1

Changes introduced in quantum

confined charge carriers on
introduction of limited periodic lattice
potentials

Abstract
Nanoscience and nanotechnology has become the format of material science.
The size effect is the backbone of nanoscience, that is, as the grain size decreases,
material characteristics vary. Today we know, this is a manifestation of quantum
behavior, best understood by the particle in a box examples from text books. This
project investigates what would happen if the charge carriers inside a nano – grain
experiences the periodic potential of the lattice? To ensure the charge carriers will
experience the lattice (with barrier height V0 ) we demand that their energy satisfy the
condition E ˂ V0. The lack of periodicity extending to infinity rules out the
application of Bloch theorem and hence Kronig penney model.
 2

Introduction

1.1 Introduction to Nanotechnology

In the past, Nanotechnology was not present but nowadays there has been a lot
of progress in the field of nanotechnology. In today’s era, we notice the increasing
trend of research in the field of nanotechnology and nanoscience. Nanotechnology is
the future miniaturization technology with a lot of variety of potential applications.
Nanotechnology is basically the technology and science of small things that is, the
things which have size less than 100 nm. Nanotechnology unites solid state physics,
material science, Chemistry, engineering in electrical and chemical field. The new
thing about nanotechnology is that now we can at least understand and control the
properties and structure to make new materials and devices. It has been discovered
that the materials at smaller scale that is, thin – films, small particles etc may have
different properties at large dimension of the same material. Mainly the
nanotechnology consists of three important things which are as:

1) Unique properties due to small size

2) Small size, which is measured in nanometer of 100s or less
3) Control of composition and the structure on the nm scale

1.2 Quantum Confinement Effect

Quantum confinement effect plays a major role in semiconductor

nanostructures to explore the practical applications. Quantum confinement is related
with the nanostructure materials as the bulk materials mostly exhibit electronic
spectra and continuous absorption. The motion becomes highly quantized and
confined for the bound charge carriers (electrons and holes) and this spatial
confinement is called the quantum confinement effect. The quantum confinement
effect is investigated very deeply regarding the semiconductor nanomaterials. In
semiconductor materials, the two charge carriers (electrons and holes) in the allowed
energies are separated by the gap known as band gap or simply we can say that it is a
range of energy in a solid where no electron state exists.
 3

Quantum confinement can be observed when the diameter of the material is of same
magnitude as of de Broglie wavelength of an electron wave function. The particle
behaves as if it is free when the dimensions of the confinement are large as compared
with the wavelength of the particle. At this state, the band gap stays at its original
energy due to the continuous energy state. As we decrease the dimension of the
confinement at a certain limit say in nano scale, the energy spectrum becomes
discrete. As a result of this, the band gap becomes dependent on size. This results in
the phenomenon which is known as “Blue Shift” as the particle size decreases.

So, the term “Blue Shift” in nano particle physics says that as the size of the particle
decreases the Energy Band Gap increases and with increase in the size of particle
there is a decrease in the Energy Band Gap. The blue shift is observed in the optical
absorption spectra due to band gap increment of semiconductor nanostructure. The
Blue Shift shows that energy is inversely proportional to the distance. The band gap
can be calculated by Brus Equation that is,

E = Eg(bulk) + ћ2/8r2(1/me* + 1/mh*)

Where, r is the radius of quantum dot (small particles, whose electrical and optical
properties are different from the larger one) and me* and mh* are the effective masses
of electron and hole respectively. The Brus equation is useful in describing the
emission energy of quantum dot in terms of energy band gap. The length of the box is
actually the size of the quantum dots. So, for one dimensional particle, we consider
the energy of a “Particle in a box”, to describe the energy band gap. In quantum
dots, as the size varies the energy changes because the exciton in the quantum dots
behaves like a “particle in a box”.

Let us have a look over the problem of particle in a box.

1.3 Particle in a One - Dimensional Box

Figure (i) shows that a particle is trapped in a box of length (L). The particle in
a box is a problem in which a particle is trapped in a box with infinitely hard
walls. In it, we assume the potential energy to be zero inside the box. Let us
consider a particle of mass (m) bouncing back and forth in between the box in
one dimensional box. And the movement of the particle is restricted travelling
 4

along the x- axis between x = 0 and x = L by two infinitely hard walls, so that
the particle cannot penetrate the hard walls. The total energy remains constant
as the particle does not lose energy when collide with hard walls.

