Module IV

Quantum Mechanics and Instrumentation Techniques for Material

Characterisation
Dr. F. Jyothi Serrao
Dept. of Physics. SCEM
Introduction:
The aim of the physics is to understand the natural phenomena around us. 19 th century witnessed a
rapid growth in physics. Towards the end of the 19 th century it was generally believed that all that to
be discovered in nature was discovered, and all the laws of nature were formulated. The Newtonian
mechanics, Maxwell’s electromagnetic theory and thermodynamics were the major theories of 19 th
century Physics, came to be known later as classical Physics. Classical Physics successfully
explains the behavior of macroscopic (visible) bodies.
Even though the majority of experimental evidence agreed with the classical physics, a few
experiments gave results that could not be explained satisfactorily. One experimental phenomenon
that could not be adequately explained by classical physics was blackbody radiation. The exact
spectrum depends upon properties of the material and the temperature. It was found that the
observed intensity of blackbody radiation as a function of wavelength varies with temperature.
Attempts to explain or calculate this spectral distribution from classical theory were complete
failures. After the failure of Rayleigh’s attempt to explain black body spectrum using equipartition
theory, Max Planck came out with his famous quantum theory of radiation in 1900 in order to
explain the black body problem and it is the beginning of Modern Physics.

Planck’s Quantum Theory of Radiation:

The wave theory of light failed to explain the black body spectrum. So, in 1900, Max Planck
proposed an empirical formula to explain the spectral-energy distribution of radiation emitted by
a blackbody. Max Planck derived this equation, based on the following assumptions.

1] The radiation emitted by the black body is not continuous but consists of packets or bundles of
energy called quanta.

2] Interior of the black body consists of tiny electromagnetic oscillators vibrating with certain
frequency.

3] The electromagnetic oscillators can have a discrete set of energies which are integral multiple of
hν , i.e., En =nh ν , n = 1, 2, 3, …..where ‘h’ is a constant called Planck ’s constant.
And h = 6.63x10-34JS

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4] An electromagnetic oscillator can lose or gain energy by emitting or absorbing respectively a
ΔE
ν ν=
radiation of frequency ( h ). Where ΔE is the energy difference in the value of the energy
of the blackbody before and after the emission or absorption had taken place.

Based on these assumptions, he derived the expression for energy density of radiation, which is

given as
U λ dλ=
8 π hc
λ 5
e [ 1
hν / kT
−1
dλ
]-------- (1)

where U λ dλ → is the energy/unit volume in the range of wavelengths λ∧λ+ dλ

h is Planck’s constant = 6.63× 10-34Js
k is Boltzmann constant = 1.38× 10-23 J/K
In terms of frequency the equation (1) can be written as

U ν=
8 πhν 3
c 3 [
e
1
hν / kT
−1 ]
de Broglie’s concept of matter waves:

In 1924 Louis de Broglie proposed a concept called matter waves.

According to him, when a particle of mass ‘m’ moving with a velocity ‘v’ then it exhibits a wave
nature. The wave associated with the moving particle is called matter wave and its wavelength

(de Broglie wavelength) is given as

h h
mv p
= = Where h  Planks constant, p  momentum

Characteristics of matter waves

h
1) The wavelength of the matter wave is given by λ= , it shows that lighter the particle,
mv
greater is the wavelength associated with it.
2) If V= 0, then λ =∞, that means the matter waves are generated only by the moving particles.
3) Matter waves are not electromagnetic waves and can be associated with any particles whether
charged or uncharged
4) Matter waves can propagate in a vacuum; hence they are not mechanical waves.
5) Matter wave travel faster than light (Phase velocity is greater than speed of light)

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 6) In matter wave, there is a periodic variable quantity called wave function (ψ). It is a measure
of probability of finding the particle at a given position and time.

Expression for de Broglie wavelength in terms of energy of the particle:

Consider a particle of mass m moving with velocity v. Let its kinetic energy be E.

