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Kronig–Penney Model - Free-Electron /

Quasifree-Electron Approximation: Density of
States Function

R. John Bosco Balaguru

Professor
School of Electrical & Electronics Engineering
SASTRA University

B. G. Jeyaprakash
Assistant Professor
School of Electrical & Electronics Engineering
SASTRA University

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Table of Content

1 FREE ELECTRON AND NEARLY FREE ELECTRON MODEL

& CONCEPTSLEADING TO KRONIG–PENNEY MODEL ………………………….3

1.1 FREE ELECTRON THEORY …………………………………………………………..3

1.2 FREE ELECTRON MODEL ……………………………………………………………3
1.3 ELECRON GAS IN ONE DIMENSONAL BOX ……………………………………….3
1.4 INFERENCES ………………………………………………………………………...…4
1.5 CONCLUSION …………………………………………………………………………..6
1.6 NEARLY FREE ELECTRON MODEL ………………………………………………...6
1.7 REASON FOR ENERGY GAP FORMATION …………………………………………8
1.8 CONCEPTS LEADING TO KRONIG-PENNEY MODEL …………………………….8

2 ELECTRON IN A PERIODIC FIELD OF

A CRYSTAL (THE KRONIG-PENNEY MODEL) …………………………………….10

3QUASIFREE-ELECTRON APPROXIMATION:
DENSITY OF STATES FUNCTION …………………………………………………...16

3.1 INFERENCES ………………………………………………………………………….16

3.2 ENERGY SPECTRUM ………………………………………………………………...17
3.3 NUMBER OF POSSIBLE WAVE FUNCTIONS IN A BAND ……………………….19
3.4 DENSITY OF STATES ………………………………………………………………...20

4 REFERENCES …………………………………………………………………………….21

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1 Free electron and nearly free electron model &

concepts leading to Kronig – Penney model

1.1 Free Electron Theory

In 1900, Drude first proposed that the large electrical and thermal conductivity of
metals and semiconductors is due to the presence of free electrons. Also Drude and
Lorentz jointly explained these properties based on the following assumptions,

1. Free electrons that move through the specimen suffer collisions with the atoms
2. These free electrons are treated as free particles in ideal gas
3. Hence these particles obey Maxwell-Boltzmann statistics

One of the supporting points for the acceptance of this classical free electron
theory was that it is in agreement with the Wiedmann-Frantz law, which relates electrical
and thermal conductivity.

1.2 Free Electron Model

In this model, a bulk specimen is assumed to be consisting of two parts: one is the
fixed positive charges and the other is free electrons which are nothing but the valance
electrons. And theses electrons are assumed to be free except at the specimen’s surface
and have the effect of confining them to the interior. Thus, according to this model, the
conduction electrons are free to move anywhere in the sample (totally free) except for
rare reflection from the surface and resembles much like molecules in ideal gas.

The free electron approximation, which allows the conduction electrons to move
freely within the solid material boundary implies that the total energy depends mainly on
kinetic energy and not potential energy. This model which is mainly applied for metals
considers the specimen to be a box filled with electrons. These electrons are free and the
only constraint they experience is that they are in a box.

1.3 Electron gas in one dimensional box

Let the length of the box be L with infinite potential barrier at the distance x=0
and x=L and let an electron of mass m be represented by the wave function ψ(x) can be
equated as,

Hψ=Eψ (1)

where H is Hamiltonian and E is total energy (sum of potential and kinetic energy) also it
is allowed eigen values (energies) of the electron in the orbital (i.e., here the study is for a

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system of single electron and the orbital model is valid only if when there is no
interactions between electrons)

As the total energy considered is mainly kinetic equation (1) takes the form

P2
H= (2)
2m

d
where P is the momentum and P = −i in quantum mechanics, hence,
dx

 2 d 2ψ n
Hψ n = − = E nψ n (3)
2m dx 2

The expected boundary conditions are ψ n (0)=ψ n (L)=0, i.e., the electron present
inside the box of dimension L. Rewriting Eqn. 3,

d 2ψ n 2m
2
= − 2 E nψ n (4)
dx 

The general solution of Eqn.4is,

ψ n ( x) = Ae ikx + Be −ikx (5)