Figure (i) – Particle in a one dimension box

Within the box the Schrodinger equation is written as:

(-ħ2/2m𝑑2Ѱ/dx2 Ѱ + V0Ѱ = EѰ

The above equation can be converted to a S.H.M. equation by rearrangement and

simple substitution as follows

𝑑2Ѱ/dx2 = − (2m/ħ2) (E – V0) Ѱ

𝑑2Ѱ/dx2 = - ω22Ѱ

Where,

ω22= (2m/ħ2) (E – V0) (1)

The solution of this equation is well known

Ѱ(x) = Asin(ω2x) + Bcos(ω2x) (2)

For the case that V0 = 0,

 5

ω12 = (2m/ħ2) E (3)

The solution of this equation is well known

Ѱ(x) = Asin(ω1x) + Bcos(ω1x) (4)

The solutions are subjected to the boundary conditions, Ѱ(x=0) = Ѱ(x=L) = 0, we get

Ѱ(x) = Asin(nпx/L) (5)

Here, A = √2/L

The normalized wave function of the particle is as follows:

Ѱ n (x) = (√2/L) sin (nпx/L) (6)

Where, n = 1, 2, 3 and so on

The Energy Eigen values for a quantum confined particle in a box with V0 = 0 is
given as

En = (n2п2ħ2/2m) (1/L2) (7)

That is,

E ∝ 1/L2 (8)

The problem of particle in a box, showed that the energy is inversely proportional to
the square of the length of the box.

The solid, whether it is in the form of bulk, polycrystalline or nano-crystalline we see

that the lattice is always present in it. The bulk and polycrystalline structure is
explained by the Kronig Penney model. And solving the Kronig Penney model means,
Bloch theorem holds and hence infinite lattice is there. We know that angstroms ˂
micrometer ˂ centimeter. So, in terms of nano – particles we can say that (a + b) can
be given small values in angstroms and the value of L ranges from 0 – 10 angstroms.

In one of the A. K. Ghatak research paper published in 1971 based on - Effect of size
on the Band Structure of a Finite One – Dimensional Lattice he said that the
energy band structure of a finite linear lattice behaves as a bulk (N → ∞) when the
 6

number of atoms in the lattice is twenty or greater. His calculations showed that the
band gap decreases with the decreasing value of P.

Hence, we have to do some calculation in this model to find something which is

similar to the Bloch theorem. For this, we have considered the simplest problem of
particle in a box having energy less than the potential barrier with periodic lattice
being taken into the consideration. The kronig penney model can be solved with the
help of WKB ( Wentzel – Kramers –Brillouin) approximation but no one has solved it
considering a periodic lattice potential in a box.
 7

2. SECTION – A

Particle in a Box with Rectangular Potential

Figure (ii) shows that a particle is confined in a box of length L with lattice present in
it. The region I and III have their potential energies to be zero while the region II
have energy V0. The value of the energy is taken to be less than the height of potential
barrier that is E ˂ V0. The position of the barrier is between x = a and x = a + b. the
potential barrier divides the space into three regions.

Figure (ii) - Particle in a box with rectangular potential

So,

Calculations:

The Schrodinger equation for the region I is as follows:

d2ѰI / dx2 + (2mE/ħ2) ѰI = 0

The Schrodinger equation for the region III is as follows:

d2ѰIII / dx2 + (2mE/ħ2) ѰIII = 0

 8

The Schrodinger equation for region II is as follows:

d2ѰII / dx2 - (2m/ħ2)(V0-E)ѰII = 0

The solutions of the above equations are as follows:

Ѱ1(x) = Asin(ω1x) + Bcos(ω1x)

Ѱ2(x) = Ceαx + De-αx

Ѱ3(x) = Fsin(ω1x) + Gcos(ω1x)

The solutions are subjected to the Boundary Conditions in which the wave functions
and their derivatives must be continuous everywhere as follows:

At x = 0,

The wave function Ѱ1 (x) comes out to be as:

Ѱ1(x = 0) = B = 0

Ѱ1(x) = Asin(ω1x) (1.1)