E = ½ mv2

Multiplying by ‘m’ both sides,

mE = ½ m2v2

p2
2
mE = (mv = p)

p2 = 2mE

p = √ 2 mE
h
p
de Broglies wavelength,  =
h
 = √2 mE

de Broglie wavelength associated with electrons:

Consider an electron of rest mass m and charge e, accelerated by a potential difference of V volt
from rest to a velocity v. Then work done on the electron is W = eV
This work done is converted into kinetic energy of the electron.
1
mv 2
2
eV =

√
2 eV
v= m
h h h h
= = =

√ √
m2 2 eV √2 meV
mv 2 eV
m
m m
But,  =
h
 = √2 meV

For an electron h = 6.63  10-34 Js, m = 9.1  10-31 kg and e = 1.6  10-19 C

3
 0
−34
6 . 63×10 12. 27 A
=
 = √2×9 .1×10
−31
×1 .6×10 −19
×V √V

Heisenberg’s Uncertainty principle:

Statement: “It is impossible to determine both position and momentum of the particle
simultaneously with complete accuracy and the product of uncertainties in the position and
h
momentum is always greater than or equal to ”.
4π

If Δx and Δp are the minimum uncertainties (errors) in the position and momentum of the particle,
h
Δx . ΔP ≥
then 4π
h
ΔE . Δt≥
The uncertainty principle is also expressed in terms of energy and time. i.e, 4π
Q. Give the Physical significance of Heisenberg’s uncertainty principle (HUP).
Ans: i) According to HUP, particle’s position and momentum or energy and time cannot be
measured accurately. All these measurements are just probabilistic measurements. This suggests
that in quantum world of particles, no measurement is accurate.
ii) The estimation of probabilities is made by means of a mathematical function called ‘probability
density function’ in Quantum mechanics.

Application of uncertainty principle: - i.e., Non –Existence of electron in the nucleus:

Question: Show that a free electron cannot exist inside the nucleus of an atom.
OR
Using the uncertainty principle, explain the non-existence of electrons in the nucleus on the
basis of β- decay observations.
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Ans: The diameter of the nucleus is of the order of 10 m. If the electron exists in the nucleus, it
can be anywhere within the diameter of the nucleus.
i.e, ∆x ≤10 -14 m
Then the minimum uncertainty in the momentum is determined using Heisenberg’s uncertainty
h
Δx ΔP x ≥
principle 4π

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 h 6 .63×10−34
−14
i.e., ∆px ≥ 4 π Δx = 4 π×10
6 .63×10−20
∆px ≥ 4π = 0.528 ¿ 10 -20 kg m/s

Which is the uncertainty in the momentum of the electron. But since the momentum of the
electron must at least be equal to the uncertainty in the momentum, we can write

p = 0.528 ¿ 10 -20 kg m/s --------------- (1)

2
p
we know that, the kinetic energy of the electron E= -------(2)
2m
substituting equation (1) in (2)
−20 2
(0.528 ×10 )
E= −31
2 × 9.1× 10
−11
E=1.5× 10 J
Expressing in eV
−11
1.5× 10
E= −19
eV
1.6 × 10
E=95.6 MeV which is the K.E of the electron which exist inside the nucleus by theoretical
calculation
But β-decay experimental observation reveals that the maximum kinetic energy (K.E) of the β-
particles (electrons) coming out of the nucleus is only 3 to 4MeV. This clearly shows that electrons
cannot exist within the nucleus.
Note : [ β-decay : The process that takes place in radioactive nucleus which leads to the emission
of β-rays (electrons) is called as β-decay. Β-decay is due to the decay of a neutron inside the
nucleus into a proton, an electron & a neutrino. It is represented symbolically as,
n p + e- + γ
Where p, e- and γ represents a proton, electron and neutrino respectively. An electron is emitted by
the nucleus just when this process occurs is called a β-particle].

Wave Function:- Wave function (ψ (Psi)) is a variable quantity which mathematically describes the
wave characteristics of a particle in a matter wave, it is a measure of probability of finding the
particle at a given position and time.
If  = 0, it means the particle is not there at that instant.
If  = 1, it means the particle is definitely there at that instant.
If  = 0.5, it means the probability of finding the particle is 50% etc.

