From classical mechanics the total energy of the system is described by the Hamiltonian

equation (H) which is the sum of the kinetic (T) and potential energies (V).

particle classical V
m
p
H
m
p
T
V T H
+ =
=
+ =
2
2
2
2


Under quantum mechanics this would turn into quantum mechanical Hamiltonian
operator by letting;

operator n Hamiltonia QM V
m
H
p
i
p
+


2
2
2 2 2
2
h
h
h


Also under quantum mechanics, we can represent a particle as a wave function . Such a
wave function must be normalized. And we can use the Hamiltonian operator H to
provide the Schrodingers equation which we can use to solve for the energies of the
particle.

Equation s r Schrodinge V
m
H
dV
ol
'
2
1
2
2
*
=
|
|

\
|
+
=
=

h


In setting up the wave functions of an electron within a crystal, there are two schemes.
We can use the fixed boundaries (like within infinite barriers) or used periodic
boundaries (assuming that the crystal consisting of potentials or barriers setup by
periodic ions in the lattice).

We will illustrate first the solutions for fixed boundaries and then show the solution for
the periodic boundaries.

Fixed boundary conditions:

Consider a free electron trapped in an infinite barrier of finite width L, since the electron
is practically trapped within such potential structure, we can let the electron wave
function to be similar to that of a standing wave. We assume that the electron wave
function (x) is a periodic function within a one-dimensional infinite potential barrier
and zero outside the barriers;
( )
) , ...( 3 , 2 , 1 sin ) (
) , ...( 3 , 2 , 1 ; sin 0 ) (
0 ) 0 sin( 0 0 ) 0 (
: ) (
) sin( ) (
zero not only positive n x
L
n
A x
zero not only positive n
L
n
k L k A L x
k A x
fixed conditions Boundary
kx A x
= |

\
|
=
= = = = =
= = = =
=

A proper wave function must be normalized, that is integrate the density function over
the region of interest (within the infinite well);

( ) ( ) ( )
[ ]
( )
) , ...( 3 , 2 , 1 sin
2
) (
2
2
0
2 4 2
1
) 0 sin( ) 4 sin(
2 4 2
) 0
2
2 sin( )
2
2 sin(
4
] 0 [
2
1
) 2 sin(
1
4 2
2 cos
2 2 2
2 cos 1
1
2
2 cos 1
sin
sin sin sin ) ( ) ( 1
2 2 2
2 2 2 2
0
2 2
0
2
0
2
0
2
2
0
2 2
0 0
*
zero not only positive n x
L
n L
x
L
A
L A
n
L A L A
n
n
L A L A
L
n
L
L
n
n
L A
L
A
kx
k
A
x
A
x d kx
A
dx
A
dx
kx
A
dx kx A dx kx A kx A dx x x
L
L L L
L L L
= |

\
|
=
=
= |

\
|
=

\
|
=
(

\
|
=
|

\
|
= =
|

\
|
=
|

\
|
=
= = =

We solve for the energies of the trapped electrons from the Hamiltonian operator and
using the Schrodingers equation;
) , ...( 3 , 2 , 1
2m
) ( ) (
2m
) ( sin ) (
cos ) (
) ( ) (
2m
sin ) (
1
0
'
2
2
2
2
2
2
2 2
2
2
2
2 2
2
2
2
2
2
2
2
2
2
zero not only positive n
L
n
x x
L
n
x
L
n
x
L
n
L
n
A x
x
x
L
n
L
n
A x
x
x x
x
x
L
n
A x
D
x x
electron free V
equation s r Schrodinge V
m
H
operator n Hamiltonia QM V
m
H
i i
e
e
=
|

\
|
=
= |

\
|
+

\
|
=
|

\
|
|

\
|
=

\
|
|

\
|
=

=
|
|

\
|

\
|
=

=
=
=
|
|

\
|
+
=
+ =

h
h
h
h
h


Here we see that the creation of discrete energy levels indexed by the primary quantum
number n. For fixed boundaries, we can solve for the energy differences of successive
levels as follows;

boundaries fixed n
L
n
n n
L
n
L
n

|
|

\
|
=
=

|
|

\
|
=
|
|

\
|
=
2
2m
1
2
2m 2m
) (
2
2 2
2
2 2
2
2
2 2

h
h h

Periodic boundary conditions:

For the fixed boundaries, we assumed the electron wave function to be similar to a
standing wave. For periodic boundaries, we assume a propagating plane wave as an
exponential function and similarly normalized. Note the change in the normalization
constant A and the wave number k in comparison to the solution for the fixed boundaries.
... 3 , 2 , 1 , 0
2
exp
1
) (
... 3 , 2 , 1 , 0 ;
2
) exp( 1
) exp( ) exp(
1
]) [ exp(
1
) exp(
1
) ( ) (
: ) (
) exp(
1
) (
1
) exp( ) exp( ) ( ) ( 1
) exp( ) (
2
0 0
*
= |

\
|
=
= = =
= + = + =
=
= = = =
=

n
L
nx
i
L
x
n n
L
k ikL
ikL ikx
L
L x ik
L
ikx
L
L x x
periodic condition Boundary
ikx
L
x
L
A L A dx ikx A ikx A dx x x
ikx A x
L L

Assuming the Hamiltonian of a free electron and solving the Schrodingers equation for
the electron energies.
... 3 , 2 , 1 , 0
2
2m
) ( ) (
2
2m
) ( ) (
2m
) (
2 2
exp
1 2
) (
2
exp
1 2
) (
2
exp
1
) (
2
2
2
2
2
2 2
2 2
2
2
=
|

\
|
=
= |

\
|
+ =
|
|

\
|

\
|
=
|

\
|
|

\
|
=

\
|
|

\
|
=

\
|
=
n
L
n
x x
L
n
x x
x
x
L
n
L
nx
i
L L
n
x
x
L
nx
i
L L
n
i x
x
L
nx
i
L
x

h
h h


Again taking note of the change in the energy levels, we now examine the energy spacing
between successive energy levels;

boundaries periodic n
L
n
n n
L
n
L
n

|
|

\
|
=
=

|
|

\
|
=
|
|

\
|
= =
2
m
2
1
2
m
2
m
2
) (
2
2 2
2
2 2
2
2
2 2

h
h
h


Since we are solving practically the same problem (free-electron) using two distinct
approaches, we can assert that the Fermi level of this electron system to be the same.
2
2
4
4
m
2
... 3 , 2 , 1 , 0
2m
... 3 , 2 , 1
:
) (
) (
) ( ) (
2
) ( ) 0 (
2
) ( ) 0 (
) ( ) (
2
) ( ) 0 (
2
) (
2
2 2
) (
) (
2
) ( ) 0 (
2
) (
2
2 2
) (
) (
f
F p
F
f
F
p
F
f
F
p
F
p
F
f
F
p
F
p
F
p
F
p
F
f
F
f
F
f
F
f
F
n
n
n n
n n
n n
L
n
boundaries periodic
n n
L
n
boundaries fixed
=
=
=
=
=
|
|

\
|
=
=
=
|
|

\
|
=
+ + + =

h
h


Here we see for each boundary scheme, we get different quantum numbers with the same
Fermi energy. Thus we need to see the energy spacing from both boundaries.
We look at the energy spacing for the periodic boundaries as compared to those from
fixed boundaries.

) ( ) (
) (
) ( ) ( ) ( ) (
2
2 2
) (
) ( ) ( ) (
2
2 2
) (
) (
) (
2
2 2
) (
4
2
8 8 2
m
2
2 2
2m
2 2m
f o
f
o p o p p
f o f f
f
p o
n
n
n n
L
n n
L
n
n
L

=
|
|

\
|
= =
|
|

\
|
=
=
|
|

\
|
=
= =
h
h
h


We next examine the number of states at some energy (given by n) to show the total
number of states. For fixed boundaries, n was found to be positive integer only, thus the
total number of states at some n would only be 1/8 the volume of sphere with radius n.
While those for the periodic boundaries, the total number of states is the whole sphere.