At x = a , Ѱ1 = Ѱ2

Asin(ω1a) = Ceαa + De-αa (1.2)

At x = a , Ѱ1 ' = Ѱ 2 '

Aω1cos(ω1a) = αCeαa - αDe-αa (1.3)

At x = a + b , Ѱ2 = Ѱ3

Ceα(a + b) + De-α(a + b) = Fsin[ω1(a + b)] + Gcos[ω1(a + b)] (1.4)

At x = a + b , Ѱ2 ' = Ѱ3 '

αCeα(a + b) - αDe-α(a + b) = ω1Fcos[ω1(a + b)] –ω1 Gsin[ω1(a + b)] (1.5)

At x = L ,

Ѱ3(x) = Fsin(ω1L) + Gcos(ω1L) = 0 (1.6)

 9

In equation (1.2), (1.3), (1.4) and (1.5) we put C = 0 as the particle in region II decays
exponentially.

So, our equation becomes as follows:

Ѱ1(x) = Asin(ω1x) (1.7)

Asin(ω1a) = De-αa (1.8)

ω1Acos(ω1a) = - αDe-αa (1.9)

De-α(a + b) = Fsin[ω1(a + b)] + Gcos[ω1(a + b)] (1.10)

- αDe-α(a + b) = ω1Fcos[(ω1(a + b)] –ω1 Gsin[ω1(a + b)] (1.11)

Fsin(ω1L) + Gcos(ω1L) = 0
(1.12)

Now take the values of (De-αa) and (-αDe-αa ) from equation (1.8) and (1.9)
respectively and then put them in equation (1.10) and (1.11) respectively.

We get the equations as follows:

Asinω1ae-αb = Fsin[ω1(a + b)] + Gcos[ω1(a + b)] (1.13)

ω1 Acosω1ae-αb = ω1Fcos[ω1(a + b)] –ω1 Gsin[ω1(a + b)] (1.14)

Fsin(ω1L) + Gcos(ω1L) = 0
(1.15)

The above equations are now arranged in 3 x 3 matrix, and on solving the determinant
of the matrix so formed we get the solution as:

sinω1ae-αb -sinω1(a+b) -cos ω1(a+b)

ω1cosω1ae-αb - ω1cosω1(a+b) ω1sinω1(a+b) = 0

0 sin ω1L cosω1L

 10

= - ω1sinω1ae-αb[cos(ω1L)cosω1(a+b) + sin(ω1L)sinω1(a+b)] + sinω1(a+b)ω1

cos(ω1L)cos(ω1a)e-αb - cosω1(a +b)ω1sin(ω1L)cosω1ae-αb =0 (1.16)

=-ω1sinω1ae-αbcosω[L–(a+b)]-ω1cosω1ae-αb[sin(ω1L)cosω1(a+b) - cos(ω1L)sinω1(a+b)]
=0 (1.17)

= - ω1 sin(ω1a)e-αbcos{ω1[L – ( a + b) ]} - ω1cosω1ae-αbsin{ω1[L – (a + b)]} = 0

(1.18)

= - ω1e-αbsin{ω1[L-a-b+a]} = 0

= - ω1e-αbsinω1[L-b] = 0

As, ω1 ≠ 0 and also, e-αb ≠ 0

So, sin[ω1(L-b)] = 0

ω1(L-b) = nп

As we know, that the value of sin( π, 2π, 3π, 4π and so on….) = 0

Now, squaring on both sides, we get

ω12(L-b)2 = n2 п2

2mE/ħ2(L- b)2 = n2 п2

E = n2 п2 ħ2/2m(L-b)2

From equation (1.8) and (1.9), we get the values of energy as:

E =0

E = V0 - ħ2/2ma2

Hence, the value of energy band-gap is given by

E = n2 п2 ħ2/2m(L-b)2 (1.19)

2a + b = L

2a = L – b

So, E = n2 п2 ħ2/8ma2
 11

Now, further solving the same with the help of taking into consideration the problem
of two rectangular potential barrier confined in a box.

SECTION – B

Particle in a box with two rectangular potential

Figure (iii) shows that the particle is confined within a box having length (L) with
lattice present inside it. Here, we have considered two rectangular potential barriers.
For the regions I, III and V the potential energies are taken to be zero and for the
regions II and IV the potential energy is zero. And the value of the energy is taken to
be less than the height of the potential barrier that is E ˂ V0. The position of the
barrier is between x = a , x= a +b and between x = 2a + b, x = 2a + 2b. The potential
barrier divides the space into five regions.