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Properties of wave function:
1) The value of ψ is related to the probability of finding a particle at a given space & at a given time.
2) ψ must be single valued and finite everywhere
dψ dψ
3) dx or dt must be continuous and single valued everywhere.
4) ψ must be normalizable and it should not be infinity.

Physical significance of wave function:

1] Probability Density and Max Born’s interpretation:
The wave function is usually a complex function with both real and imaginary parts. If this is the
case, then it is difficult to give physical interpretation. To get a positive and real value, the wave
¿ ¿
function ψ is multiplied with its complex conjugateΨ . Then the product ψ ψ = | is always a
positive real quantity and is called Probability Density. This interpretation is made by Max Born.

A large value of ||2 represents larger probability of finding the particle. The probability of
finding the particle is zero at a point only if ||2=0 at that point. If ||2=1, the probability of finding
the particle is 100%, if ||2=0.5, the probability of finding the particle is 50% etc.
The probability of finding the particle in a certain volume dV=dx.dy.dz is equal to ||2 dV.

2] Normalization of wave function: -

Consider a particle enclosed in a volume V. Its probability density over a small volume dV is
| dV. If you make several attempts to find the particle over the entire volume, then obviously
integral cannot be Zero or Infinity, it is equal to ONE.
V
∫|Ψ |2 dV = 1
0

This is known as Normalization.

+∞
∫
Normalization for a particle in space is −∞
2
|Ψ | dV = 1
x
∫|Ψ |2 dx = 1
Normalization for a particle in 1-dimension is 0

Note:
In classical mechanics, a particle occupies a definite place in space & possesses definite momentum
and the future history of the particle can be completely determined by these parameters. But in the
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subatomic world it is not possible due to Heisenberg Uncertainty Principle. This initiated a new
approach to solve the problems involving subatomic particles, developed in 1925 by Schrodinger
and others known as Quantum mechanics. So, quantum mechanics is a new branch of physics,
which deals with the mechanics of particle or bodies in the atomic and the sub-atomic scales.

Derive the time-independent Schrodinger’s wave equation for a particle in one dimension:
Based on de Broglie’s concept of matter waves, Schrodinger developed the wave equation which is
now known as Schrodinger wave equation, which can be used to determine the motion of an atomic
particle.
According to the de-Broglie theory, the wavelength of the wave associated with a particle of mass
‘m’ moving with a velocity ‘v’ is given by
h h
 = mv = p
The wave function describing the de Broglie wave, travelling in positive x-direction can be written
in complex notation as
Ψ =Aei(kx-ωt) ------------------(1)

Where A is the amplitude, k = , ω=2π ν and x is the position coordinate at time t

Differentiating eqn (1) twice, w.r.to x, we get

=ik Aei(kx-ωt)

= ik ik Aei(kx-ωt)
d2 ψ 2 2
∴ =i k ψ
dx 2
d2 ψ
2
=−k 2 ψ
dx
2π
k=
Substitute λ in above eqn.
d 2 ψ −4 π 2
= 2 ψ
dx 2 λ
We get

Or = --------------(2)

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If a particle is moving in a field whose potential is V then,
Total energy of the particle E = Kinetic energy + Potential energy
i.e., E = K.E +V ----------(3)
1 2
mν .
The kinetic energy of a moving particle of mass m and velocity ‘v’ is given by 2
1 2 m 2 v 2 p2 h 2 1 h
mv = = = 2. (∵ λ= )
2 2 m 2 m λ 2m p

K.E = =

Or, K.E = ------------(4)

Substitute eqn (2) in (4) We get
h2
.
K.E = 2m

−h2 1 d 2 ψ
= 2 2
K.E = 8 π m ψ dx -----------(5)
Substitute eqn (5) in (3) We get
−h2 d 2 ψ
∴ E= 2 +V
8 π mψ dx 2
−h2 d 2 ψ
∴ E−V =
8 π 2 mψ dx 2

8π2m d2 ψ
( E−V )ψ=− 2
h2 dx
d2 ψ 8 π2 m
+ 2 ( E−V )ψ=0
dx 2 h
This is the time-independent Schrödinger’s equation for a particle in one-dimension.