) (
) (
) ( ) (
3
) (
3
) (
3
) (
3
) (
3
) (
3
) (
3
) (
2
2 8
3
4
6
1
:
3
4
:
6
1
3
4
8
1
:
p
f
p f p f
p f
p
f f
n
n
n n n n
n n
states of number total Equal
n states of number total boundaries periodic
n n states of number total boundaries fixed
= = =
=
=
= |

\
|
=

From the total number of states, we determine the degeneracy as the number of states at
specific energy (defined by n). The degeneracy is the surface area of the sphere with
radius n.

( )
2
) (
2
) (
2
) (
2
) (
2
) (
2
4 4 :
2
1
4
8
1
:
f
f
p
f f
n
n
n degeneracy boundaries periodic
n n degeneracy boundaries fixed


=
|
|

\
|
= =
= =

Such variation in the energies depending on the applied conditions is very small. For
instance, the change in energy here is ~10
-17
eV and one needs a sample size of around
10
-7
cm to gain significant energy variation. Realistically, electrons within macroscopic
samples encounter collisions depending on the type of material (since the mean free path
of electrons is around ~100 lattice spacings).
In quantum mechanics, a free electron can be represented by a wave function (x).
For solids, it is important to determine the density of states of the charge carriers, say
electrons, since they affect the electronic properties of the material.


Let us consider a free electron confined in L within infinite barriers in one-dimension.
Leading towards the idea that ideal crystals are periodic, it is customary to test the wave
functions for periodicity. Here we chose a typical plane wave consisting of sine function.
( ) ( )
) (
sin
sin cos cos sin sin
sin cos cos sin ) sin(
sin sin
] [ sin ) (
sin ) (
x
x
L
n
A
n x
L
n
n x
L
n
A n x
L
n
A
n x
L
n
A L
L
n
x
L
n
A
L x
L
n
A L x
x
L
n
A x
n
n
n
=
|

\
|
=
|

\
|
+ |

\
|
= |

\
|
+ =
+ = +
|

\
|
+ = |

\
|
+ =
|

\
|
+ = +
|

\
|
=

We need to solve for the Schrodinger equation to determine the energies of the electron.
This will then be used to determine the density of states. We first take the first and second
derivatives of the electron wave function with respect to position.
) ( sin ) (
cos ) (
) ( ) (
2
2 2
2
2
2
2 2
x
L
n
x
L
n
L
n
A x
x
x
L
n
L
n
A x
x
x x
x m
n n
n
n n n

\
|
=
|

\
|
|

\
|
=

\
|
|

\
|
=

=
|
|

\
|

h

Replacing the derivatives into the Schrodingers equation will provide us with the energy
values. Energies are typically written in terms of k rather than the arbitrarily chosen
confinement region L.
L
n
k
k
L
n
x x
L
n
x x
x
k
n
n n k
n n n

= =
|

\
|
=
= |

\
|
+
=
|
|

\
|

;
2m
2m
) ( ) (
2m
) ( ) (
2m
*
2 2
2
2
2
2
2
2 2
h
h
h
h


We can see that the energies are parabolic with respect to k. Within a material the
electron experiences a force field generated by the ions in the crystal which in effect
reduces the effective mass of the electron (m*). Such effective mass can vary with the
material, thus the energy band diagram also changes.


In an N-electron system, not all the energies are occupied and the highest occupied
energy level is known as the Fermi level. Following the energy equation above, the
energy states up to the Fermi energy level is filled up by N-electrons. A factor of 2 was
introduced to accommodate the electron-spins.


2
2
2
2
2 2
2
2
2 2
2
2
2
2 2
2
2
2m 2 2m
2
2m 2m
h
h
h h
h h
F
F
F
F
F
F
F
F F
F
m L
k
L
N
m
L
N
k
k
L
N
n N
k
L
n

\
|
= |

\
|
=
= |

\
|
=
=
|

\
|
=
=
= |

\
|
=




k
m*

k
y

k
x

We rearrange the Fermi energy equation to obtain an expression of the total number of
electrons in terms of energy () or wave-vector (k). This will facilitate ease in
computation of the density of state.

