Chapter:4

Specific Surface Energy:

The specific surface energy (γ) can be represented as the energy produced by
cleaning a crystal divided by the surface area thereby created. It means γ is
represented as the amount of work done per unit area needed to elastically stretch a
pre-existing surface.

Mathematically, dω= The amount of work done

γ = dω/dA dA= Charge of the surface area of an object

Size effect on the lattice parameters of Nanoparticles:

Let the boundary diameter of a spherical particle Po be d₀. The particle P₀ can be
changed into n smaller identical spherical particles Pn whose diameters are d
without changing its volume.

Mathematically,

Every atom on the particle surface contributes half its surface area to the whole
surface area of the nanoparticle so the surface area of Pn is:

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 ……………….…………………… (1)

…… ……………….…………………. (2)

The surface energy variation (Δγ) can be written as, Δγ = sγo – γoso …………… (3)

Here,
So = surface area of P₀
γo = surface energy per unit area at room temperature

However, the surface energy increase of nanoparticles will tend to contract their
size by distorting their crystal lattice elastically. This kind of distortion is very
small comparing the whole particle size. Let us suppose that a small displacement
εd results from this elastic distortion.

Now eqn (3) can be written as:

Δγ = sγo – γoSo
=

………………………………………… (4)

By considering these particles as ideal spheres, we find that the elastic energy (f)
is associated with the contraction of nanoparticles by using elastic theory.

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 ………………………………………… (5)

Here, G= Rigidity modulus

Taking into account the reduction in surface energy increasing due to the
contraction of the particles, we can write the total energy F:

Total energy F = surface energy + elastic energy

= Δγ + f

Now,

…………………………………… (6)

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 …………………………… (7)

……………………………. (8)

For an ideal crystal lattice, the lattice parameter contraction is proportional to the
diameter of the nanoparticles.

…………………………………………. (9)

Where Δa = aparticle – a aparticle = lattice parameter of nanoparticle

a = lattice parameter of bulk material

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Putting the value of ε in eqn (9),

K= πG/2γo

……………………………………………. (10)

Eqn. (10) indicates that the lattice parameters of nanoparticles contract with
decreasing particle size.

✓ Difference Between Photon and Phonon

✓ What is quasiparticle and bound state?

Exciton:
An electron and a hole that are attracted to each other by Coulomb force can form a
bound state called an exciton. Exciton is the combination of an electron and a hole
which are attracted to each other by Coulomb force. The electron and hole have
equal but opposite electrical charges; the exciton as a whole has no electrical charge.

So, it is an electrically neutral quasiparticle that exists in insulators, semiconductors,

and some liquids. The exciton is regarded as an elementary excitation of a condensed
particle that can transport energy without transporting net electrical charge.

An exciton in a semiconducting material can form when a material absorbs a photon

of higher energy than its bandgap. This excites an electron from the valence band
into the conduction band. In turn, this leaves behind a positively charged

hole. The electron in the conduction band is then less attracted to the localized hole
due to the Coulomb forces from the large number of electrons surrounding the hole
and excited electrons. These repulsive forces provide a stabilizing energy valence.
Consequently, the exciton has slightly less energy than unbound electrons and hole.
The concept of exciton was first proposed by Yakov Frenkel in 1931.

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What is the classification of exciton?
Answer: Two types

1. Frenkel exciton/tight binding exciton

2. Wannier-Mott exciton/weak binding exciton

1. Tight binding exciton:

This excitons are observed in ionic crystal with relatively small dielectric constant,
large effective masses, and strong coupling with lattice as well in organic
molecular crystal (such as anthracene, tetracene etc.)

For strong electron-hole attraction as in ionic crystal, the electron and the hole one
tightly bound to each other within the same or nearest neighbor unit cells. In
materials (insulators) with a relatively small dielectric constant, the Coulomb
interaction between an electron and a hole may be strong and the exciton

thus tends to be small. The binding energy is on the order of 0.1 to 1 eV. This
excitons are found in alkali halide crystals and in organic molecular crystals.

2. Weak binding exciton:

This exciton are observed in semiconductor crystals, small energy gaps, and high
dielectric constant. Its also identified in some liquids such as liquid xenon.

In most semiconductors, the Coulomb interaction is strongly screened by valence

electron via the large dielectric constant. Consequently, electric field screening tends
to reduce the Coulomb interaction between electron and hole.

The result is a weaker Wannier-Mott exciton which has a radius larger than lattice
spacing. Because of lower effective masses and screen Coulomb interaction, its
binding energy lies in the order of 0.01 eV.

✓ Difference between tight binding and weak binding exciton

✓ What is effective mass?
✓ What is the difference between linear optics and nonlinear optics?

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Non-Linear optics:
It is the branch of physics/ optics that describes the behavior of light in non-linear
medium. It is the study of how intense light interacts with matter. It is also the study
of modification of the optical properties of a material system by the presence of light.

Typically, only laser light is sufficiently intense to modify a material system's optical
properties. (Franken-1961) The non-linearity is observed at very high light
intensities such as those provided by laser. In non-linear optics, the principle of
superposition no longer holds.

Linear optics:
Linear optics is a subfield of physics consisting of linear systems. It includes most
applications of lenses, mirrors, diffraction grating, etc. than the following properties:

1. If monochromatic light enters an unchanged linear optical system, the output

will be at the same frequency. For example, if red light enters a lens, it will
still be red when it exits the lens.

2. The superposition principle is valid for linear optics or linear optical systems.
For example, if a mirror transforms light input A into output B and input C
into output D, then input A and C simultaneously give an output of B and D
respectively.

✓ (Write more points, HW)

✓ (Graphical representation from the internet)
✓ (Difference between linear and non-linear optics)

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Non-linear susceptibility/ polarization:
Let us consider the dipole moment per unit volume or polarization, P(t) of a material
system that depends upon the strength E(t) of the applied optical field strength. In
the case of linear optics, the induced polarization depends linearly upon an electric
field strength in a manner that can be represented by the following impression:

……………. (1)

Where χ(1) = linear susceptibility.

In nonlinear optics, the optical response can be described by generalizing equation

(1), expressing the polarization P(t) as a power series in the field strength E(t).

……… (2)

Where, χ2, and χ3 = 2nd and 3rd-order susceptibilities, respectively.

In general, nonlinear susceptibilities depend on the frequency of the applied field.

Nonlinear optical interactions can be described in terms of nonlinear polarization
given in eqn (1) only for a material system that is lossless and dispersionless. In
this general case, the nonlinear susceptibility becomes a complex quantity relating
to the complex amplitude of the electric field and ed polarization. We assume that
the electric field vector of the optical wave is the sum of a number of frequency
components.

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 ………….. (3)

The prime on the summation of equation (3) is to be taken over the +ve frequencies
only. So in general E(r,t) can be represented as the sum of its +ve and -ve
frequency parts.

………. (4)

…………. (5)
…………..(6a)
-

………….. (6b)

It is also convenient to define the spatially slowly varying field amplitude An by

the relation:

…………………….. (7)

From equation (3) and (4),

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 C.C

C.C

conjugate
…………… (8)

Let,
………..…… (9)

Putting (9) in (8),

……………(10)

In the case of nonlinear polarization, this is the electric field. According to eqn (10)
we can summarize that:

Where unprimed summation denotes an ∑ over all frequency of both (+ve) and (-
ve).

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