Operator mechanism in Quantum Mechanics

An operator is a symbol or a code which directs one to perform an operation on the function, which
follows the symbol.
Eg: Mathematical operators
Example Operator Operation
√3 √ Take the square root.

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d 3 d Take the first derivative w.r.to x.
( x + 3) dx
dx

Quantum Mechanical operators

Physical observable Operator Operator symbol
Momentum h ∂ ^
P
2π i ∂ x
Kinetic energy −h 2 ∂2 T^
8 π 2 m ∂ x2

Eigen Functions :- The wave function which possess the following properties is called the Eigen
function and the properties are:
1) ψ must be single valued and finite everywhere
dψ dψ
2) dx or dt must be continuous and single valued everywhere.
3) ψ must be normalizable and it should not be infinity.

Eigen Values:- Once the Eigen function is known, quantum mechanical operators could be used to
evaluate the physical observables such as momentum values, energy values etc. These values are
called Eigen values.
In general, we can write an Eigen value equation as

A^ ψ=λψ
^ operates on a function ψ and this yields a constant ' λ ' times the function. Then
Here the operator A

the function ψ is called an Eigen function of the operator A^ , and the corresponding value for λ is
called the Eigen value.

( Eg: = a. )
(Note: If an energy operator operates on ψ, then the Eigen values are called energy Eigen values. If
a momentum operator operates on ψ, then the Eigen values are called momentum Eigen values.)

Application of Schrodinger Wave Equation: We can apply the Schrodinger wave equation to the
case of a particle confined to move in a one-dimensional potential well and obtain the information
regarding the energy values, probability density etc.

Particle in one dimensional potential well of infinite height (or particle in a box)
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 Consider a particle moving in one dimensional potential well of infinite height and of width ‘a’.
The condition for particle motion is

1. The particle moves along x – axis between x = 0 and x =a

2. The particle is a free particle i.e., not subjected to any external force.

Therefore, the potential energy, V = 0 inside the box

The potential outside the box is infinite

V= V=0 V=

3. The value of the wave function  outside the box is zero.

i.e.,  = 0 2
=0 x=0 x=a

which means that the particle cannot be found

at all outside the box

We have Schrodinger equation for a particle in one dimension as

d2 ψ 8π2m
dx 2 h2
+ (E – V) = 0

Inside the box the equation becomes

d2 ψ 8π2m
dx 2 h2
+ E = 0 (Since V = 0) ---------- (1)

8 π 2 mE
h2
Let = K2 ---------------------- (2)

d2 ψ
dx 2
 Equation (1) becomes, + K2 = 0 ------------- (3)

This is second order homogeneous differential equation.

The solution of Equation (3) is given by

 = C cos Kx + D sin Kx ------------- (4)

Where C and D are the constants depending on the boundary condition

Applying the boundary conditions

1. At x = 0,  = 0 as per condition (Ị)

Hence equation (4) becomes 0 = C cos 0 + D sin 0 . but cos 0=1 and sin0=0

 C = 0 ------------ (5)

2. At x = a,  = 0

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  Equation (4) becomes, 0 = C cos Ka + D sin Ka

But C = 0 from equation (5)

 0 = D sinKa

Or, D sinKa = 0

D need not be equal to zero

 sin Ka = 0 ------------ (6)

We have

Sin 0 = 0

Sin  = 0
Sin 2 = 0
Sin 3 = 0
Sin n = 0 ------------- (7)
n = 0, 1, 2, 3,……………….

