles underlying the operation of each device.

38
5a. In semiconductor nanocrystals the band gap increases over the bulk value by an amount inversely
proportional to particle size. What is this effect called? Use a particle in a box model to explain this
behaviour.
When the nanocrystals decreases in volume, the number of atoms decrease, which results in a loss of
overlapping bands. The effect is called quantum confinement effect. Using particle in a box model, when the
semiconductor crystal is reduced in size, the width of the box will be altered as well as the electron is now
confined to the smaller particle. The formula used is:

Considering that n is discrete (discrete levels), En will be effected by change in L, which is the width. This will
inversely affect the energy levels.
5b. Plasmonics also deals with light at the nanoscale. What is a plasmon and why does it not require a band
gap?
Plasmons are plasma-state of bulk oscillation of the electron sea. OR
“Plasmons are collective oscillations of the electrons which are present at the bulk and surface of conducting
materials and in the neighborhood of conducting particles.” https://www.sciencedirect.com/topics/chemistry/plasmon
Plasmons oscillate, which suggest that there will be a frequency where resonance occurs. Like other waves, it
can be refracted, reflected or absorbed. This would mean that with the emission of the right wavelength and
frequency, there will be absorption and scattering. Usually, for particles smaller than 15nm, absorption
dominates. For particles bigger than 15nm, vice versa. The shape of the particle matters as well. This would
suggest that a bandgap is not needed as light exciting an electron and the electron falling back to VB whilst
emitting photon is not needed to give out light.
5c. What is a surface plasmon? Why is its frequency shape dependent?
Surface plasmons are surface electromagnetic waves that propagate in a direction parallel to the
metal/dielectric (or metal/vacuum) interface.
The shape of the nanoparticle will also show where electrons can be found. Its symmetry plays a role in how
oscillation occurs. “complex structures will have multiple degenerate states”. For example, cube have more
rotation axis as compared to a sphere.
6a. Passing a current across a semiconductor p-n junction can result in light emission. Draw a band diagram
to explain this phenomenon.
6b. How may the efficiency of light emission from a semiconductor p-n junction be improved by carrier
confinement?

39
6c. The development of the blue light emitting diode (LED) has revolutionized lighting due to huge energy
savings compared to previous forms of lighting. How does a white LED work?
LEDs are simply diodes that are designed to give off light. N-type silicon (extra electrons) and P-type silicon
(extra holes) are place together to form a P-N junction. When a battery is connected across the p-n junction,
diode is forward biased, pushing electrons from the n-type to the p-type and pushing holes in the opposite
direction. Electrons and holes cross the junction and combine.
Photons (particles of light) are given off as the electrons and holes recombine.
6d. A semiconductor laser is even more efficient at producing light. How does this device work?
Electrons are injected into the diode, they combine with holes,
and some of their excess energy is converted into photons,
which interact with more incoming electrons, helping to produce
more photons—and so on in a kind of self-perpetuating process
called resonance. This repeated conversion of incoming
electrons into outgoing photons is analogous to the process of
stimulated emission that occurs in a conventional, gas-based
laser.
Photons bounce back and forth in the microscopic junction (roughly one micrometer wide) between the slices
of p-type and n-type semiconductor. The amplified laser light eventually emerges from the polished end of the
gap in a beam parallel to the junction.
A laser device comprises of
- an amplifying/gain medium that produce increase light intensity
- a optical resonator (made up of 2 highly reflective mirrors) to feedback the amplified light beam
into the amplifying/gain medium for further amplification → finally produce beam like coherent
light (laser)
Mechanism in terms of energy conversion
1. Electrical energy supplied to electrons at low energy level, absorbs the energy and jump from valence
band to conduction band. → adsorption
2. Electrons a higher energy state is unstable and hence falls back to valence band & releases energy in
the form of light (emit photon) → spontaneous emission
3. Typically, electrons will fall to ground state where there are lesser electrons in the higher energy level.
We want population inversion where there are more electrons in the higher energy level than in the
lower energy level. To achieve population inversion, we can perform optical pumping where atoms in
the ground state are excited to higher states by absorption of pump light. The electrons in the excited
levels decay by non-radiative transitions to a metastable level which is the upper laser level. The pump
light source may be a flash lamp emitting a broad band of visible radiation.
4. When a photon interacts with the excited electrons in the metastable state, electrons will be
stimulated to transit to the ground state. The transition will result in emission of a photon in addition
with the original photon → stimulated emission

40
 Under the condition of population inversion, when a beam of light passes through the amplifying/gain
medium, more photons will be stimulated than absorbed (stimulated emission dominates spontaneous
emission ) → net increase in the number of photons
The photons will bounce back and forth inside the optical resonator. Light gets amplified and emerge
as beam, coherent light.

17/18 paper

1i. Plot the density of states (DOS) vs. energy of a Quantum wire.