Figure (iii) – Particle in a box with two rectangular potential

So,

Calculations:
 12

The Schrodinger equation for the region I is as follows:

d2ѰI / dx2 + (2mE/ħ2) ѰI = 0

The Schrodinger equation for the region III is as follows

d2ѰIII / dx2 + (2mE/ħ2) ѰIII = 0

The Schrodinger equation for the region V is as follows:

d2ѰV / dx2 + (2mE/ħ2) ѰIII = 0

The Schrodinger equation for the region II is as follows:

d2ѰII / dx2 - (2m/ħ2)(V0-E)ѰII = 0

The Schrodinger equation for the region IV is as follows:

d2ѰIV / dx2 - (2m/ħ2)(V0-E)ѰIV = 0

The solutions of the above equation are as follows:

ѰI(x) = Asin(ω1x) + Bcos(ω1x)

ѰII(x) = Ceαx + De-αx

Ѱ1II(x) = Fsin(ω1x) + Gcos(ω1x)

ѰIV(x) = Heαx + Ie-αx

ѰV(x) = Jsin(ω1x) + Kcos(ω1x)

Now, the solutions are subjected to the Boundary Conditions in which the wave
functions and their derivatives must be continuous everywhere as follows:

At x = 0 ,

The wave function Ѱ1 comes out to be as

Ѱ1(x = 0) = B = 0

Ѱ1(x) = Asin(ω1x) (2.1)

At x = a , Ѱ1 = Ѱ2
 13

Asin(ω1a) = Ceαa + De-αa (2.2)

At x = a , Ѱ1 ' = Ѱ 2 '

Aω1cos(ω1a) = αCeαa - αDe-αa (2.3)

At x = a + b , Ѱ2 = Ѱ3

Ceα(a + b) + De-α(a + b) = Fsin[ω1(a + b)] + Gcos[ω1(a + b)] (2.4)

At x = a + b , Ѱ 2 ' = Ѱ3 '

αCeα(a + b) - αDe-α(a + b) = ω1Fcos[ω1(a + b)] –ω1 Gsin[ω1(a + b)] (2.5)

At x = 2a + b , Ѱ4 = Ѱ3

Fsin[ω1(2a + b)] + Gcos[ω1(2a + b)] = Heα(2a + b) + Ie-α(2a + b) (2.6)

At x = 2a + b , Ѱ4 ' = Ѱ3 '

ω1Fcos[ω1(2a + b)] - ω1Gsin[ω1(2a + b)] = αHeα(2a + b) - αIe-α(2a + b) (2.7)

At x = 2a + 2b , Ѱ4 = Ѱ5

Heα(2a +2 b) + Ie-α(2a +2b) = Jsin[ω1(2a + 2b)] +Kcos[ω1(2a + 2b)] (2.8)

At x = 2a + 2b , Ѱ4 ' = Ѱ 5 '

αHeα(2a + 2b) - αIe-α(2a + 2b) = ω1Jcos[ω1(2a + 2b)] - ω1Ksin[ω1(2a + 2b)] (2.9)

At x = L ,

Ѱ5 = Jsin(ω1L) +Kcos(ω1L) = 0 (2.10)

Now, taking C and H to be zero as the particle decays exponentially in the region II
and IV respectively.

So, the equation takes the form as follows:

Ѱ1(x) = Asin(ω1x) (2.11)

Asin(ω1a) = De-αa (2.12)

Aω1cos(ω1a) = - αDe-αa (2.13)

 14

De-α(a + b) = Fsin[ω1(a + b)] + Gcos[ω1(a + b)] (2.14)

- αDe-α(a + b) = ω1Fcos[ω1(a + b)] –ω1 Gsin[ω1(a + b)] (2.15)

Fsi[(ω1(2a + b)] + Gcos[ω1(2a + b)] = Ie-α(2a + b) (2.16)

ω1Fcos[ω1(2a + b)] - ω1Gsin[ω1(2a + b)] = - αIe-α(2a + b) (2.17)