Comparing equation (6) and (7)

nπ
a
n = Ka or K= ----------- (8)

Substituting the value of C and K in equation (4)

nπ
a
 = D sin x -------------- (9)

To evaluate D in equation (9) we have to perform the normalization of the wave function. Since
the particle is inside the box, the probability of finding the particle is 1. Hence
a
∫0 2
dx = 1
a
∫0 D sin 2 2
nπ
a
x dx = 1 But sin2  =
1
2
(1 – cos 2)

a
∫0 D 2 2 (
1 1−cos 2nπ x
a ) dx = 1
D2
2 [
∫ 0 (1−cos
a 2nπ
a )
x dx
] =1

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 D2
2 [
∫ 0 dx−∫0 cos 2 anπ xdx
a a
] =1

[ [ ]]
a
D2 a a 2 nπ
[ x] 0− sin x sin nθ
2 2 nπ a 0
=1 Using
∫ cos n d = n

2 [
D 2 ( a−0 )− a sin 2 nπa −0
2 nπ a
=1
]
2 [
D 2 a− a sin2 nπ
2 nπ
=1
] (sin 2n = 0)

D2 a 2
a
 2 = 1  D2 = or D= √ 2
a ----------- (10)

 The normalized Eigen function of a particle in a one dimensional box is given by

From equation (9), n = √ 2 nπ

a sin a x ---------- (11)

Energy Eigen values:

8 π 2 mE nπ
h2 a
From equation (2) = K2 From equation (8) K =

8 π 2 mE n2 π 2
h2 a2
=

n 2 h2
8 ma 2
E=

n 2 h2
8 ma 2
En = --------------- (12)

The particle has discrete energy levels (n). The energy Eigen values and corresponding Eigen
functions at different energy levels can be given as

For n = 1, E1 =
h2
8 ma 2
and 1 = √ 2 π
a sin a x (ground state)

For n = 2, E2 =
4 h2
8 ma 2
and 2 = √ 2 2π
a sin a x (First excited state)
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For n = 3, E3 =
9 h2
8 ma 2
and 3 = √ 2 3π
a sin a x (Second excited state)

Note: The energy corresponding to n = 1 is called the ground state energy (or zero point energy)).

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Instrumentation For Material Characterization
Nanotechnology: Nanotechnology is a branch of engineering that deals with the design and
manufacturing of materials at the molecular scale i.e. in the nanoscale.
Nanomaterials: If the size of at least one dimension is less than 100nm, then the material is called
as nanomaterial.
On the Basis of Dimension, Nanomaterials are Classified as
 Zero dimensional nanostructures (e.g. Spheres and Clusters etc.)
 One dimensional nanostructure (e.g. Film. Coatings, Multilayer’s etc.)
 Two dimensional nanostructures (e.g. Tubes, Fibers, Wires etc.)
 Three dimensional nanostructures (e.g. Particles, Quantum Dots, Hollow Spheres etc.)

Material Characterization: Material characterization is the process of measuring and determining

physical, chemical, mechanical and microstructural properties of materials. It is a fundamental
process in the field of materials science, without which no scientific understanding of engineering
materials could be ascertained. Understanding the material properties is important for the engineers
to design and develop the devices and products.

Popular Material Characterizations techniques are:

1. X-Ray Diffraction (XRD) : Used to analyse the crystalline structure of the sample
2. X-ray Photoelectron Spectroscopy (XPS) : XPS examines the elemental composition of a
sample
3. Atomic Force Microscopy (AFM): Used to study the atomic-scale topography of a surface of
the sample
4. Scanning Electron Microscopy (SEM): Used to study the surface topography and chemical
composition of the sample.
5. Transmission Electron Microscopy (TEM) : Used to study the details of individual atoms.

1. X-ray Diffractometer (XRD):

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X-ray diffraction is a powerful non-destructive technique to analyse the structural properties of solid
materials. This technique is applied to derive information like lattice constant, preferred orientation,
lattice strain, chemical composition and crystallographic structure of the materials.

Principle: X-ray diffraction is based on the principle of constructive interference of monochromatic

X-rays and a crystalline sample.
Construction: The essential parts of an X-ray Diffractometer are
1) Source of X-rays,
2) A crystalline sample held on a circular table,
3) A detector
X-rays are generated by a cathode ray tube, filtered to produce monochromatic radiation,
collimated to concentrate, and directed toward the sample kept on a circular table as shown in
the figure. The X-rays interact with the set of planes in the sample and get reflected from the
sample planes. The incident angle θ is defined between the X-ray beam and the sample and the
diffracted angle 2θ is defined between the incident beam and the detector as shown in Figure.
The reflected x-rays from the sample undergo constructive interference and are received by the
detector and it produces the diffraction pattern in terms of peaks in which peak intensity is
plotted on the Y-axis and the diffraction angle (2θ) along X-axis, as shown in the figure.