2m
where k2 = En (6)
2

We get A=-B by substituting the first boundary condition ψ n (0)=0 and this shows that the
wave function takes the sine like shape.
Applying the second boundary condition ψ(L)=0,

we get, SinkL=0 k=nπ/L ; with n=1,2,3,…

 2  nπ 
2

On substituting in Eqn. 6, En =   (7)

2m  L 
And their wave function representation is,

 nπx 
ψ n = A sin   (8)
 L 

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1.4 Inferences

1. Hence the wave function exists only for integral values of n, ultimately n is the quantum
number.
2. From Eqn.7 the energy consists of discrete value with their spacing depends on the terms
 n2 
 2  , the energy levels are closer when L is large.
L 
3. The value of the constant A in Eqn.8 is determined by considering the normalization
condition (i.e. the electron exists somewhere within the box) and their probability is
L
maximum, 1. Hence, ∫ψ n* ( x)ψ n ( x)dx = 1
0

 nπx 
L
2 2
∫A Sin 2   = 1 ⇒ A = orA =
2 2

0  L  L L
2  nπx 
So the existing wave function is ψ n ( x) = Sin 
L  L 
4. Suppose if the box has to accommodate N number of electrons, the placing of electrons in
the allowed energy levels is done by following Pauli’s exclusion principle. Hence each
quantum level with quantum number n obeying Pauli’s principle can accommodate two
electrons; one with spin up and another with spin down.

Consideringeven number of electrons N, these electrons are filled sequentially from the
bottom most level(n=1) to the top most energy level (n f ), with

2n f =N

The upper most energy is nothing but the Fermi energy at 0K, which can be obtained
from Eqn. 7 with n=n f ,
2  n f π 
2
 2  Nπ 
2

Ef =   =  
2m  L  2m  2 L 

Now the total energy E o is obtained by individually summing the energies E n

between n=1 and n f =N/2. (Where 2 is introduced due to spin degeneracy)

2 2  π 
N /2 2 N /2

Therefore, E o = ∑ En =
n =1
 
2m  L 
∑n
n =1
2

On simplification, we get,
1
Eo ≅ NE f
3

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1.5 Conclusion
Free electron model helps in better understanding of several key parameters of metals
like heat capacity, thermal conductivity, electrical conductivity, magnetic susceptibility
and electrodynamics.

However, it fails to explain the positive values of Hall co-efficient observed, fails
to differentiate insulator, semiconductor and conductor materials. It also fails to relate
conduction electron in metals to the valence electron of free atoms and cannot explain
transport properties like magneto transport.

1.6 Nearly Free Electron Model

The concept of energy bands was introduced to have a better understanding of
metals and crystals. Every solid has electrons. However, to understand the difference in
the behavior of these electrons in insulators and conductors, we have to take into account,
the presence of lattice in the specimen. Hence the electrons from now are not totally free
instead they are nearly free since the presence of lattice (ions) has its own influence
(though weak).

Following the free electron model, the allowed energy values when the form extends in 3
dimension takes,
Ek =
2
2m
(K x2 + K y2 + K z2 )

Over a cube of side L, where K x , K y , K z =±nπ/L; n=0,2,4,…

According to nearly free electron model, electrons present in a specimen are slightly
perturbed by the weak periodic potential produced by the lattice. Qualitative analysis
about the metals and crystals can be done by studying their band structures.

Energy gaps are caused when electrons’ undergo Bragg’s reflection. In these gaps
Schrodinger equation which depicts the wave like nature of electron does not exist.
These energy gaps detected plays a vital role in discriminating / identifying a solid as an
insulator or a conductor. The energy of the electron based on free electron and nearly
free electron model are shown in Fig. 1a. and Fig. 1b respectively.