Density of state g() is the number of electrons states at some energy, say in this case the
Fermi energy. From the rearranged equations, we take the derivatives to determine the
number (or density) of states at the Fermi energy. Here we see that for a one-dimensional
N-electron system, the density of state is proportional to inverse square root of the
energy level. This is typical to a free electron system in one-dimension.

( )
2 / 1
2 / 1
2
2 / 1
2 / 1
2
2 / 1
2
2 / 1
2
2 / 1
2 2
2
) (
2
2
2
2 ) (
2 2
2
2 2 2
) (

\
|
=
|

\
|
=
(

|
|

\
|

\
|
=
=
|

\
|
=
|
|

\
|
|

\
|
=
|
|

\
|
= =
|
|

\
|
=
= =
F F
F
F
F
F
F
m L
g
m L m L
g
L
k
L
dk
d
dk
dN
m
d
d m m
d
d
d
dk
d
dk
dk
dN
d
dN
g

h
h h
h h h



We can now extend this to cover three-dimensional electron systems, wherein the
electrons are still confined in L within 3-axes infinite barriers. Just like previously shown,
we test the electron wave function for periodicity. Then solve for the electron energies
using the Schrodingers equation. This will be followed by showing an expression of the
Fermi energy level at a fixed number of electrons. Finally the density of state is obtained
for a three-dimensional electron system.

The electron wave function may be written in terms of the confinement region L or in
terms of the wave number k; with all their necessary vector components.

=
+ + = + + =
|
|

\
|
|
|

\
|
|
|

\
|
=
z y x
z y x
z y x z y x
z y x
z y x
z
z
y
y
x
x
k
L
n
L L
k k k
k k k k and k z j y i x r where
z
L
n
y
L
n
x
L
n
A r
, ,
, ,
, , , ,
2
..., ,
4
,
2
, 0 , ,

sin sin sin ) (

v v v
v v v v
v


Alternatively, we may write the electron wave function as an exponential function in
terms of the position (r) and wave (k) vectors. We will use the exponential form here to
facilitate ease of computation. A wave function consisting of three mutually independent
variables maybe solved separately. Here we show the periodicity of the x-component of
the wave function. Similar results are also obtained for the rest of the axes.
( ) ) ( ) exp(
2
exp 2 exp
2
exp
2
exp
2
exp ] [
2
exp
]) [ exp( ]) [ exp( ) (
) ( ) ( ) ( ) exp( ) exp( ) exp(
]) [ ] [ exp( ) exp( ) (
x x ik x
L
n
i n i x
L
n
i
L
L
n
i x
L
n
i L x
L
n
i
L x ik L x ik L x
z y x A z ik y ik x ik A
z y x k k k i A r k i A r
kx x
x
x
x
x
x
x
x
x
x
x
x
x
x
x x x x x kx
kz ky kx z y x
z y x k
= =
|
|

\
|
=
|
|

\
|
=
|
|

\
|
|
|

\
|
=
|
|

\
|
+ =
+ = + = +
= =
+ + + + = =

v
v



We now solve for the electron energies using the Schrodingers equation. Again taking
advantage of the property of a wave function consisting of mutually independent
variables, we can solve each component separately to obtain the energy contributions
from each axis. Here we show on the derivatives for the x-axis. Similar results can be
obtained from the remaining axes.
( ) ( )
( )
( )
2
2
2
2
2
2
2
2 2
2 2 2
2
2
2
2
2
2
2
2 2
2m 2m
) ( ) (
2m
) ( ) (
2m
) ( exp ) (
) ( exp exp ) (
) ( ) (
2m
|
|

\
|
= =
=
=
|
|

\
|

= =

= =

=
|
|

\
|

x
x
x nx
kx nx kx x
kx nx kx
kx x x x kx
kx x x x x kx
k k k
L
n
k
x x k
x x
x
x k x ik A k i x
x
x ik x ik A ik x ik
x
A x
x
r r
z y x

h h
h
h
h


The result from the y-axis and z-axis are given below. From total electron energies is
computed by substituting the wave vector k. Observe that in three dimensions, there is a
primary quantum number (n) for energy associated for each axis. A more general solution
is provided by supposing that the effective mass (m*) is anisotropic (varying with
direction). We can see that the electron energies is spherical in k-space for isotropic
effective mass and becomes ellipsoidal when the effective mass becomes anisotropic.