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Working: Monochromatic X-rays are made to incident on the sample. The interaction of the
incident rays with the sample produces constructive interference resulting in diffraction peak. The
condition of the constructive interference is given by the Bragg law, 2d sin  n where d is lattice
spacing, λ is the X-ray wavelength, n is the order of diffraction and θ is diffraction angle. The d
values are calculated using the above relation for known values of θ, λ and n.
The typical XRD pattern consists of a series of peaks and are called “reflections”. Each peak in the
diffraction pattern corresponds to x-rays diffracted from a specific set of planes in the material
(sample). The height of the peak represents the corresponding intensity of the peak. The positions of
the peaks in the XRD pattern depend on the crystal structure of the material while intensities depend
on many factors like atomic structure, incident intensity, slit width, the number of grains, etc.
Experimentally obtained diffraction pattern of the material is compared with Joint Council Powder
Diffraction (JCPDS) data for standards. This gives information of different crystallographic phases,
relative abundance, and preferred orientation etc,.
From the width of the diffraction peak, the average grain size can be estimated using Debye
kλ
Scherrer’s formula D= , where k is a constant determined by the geometry of the crystallites
β cosθ
and it is approximately 0.9 for spherical particles, D is the grain size, λ is the X-ray wavelength, β is
the full width at half maximum of the peak (FWHM) in radians and θ is the angle of diffraction.

Advantages of XRD:

1) XRD is a powerful and rapid technique which produces clear and accurate results of the
sample.
2) It identifies crystal structures of unknown substances
3) It only requires preparation of a minimal sample for analysis

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Disadvantages of XRD:

1) The sample should be homogeneous.

2) The sample must also be very small in quantities so proper preparation of samples is crucial.
3) XRD analysis requires access to standard reference data.

AFM (Atomic Force Microscope): The atomic force microscope (AFM) is a type of scanning
probe microscope, used to obtain high-resolution surface topographical images (2D and 3D) of the
sample. AFM is one of the important tools for imaging, measuring and manipulating the materials at
the nanoscale.
Principle: AFM microscope operates on the principle of surface sensing by measuring the changes
in the force between the tip of the cantilever and the surface of the sample by raster scanning across
the surface line by line and an image is formed by detecting this force.
Construction: AFM consists of a microscale cantilever with a sharp tip (probe) at its end which is
used to scan the sample surface kept on a piezoelectric scanner. A laser beam is used to detect
cantilever deflections towards or away from the surface. The laser beam is made to fall on the back
of the cantilever tip, which is coated with a reflective (Shiny) material and light gets reflected from
the shiny surface. The cantilever deflection will cause slight changes in the direction of the reflected
beam. To track these changes, a position-sensitive photo diode (PSPD) is used. Thus, when an AFM
tip passes over the surface of the sample, the resulting cantilever deflection is recorded in the PSPD
and the image of the surface topography will be displayed in the monitor. A feedback mechanism is
employed to enable the piezoelectric scanner to control the height of the tip from the sample
surface.

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Working: The sample under study is placed on a piezoelectric scanner. Then a cantilever with a
sharp tip is made to pass over the surface, line by line so as to raster scan the sample surface. During
the scanning process, a laser beam is made to fall on the back of the tip, which is coated with a
reflective (shiny) material. The laser beam gets reflected from the shiny surface and falls on a
photodetector screen. When the AFM tip encounters bumps or depressions on the sample surface, it
gets deflected from its original position, causing the laser beam to move too. This movement is
detected by a position sensitive photodetector and the image of the surface topography will be
displayed in the monitor.

Advantages of AFM:

1. It Measures the particle size accurately

2. It gives high-resolution surface topographical images both in 2D and 3D.
3. It can be used to study living and non-living elements

Disadvantages of AFM:

1. It can only scan a single nanosized image at a time of about 150x150nm.

2. The tip and the sample can be damaged during detection.
3. It has a limited magnification range.

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