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K
Fig. 1a.Energy curve of a free electron.

Second allowed
band
B B
Forbidden
gap

A A
First allowed
band

-π/a +π/a
Fig. 1b.Energy curve of an electron in a monoatomic linear lattice; a – lattice constant. i.e., I reflection at ± π/a

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The Fig. 1b shows an energy gap at k=±π/a, where Bragg’s first reflection is observed.
As per Bragg’s concept other gaps occur for integer values of n. The reason for the
occurrence of reflection at k==±π/a is because the reflected wave from one atom in the
linear lattice interferes constructively with a phase difference of 2π.

1.7 Reason for energy gap formation

The wave function at the point k=±π/a do not have traveling waves instead
standing waves. The standing waves are formed when wave is Bragg reflected; its
direction of travel is opposite to its incident direction and subsequent reflection reverses
the direction again there by producing standing waves since the wave by itself should be
time independent. The two different forms of standing waves in terms of traveling waves
e iπx / a ande − iπx / a are,

 πx 
ψ (+) = e iπx / a + e −iπx / a = 2Cos  (real part)
a

 πx 
ψ (−) = e iπx / a − e −iπx / a = 2iSin  (imaginary part)
a

These two different standing waves ψ(+) and ψ(-) group electron at different
region with different potential energy. This gives raise to the formation of forbidden
energy gap.

1.8 Concepts leading to Kronig–Penney Model

The fundamental nature of insulators, conductors and semiconductors can be
functionally explained based on band theory. The recent development in semiconductor
physics, the semiconductor hetero-structures are also analyzed using the concept of band
theory.

Another notable theory, the free-electron theory, can help in understanding the
electron movement in metals. It assumes that, the valence electron in a metal absorbs
thermal energy which ultimately is converted into kinetic energy with an average of
(3/2)K B T based on law of equipartition of energy. But the calculated molar electronic
specific heat does not match with the experimental value.

Hence it can be concluded that the equipartition law and the classical Maxwell-
Boltzmann statistics are not adequate for evaluating electronic specific heat in metals.
Another failure of classical free electron theory is that, it does not account for the
magnetic moment of electron due to its spin.

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The free-electron theory, which neglects the magnetic moment of electrons

arising from their spin predicts that, paramagnetic susceptibility is proportional to the
temperature for each electron. On the contrary, the experimental results show that the
susceptibility is almost independent (constant) of temperature.

The reason is, the classical theory allows all the free electrons to gain energy
which does not actually happen in reality, which leads to drastic difference between the
calculated and the observe values.

At this juncture, the quantum free-electron theory steps in, assumes that an
electron in a metal experiences a constant or zero potential and hence is free to move
within the lattice.

The quantum free-electron theory thus successfully explains the specific heat,
electrical conductivity, thermionic emission, thermal conductivity and para magnetism of
materials. However, the concept fails to differentiate the conductivities in conductors,
semiconductors and insulators.

In a real crystal, electrons move in a regularly arranged lattice of positive ions.

The electrons have the zero potential at the positive ion site and possess maximum value
at the intermediate lattice points.

This could be schematically represented as shown in Fig. 2(sine wave notation).

The observed potential is periodical as the lattice planes. Bloch has the solution as
ψ ( x) = U k ( x)e ikx for the Schrödinger equation, which describes the electron motion:

d 2ψ 2m
+ 2 [ E − V ( x)]ψ = 0 (9)
dx 2 

where, ψ is the wave function and U k (x) in the Bloch’s solution, which has the
periodicity of the lattice.

Hence, the wave function includes both a plane wave eikx which is modulated by
the periodic function U k (x) and the state of motion of electron, which is represented by
the wave vector k. However, it is difficult (not tractable) to solve the Schrödinger’s
equation with the sinusoidal periodicity. Therefore, Kronig and Penney suggested a
simpler model, where the inner potential of the crystal system has the rectangular shaped
potential.