1ii. Name one similarity and one difference between the DOS of the Quantum wire and the DOS of a
Quantum dot.
Difference – DOS of 1D VS 0D is that for 1D there is a sharp increase in the DoS at certain energy levels
followed by a decrease in available states. For 0D QDs, there are only energy states at certain energy levels,
thus DoS is only present at specific energy states.
Similarity – there is an increase in the Dos with increasing energy

41
1b. ErSh can self-assemble to form nanowires of 2 nm width and up to 500 nm length along the <11 O> axis
on Si( l 00) surface. The electrical resistance of the
nanowires was measured along its length and is
shown in Figure 1. What is the resistance per unit
length?

500 x106 / 500 x10-9 = 1 x 1015

600x106 / 500x10-9 = 1.2 x 1015

1ii. Compare the resistivity of ErSh nanowires with that of bulk ErSh, given bulk resistivity is 35
1iii. Give an explanation for your answers in (ii).

Nano Resistivity = (R/L)(A) = (1.2 x 1015 ) x pi (1x10-9) 2 = 3.14 x10-3 m

Bulk resistivity = 3.5 x10 -7 m
Resistivity is larger in nano than in bulk.
When reduced to nano-size, number of atoms reduce significantly which will result in a loss of overlapping
bands/orbitals. This will widen the band gap. Even metal nanowires will act like semiconductors due to the
separation of the conduction and valence band.

42
1ci. What is ballistic transport
It is the unimpeded flow of charge carrying particles over a long distance in a material. This means that the
mean free path of the electrons is longer than the geometric dimensions of the conductor.
Inelastic mean free path: index of how far an electron travels before losing its energy
(From 0D to 1D)
1cii. Name one similarity and one difference between ballistic transport and impurity scattering.
Difference: In ballistic transport there is negligible heat dissipation, free from scattering and motion of carrier
is only altered when colliding with outer wall.
Similarity: Both are a form of electron transport

1ciii. Is ballistic transport phenomenon observed in Question 1 (b) above? Give a brief explanation for your
answers.
Ballistic happens when lMFP > length of wire

3a. Sketch the variation of coercivity from the bulk to the nanoscale. Explain the behaviour and the
importance for applications.

43
3b. You measure a ferromagnetic loop for a nanoparticle sample as a function of temperature, and find that
ferromagnetism disappears above -50 °C. The anisotropy constant K of this material is 10 6 J/m3 . Estimate
the diameter of the nanoparticles. You may assume they are cubic in shape.

Use this KV = KBT

3c. Find the diameter needed for these nanoparticles if a retention time of 100 years is required at an
operating temperature of 50 °C. You may assume one nanoparticle represents one bit.
Blocking temperature formula

KV = KBT (lnt/t0)

3d. You experiment with synthesis conditions and find one that produces nanodiscs. You find the coercivity
is increased even though the nanoparticles have the same volume as before. Explain this phenomenon.
Surface area and hence shape changes from spherical to elongated (nanodiscs). This affected the aspect ratio
and hence nanodics favours the coherent rotation of the magnetization, which increased the coercivity.
Shape anisotropy
Aspect ratio → ratio between the length of the object 𝐿 and its middle diameter 𝐷.
Ellipsoidal or cylindrical shapes favor a coherent rotation of the magnetization and thus large coercive fields.
Complex tip shapes act as nucleation points and significantly reduce the coercive field.
4a. Why does the band gap of a nanocrystal increase as the size decreases? What is this phenomenon
called? Derive an expression for the increase in band gap as a function of diameter.
4b. The bulk band gap of a semiconductor is 1.85 eV. When made into nanocrystals of 6 nm diameter, it
emits light of wavelength 300 nm. What size should you aim to synthesize to achieve an emission
wavelength of 200 nm?
4c. You manage to synthesise such small particles but they are not efficient light emitters. Give a possible
explanation. What could you try to do to improve their efficiency. Justify your answer.
4d. Explain how light can travel down a metallic nanowire. What is this phenomenon called? Why is it useful
for applications in optical computing and medicine?

44
 16/17 paper
1a. What is the density of states (DOS) for a 3D and a ID solid?
1d – number of electronic or quantum states per unit energy range per unit length

3d –number of electronic or quantum states per unit energy ranger per unit volume

1b. Describe the electrical conduction behaviour for (i) single-walled and (ii) multiwalled carbon nanotube.
Q3 covered in Tut 3
4a. Why does the band gap of a nanocrystal increase as the size decreases?
With the holes in the valence band and the electrons in the conduction band being confined by the potential
barriers of the surface or the potential well of the quantum box (Quantum Confinement effect). As particle
size decreases, the surface to volume ratio in increases, the number of overlapping orbitals or energy levels
decreases, and the width of the band becomes thinner. This causes and increase in the energy gap between
the valence and conduction band.