( )
*
Z
2 2
*
y
2 2
*
x
2 2
2 2 2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2m 2m 2m
2m 2m
2m
;
2m
;
2m
2m 2m
2m 2m
z
y
x
k
z y x k
z nz y ny x nx
z
z
z nz
y
y
y ny
k
k
k
k k k k
k k k
L
n
k
L
n
k
h
h
h
h h
h h h
h h
h h
+ + =
+ + = =
= = =
|
|

\
|
= =
|
|

\
|
= =

For an N-electron system, the highest occupied energy level is known as Fermi level.
This is represented as a sphere in k-space (assuming effective mass isotropy). The radius
of such sphere is denoted as k
F
. The total number of energy levels is n
F
and each level
occupied by 2 electrons (due to spin).

( )
( )
3 / 2
3
2 2
2
3 / 1
3
2
3
2
3
3
3 3 3
3
2
2
3
2
2 3
3 / 8 3
4
2
2
3 4
2
2
2
|
|

\
|
=
=
|
|

\
|
=
=

= =
= = =
N
L m
m
N
L
k
k
L
k
L L
k
volume reciprocal
sphere Fermi of vol
n and n N and k
m
F
F
F
F F
F
F
F F F F

h
h
h


k
x
k
y
k
z


m
x
*
m
y
*
m
z
*
k
x
k
y
k
z

Just like previously shown, we obtain the density of state from the expression of the total
number of electrons in terms of energy () or wave-vector (k). Here the show that the
density of state for N-electron system in 3-dimensions is proportional to square-root of
energy.

( )
2 / 1
2 / 3
2 2
3
2 / 1
2 / 3
2 2
3 2 / 1
2
2
2
3
2
2
2
3
2
2
2 2
3
2
2
3
3
2
3
2 / 1
2
2 / 1
2 2
2
2
) (
2
2 2
2 2
) (
2 2
3
3
3
3 3
2
2 2 2
) (
+
+

\
|
=
|

\
|
=
(

|
|

\
|

|
|

\
|
=
|
|

\
|
= |

\
|
|
|

\
|
=
|
|

\
|
=
|
|

\
|
=
|
|

\
|
= =
|
|

\
|
=
= =
F F
F
F
F F
F F F F
F
F
F
m L
g
m L m L m
g
L m m L
k
L
k
L
dk
d
dk
dN
m
d
d m m
d
d
d
dk
d
dk
dk
dN
d
dN
g

h
h h h
h h
h h h





Free electrons can be confined in space, reducing their degrees of freedom in motion.
Such confinement would lead to variation of the density of states g() depending on their
dimensionality. We start by writing the electron wave function and limit the electron
number to N (which also varies with dimensionality).


1. Show that the total number of electron N and the density of state can be written as;

2
3
) (
2
3 N
d
dN
g and
d
N
dN
= = =


2. For anisotropic effective masses with
*
2 2
*
2 2
*
2 2
2 2 2
z
z
y
y
x
x
k
m
k
m
k
m
k h
h
h
+ + = ;
show that the density of state can be expressed as;
2 / 1 * * *
3 2
3
2
) (
+
=
F z y x F
m m m
L
g

h


Free electrons that are not confined maybe considered as electrons within a bulk material.
While those confined in one-dimension behave like those electrons within a quantum
well. And those confined further to two-dimensions behave like they are within quantum
wires. And finally those confined in all three-dimensions behave like in quantum dots.