Ie-α(2a +2b) = Jsin[ω1(2a + 2b)] +Kcos[ω1(2a + 2b)] (2.18)

- αIe-α(2a + 2b) = ω1Jcos[ω1(2a + 2b)] - ω1Ksin[ω1(2a + 2b)] (2.19)

Ѱ5 = Jsin(ω1L) +Kcos(ω1L) = 0 (2.20)

After removing the component of C and H from the above equations, we get the
following above equations as:

Ѱ1(x) = Asin(ω1x)

Asin(ω1a)e-αb = Fsin[ω1(a + b)] + Gcos[ω1(a + b)]

Aω1cos(ω1a)e-αb = ω1Fcos[ω1(a + b)] - ω1Gcos[ω1(a + b)]

e-αb Fsin[ω1(2a + b)] + Gcos[ω1(2a + b)] = Jsin[ω1(2a + 2b)] +Kcos[ω1(2a + 2b)]

e-αbω1Fcos[ω1(2a + b)] - ω1Gsin[ω1(2a + b)] = ω1Jcos[ω1(2a + 2b)] - ω1Ksin[ω1(2a +

2b)]

Jsin(ω1L) +Kcos(ω1L) = 0

So, after arranging the above equations in the form of 5 x 5 matrix form and then
solving its determinant with the help of a software called mathematica.

-sinω1ae-αb sinω1(a+b) cos ω1(a+b) 0 0

-ω1cosω1ae-αb ω1cosω1(a+b) -ω1sinω1(a+b) 0 0

0 -e-αbsin[ω1(2a+b)] -cos[ω1(2a+b)] sin[ω1(2a+2b)] cos[ω1(2a+2b)]

0 -e-αbω1cos[ω1(2a+b)] ω1sin[ω1(2a+b)] ω1cos[ω1(2a+2b)] -ω1cos[ω1(2a+2b)]

0 0 0 sin(ω1L) cos(ω1L)
 15

We get the value of E as follows:

E = n2п2ħ2/ 2m (L – 2b) 2

So, the energy band gap value is

E = n2п2ħ2/ 2m (L – 2b) 2 (2.21)

 16

SECTION – C

Particle in a Box with N Rectangular Potential Barriers

Similarly, if we take the case of particle in a box with N Potential Barrier inside the
box as shown in the figure (iv) then,

With the help of the above similar process of solving the problem of potential barriers
using Schrodinger equation and then arranging the equations in the form of matrix
and then taking the determinant of the equations and solving the matrix with the help
of Mathematica software.

Figure (i v)

So, finally the value of Energy Band Gap comes out to be as follows:

E = n2п2ħ2/ 2m (L – N b) 2 (2.21)

Here, the value of N = L – a / a + b

N = is the number of rectangular potential barrier

 17

L = length of the box

a = width of the valley

b = width of the barrier

Figure (v)

The value of N comes out to be so, as we see in the figure (v), if we take (N + 1)
number of a and N number of b then we can write this in the form of equation which
is as follows:

(N + 1) a + (N) b = L

Na + a + Nb = L

N(a + b) = L

N = L –a / a + b

Hence, we get the value of N

Now, put the value of N in equation (2.21) we get the Energy Band Gap value as:

E = n2π2ћ2 / 2m[L- (L-a / a + b) b]2

 18

On further rearranging the above equation in more simpler form we get the value of
energy band gap as follows:

E = n2π2ћ2 / 2m[La + Lb – Lb +ab/ a +b ]2

E = n2π2ћ2 / 2m[ a ( L + b ) / a +b ]2 (2.22)

Equation (2.22) shows that the two variables (a) and (L) are dependent on each other.

In one of the research paper based on the topic – (Grain Size and Lattice Parameter’s
Influence on Band Gap of SnS Thin Nano – crystalline films) there the band gap
depends on the two variables which are grain size and lattice’s unit cell volume. And
it was found that the two variables are acting independently of each other and hence
they can be separable. However, theoretically it shows that the variation of band gap
can be studied only as a function of lattice parameters. But in our research we showed
that the two variables a and L depend on each other and are not independent of each
other.

3. METHODOLOGY

This project work is carried out by using the following methods:

 The literature survey of the topic has been done.