45
4b. The bulk band gap of a semiconductor is 1.5 eV. You synthesize some nanocrystals of the same material
and find they emit at a wavelength of 600 nm. Examination in a SEM shows they have a diameter of 20 nm.
What size should you aim to synthesize to achieve an emission wavelength of 400 nm?

4c. Explain how light can travel down a metallic nanowire. What is this phenomenon called? Why is it useful
for applications in optical computing and medicine?
This phenomenon is called surface plasmon resonance brought about by collective conduction band electron
oscillation. When photon incident light hits the metallic nanowire surface, at a certain angle of incidence, a
portion of the light energy couple through the metal coating with the electrons in the metal surface layer,
which travels down the nanowire due to excitation, which propagate parallel to the nanowire surface.
15/16 paper
2d. Define the quantised electrical conductance in nanomaterials. Briefly describe an experimental
technique that you can use to demonstrate the quantised electrical conductance in a 1 D nanomaterial.
Quantised conductance is the change in conductance in discrete steps.
In bulk material, electron transport is described by Drude’s model. In
nanomaterials, the dimension of the system is less than free electron path, the
impurity scattering is negligible, so the electrons transport can be regarded as
ballistic.
Quantum conductance characterizes the ballistic regime, when the size of the
nanoscale conductor (molecule, nanotube, quantum dot, etc) is much smaller
than the electron mean free path. In this case electrons pass through the
nanoconductor essentially without any interaction, and resistivity arises from scattering on end (metal)
contacts that act largely like walls to a box. The electrons become quantum particles in a box under applied
voltage, while conductance becomes independent of the size of the conductor and quantized, with a
conductance quantum of 2e2/h.
46
3a. You synthesize a set of nanoparticles with diameters 5, 10, and 50 nm. Observing them in a scanning
electron microscope you see they are approximately spherical in shape. You measure their hysteresis loops
at low temperature and find the highest coercivity for the 10 nm particle. The 5 nm particles show no
coercivity and the 50 nm particles show a ferromagnetic loop, but half the coercivity of the 10 nm particles.
Explain these observations.
50 nm → multidomain
10 nm → has single domain
when particle size decreases to nanometre, domain wall becomes unstable hence cannot exist. Formation of
single domains make magnetization reversal difficult as it is hard for the domains to rotate to demagnetize in
the given magnetic field. Hence, coercivity is higher in 10nm than in 50 nm.
5nm → exhibit superparamagnetism where magnetization fluctuates and spin flipping occurs. Coercivity falls
to 0.
3b. For the 10 nm particle you find its hysteresis loop vanishes at a temperature of T= 123 K. What is the
anisotropy constant?
Hysteresis loop vanishes → superparamagnetism

3c. The figure on the right shows that nanorods have higher
coercivity than spherical particle: Explain this phenomenon.
Shape anisotropy
Aspect ratio → ratio between the length of the object 𝐿 and its
middle diameter 𝐷.
Ellipsoidal or cylindrical shapes favor a coherent rotation of the
magnetization and thus large coercive fields. Complex tip shapes
act as nucleation points and significantly reduce the coercive field.
For objects such as the nanowires and the capped nanowires, the behaviour is very close to ellipsoids.
Other extra features at the end of nanowires promote the formation of vortex states which significantly
decrease the shape anisotropy. Aspect ratios of at least 20 should be used to reach a value close to the
maximal theoretical shape anisotropy.

47
d) You find a method to grow your material as nanorods of various diameters, and find the anisotropy is
increased by 50% for an aspect ratio of 4. In a perpendicular recording geometry, what maximum bit density
(Tbits/sq. inch) could you achieve for a 100-year retention time at 50 °C? You may assume your bits are
square in cross section.

4a. Discuss the concept of the Bohr radius in a semiconductor. Why is it much larger than the size of a H
atom?
In semiconductors, the electron-hole pairs form excitons at low temperatures. The Bohr radius represents the
natural distance of the electron from the proton in a hydrogen atom. In semiconductors, the excitons are
confined in the nanocrystal and move in a screening medium as compared to in an H atom where electrons
travel in a vacuum. This results in a much larger effective Bohr radius which means that the electron-hole pairs
in the excitons are less confined in space than the hydrogen atom
4b. What happens to the band gap of a semiconductor nanocrystal as its size approaches the Bohr radius?
What is this phenomenon called?
Band gap increases. Quantum confinement effect.
4c. You synthesize CdSe nanoparticles of diameter 7.5, 3.2 and 2.1 nm and measure their emission spectra
when excited by ultraviolet light. The spectra peak at wavelengths of 650, 570 and 480 nm, respectively.
Calculate the band gap Eg as a function of particle size. Explain the dependence. Estimate the bulk band gap.
What size nanoparticle would you need for a band gap of 3 e V?

d) Explain why such a small nanoparticle may not have a high emission efficiency. What could you do to
improve it?

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49