( )
materials bulk for S O D
m L
d
dN
g
L
k
N
volume reciprocal
space k of volume
N
k k k
m
k
m
k k k k
z ik y ik x ik A r k i A r
D
D
D
z y x
D
k
z y x
z y x
D
k
. .
2
2
) (
) / 2 (
3 / 4
2
2
2 2
) exp( ) exp( ) exp( ) exp( ) (
2 / 1
2 / 3
2
*
2
3
3
3
3
3
3
2 2 2
*
2
2
*
2
3
2 2 2 2
3

|
|

\
|
= =
=

=
+ + = =
+ + =
= =

h
h h
v
v



( )
wells quantum for S O D
L m m
L d
dN
g
m
L L
k
N
area reciprocal
space k of area
N
k k
m
k
m
k k k
y ik x ik A r k i A r
D
D
k
D
D
y x
D
k
y x
y x
D
k
. .
2
) / 2 (
2 ) (
2
) / 2 (
2
) / 2 (
2
2
2 2
) exp( ) exp( ) exp( ) (
2
2 *
2
*
2
2
2
2
*
2 2
2
2
2
2 2
*
2
2
*
2
2
2 2 2
2
=
|
|

\
|
= =
|
|

\
|
= =

=
+ = =
+ =
= =
h h
h
h h
v
v

1. Assuming that the number of electrons confined in two-dimensions is given by;
L
k
length reciprocal
space k in length
N
D
/ 2
2 2
1

= ;
show that the density of state in 1D is,
|
|

\
|
=
D
k
D
m L
g
1
2
*
1
1 2
2
) (

h
.

2. Assuming that the number of electrons confined in three-dimensions is given by;
d N
n
D

= ) ( 2
0
;
show that the density of state in 0D is,
) ( 2 ) (
0
n
D
d
dN
g

= = .

x

y

z

x

y

z

x

y

z

x

y

z

k
k
k

k
k
k

k
k
k

k
k
k



g()



g()



g()



g()

Once the density of state is well defined, we can compute for the carrier concentration (n)
and total number of density of states per unit volume (N) at some specified energy ().

Let us consider our carriers to be electrons which follow the Fermi-Dirac distribution
f
0
(). The Fermi-Dirac distribution can be reduced to the Maxwell-Boltzmann equation
under the assumption that the electron energy is much higher than thermal energy.

Dirac Fermi
T k
f
volume per states of density total d g N
ion concentrat carrier d f g n
B
F
o
o

+
|
|

\
|
=
=
=

1 exp
1
) (
) (
) ( ) (
0
0
0 0

Let us start by using 3D density of state g
3D
(). Here we consider a semiconductor, such
that we are looking for the carrier concentration at some energy () in the conduction
band.
|
|

\
|

|
|

\
|
=
|
|

\
|
(
(

|
|

\
|
=
|
|

\
|
=
(
(

|
|

\
|
=

|
|

\
|
=

T k
T k
m L
n
d
T k
m L
n
T k
m L
d
m L
N
m L
g
B
F C
B
D
C
B
F
C
D
C
B C
D
C
C
D
C
C
C

exp
2
exp ) (
2
2
2
) (
2
2
) (
2
2
) (
2 / 3
2
* 3
3
2 / 1
2 / 3
2
*
2
3
3
2 / 3
2
* 3
2 / 1
2 / 3
2
*
2
3
3
2 / 1
2 / 3
2
*
2
3
3
h
h
h h
h


Show that the Fermi-Dirac distribution can be approximated as;
Boltzmann Maxwell
T k
f
T k
B
F
B F

|
|

\
|

>>

exp ) (
0






Show that the carrier concentration (n) and the total density of states per volume (N)
for quantum wells, quantum wires, and quantum dots are as follows;

2
exp 2
: 0
2
exp
2
: 1
exp
: 2
0
0
2 / 1
2
*
1
2 / 1
2
*
1
2
*
2
2
*
2
=
|
|

\
|
=
|
|

\
|
=
|
|

\
|

|
|

\
|
=
=
|
|

\
|

|
|

\
|
=
D
C
B
F C D
C
B
D
C
B
F C
B
D
C
B
D
C
B
F C
B
D
C
N
T k
n
D
T k
m L
N
T k
T k
m L
n
D
T k
m
N
T k
T k
m
n
D

h
h
h
h