For this, first of all one research paper based on the topic – Grain size and
lattice parameter’s influence on band gap of SnS Thin Nano – crystalline films
was studied thoroughly in order to know what exactly is to be found out in the
project.

 The problem of particle in a box has been taken into account by confining the
particle in a box of length (L) with lattice being present inside it, we solved the
problem using Schrodinger equations and applying boundary conditions in
order to find out the value of energy band gap.
 The kronig penney model has also been taken into consideration to study the
Bloch theorem.
 19

 The Schrodinger equations have been taken into account in order to get the
solutions of the regions in which the particle is confined.
 The Mathematica software has been used in order to solve the determinant of
high order matrix for example 5 x 5 matrix form or 9 x9 matrix form cannot be
calculated very easily. So, in order to make our calculations easier and faster
this software has been used.
 Various mathematical formulas and properties have been used in order to
make our calculations easier.
 For plotting the graph between energy and the length of the box (L) and
between energy and (N) the Microsoft excel sheet has been used in the project
in order to get the fine values of the graph.

4. APPLICATIONS

Here are some of the applications based on the project:

 The particle in a box for its simple mathematical calculation is used for
finding out the approximate solutions for more complex physical systems for
which the particle is trapped in a narrow region of low potential between two
or more higher potential barriers.
 The quantum well systems plays a very crucial role in optoelectronics and are
also useful in the devices such as the quantum well infrared photo detector, the
quantum well lasers and the quantum – confined stark effect modulator.
 The particle in a box is also used in kronig penney model to model a lattice.
 20

5. CONCLUSION

Discussions and Result

The graph curves of graph (1) and graph (2) comes out by putting the different data
into the energy band gap equation that is, equation (2.21) such as by putting the
different values of N from 1 to 10 and putting values of other variables also such as of
L, a, b, mass of electron, value of planck’s constant.

2.00E-01
1.80E-01
1.60E-01
1.40E-01
1.20E-01
1.00E-01
8.00E-02
6.00E-02
4.00E-02
2.00E-02
0.00E+00
0 1 2 3 4 5 6

GRAPH – 1

The graph (1) is plotted between Energy (E) and (n) which shows the presence of
energy band gap in the figure. The following data shows that the energy band gap
goes on increasing. Here, in this graph b = 0 in Series 1(blue dotted) as the value of N
= 10 and b = 1.01 x 10-11m in Series 2(red dotted) as the value of N = 9.

The value of n = √n12 + n22 + n32.

 21

We get two conclusions from this graph:

(i) If we increase the value of (n) the bands appear.

(ii) And if we go on increasing the value of (b) the band gap widens.

The graph (2) is plotted between energy (E) and (N) as shown by red(series 2) and
blue(series 1) dotted curves. Let us assume that the blue dotted (series 1) is L1 and the
red dotted (series 2) to be L2. Then according to the graph, L1 > L2. From this graph,
we conclude that as the value of L decreases the band gap increases.

1.20E+00

1.00E+00

8.00E-01

6.00E-01
Power ()
4.00E-01 Power ()

2.00E-01
0.6061x-1.508
y = 1.0088x
R² = 0.9934
0.9933
0.00E+00
0 2 4 6 8 10 12

GRAPH - 2

From the above results we conclude that as we go on inserting more and more
periodic lattice potential into the box having length (L), the width of the barrier that
is, (b) widens and because of its widening the potential appears to be a straight line
and hence it acts as a particle in a box.
 22

6. REFERENCES
From Books:

1) Concepts of Modern Physics, sixth edition, Tata McGraw Hill Education

Private Limited
2) Solid State Physics, by R.K.PURI and V.K.BABBAR
3) Solid State Physics, S.O. PILLAI Fifth Edition (2002)
4) Introduction To Solid State Physics, Seventh Edition, by Charles Kittel
5) Introduction to Nanotechnology, by Charles P. Poole Jr. and Frank J. Owens

From Research Articles:

6) Effect of Size on the Band Structure of a Finite One – Dimensional lattice, by

A.K.GHATAK, S.BALA, and M.S. SODHA (1971)
7) Grain Size and Lattice Parameter’s Influence on Band Gap of SnS Thin Nano-
crystalline Films, by P. Arun, Yashika Gupta, A.A. Naudi, M.V.Walz, E.A.
Albanesi