Thus, in the Kronig Penney model, instead of experiencing a gradual variation in

the strength of the potential electrons experience a maximum potential (potential well)
and minimum value (potential barrier) in the presence of the lattice planes.

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Fig. 2. One dimensional periodic potential distribution for a crystal

2 ELECTRON IN A PERIODIC FIELD OF A CRYSTAL (THE

KRONIG - PENNEY MODEL)
For the treatment of our problem, a periodic repetition of the potential well of Fig.3, i.e.,
a periodic arrangement of potential wells and potential barriers, is most probably very close to
reality and is also best suited for the calculation. Such a periodic potential is shown in Fig. 3 for
the one-dimensional case.

Fig. 3. Ideal periodic square well potential used by Kronig and Penney.

Although this model is highly artificial, yet it illustrates many of the characteristic features of the
behaviour of electrons in a periodic lattice. The wave functions associated with this model can

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be calculated by solving Schrodinger equations for the two regions I and II. The time-
independent Schrodinger equation takes the following forms for the two regions

+ E = 0; for 0 < x < a (10)

And

+ (E- ) = 0; for –b < x < 0 (11)

Making use of Bloch’s theorem, the solution can be written in the form

(x) = (x) (12)

Assuming that the total energy E of the electron is less than the potential energy , we define
two real quantities α and β such that

= (13)

and = -E) (14)

Thus

= 0; for 0 < x < a (15)

= 0; for –b < x < 0 (16)

The solution that will be appropriate for both the regions suggested by Bloch is of the form

(x) = (x) (17)

On differentiating this equation, one gets

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= +

and = + –

i.e., -

Substituting these values, we get

+2iK +( =0; for 0<x< (18)

and +2iK -( = 0; for -b<x<0 (19)

where represents the value of (x) in the interval 0<x<a and the value of (x) in the
interval -b<x<0.

The solution of the differential Eqn. (18) is of the form

=m and =

Substituting these values in Eqn. (18), we get

=0

m=
m = -iK ± iα

i.e., = -iK + iα = i(α - K)

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and = -iK - iα = -i(α + K)

Thus the general solution is

=A +B
=A +B (20)

Where A and B are constants.

Similarly Eqn. (19) can be written as

+ 2iKm – ( + )=0

m=

m = -iK ± iβ

i.e., = -iK + β = (β - iK)

and = -iK - β = - (β + iK)

Thus =C +D

=C +D (21)

Where C and D are constants. The values of the constants A, B, C and D can be obtained by
applying the boundary conditions.

= ; =

and = ; =

Applying these conditions, we get

(i) (A + B) = (C + D) (22)

(ii)
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i.e., i(α – K)A – i(α+K)B = (β – iK)C – (β +iK)D (23)

(iii) A +B = C +D (24)

(iv)

i.e.,

= (25)

Eqn. 22,23,24 and 25 will have non- vanishing solutions if and only if the determinant of the
coefficients A, B,C and D vanishes. This requires that

1 1 1 1
i(α-K) -i(α-K) (β-iK) -(β-iK) =0
ei(α-k)a e-i(α+k)a e-(β-iK)b e(β+iK)b
i(α-K) ei(α-k)a -i(α-K) e-i(α+k)a (β-iK) e-b(β-iK)b -(β-iK) e(β+iK)b

Thus the solution of the determinant (Eqn. 25) is

(26)

Eqn. (26) is complicated but a simplification is possible. Kronig and Penney considered the
possibility that remains finite. Such a function is called delta function. Under these
circumstances, and as .

Hence Eqn. (26) becomes

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Since

Substituting this in the above equation, we get

Where

ie., (27)

The term is called the barrier strength. The term in Eqn. (27) is sometimes
referred as the scattering power of the potential barrier. It is a measure of the strength with which
electrons in a crystal are attracted to the ions on the crystal lattice sites. Also

or

and (28)

Eqn. (27) is a condition of the existence of a solution for the electron wave function.

There are only two variables in Eqn. (27), namely and K. The right hand side of Eqn.
(27) is bounded since it can only assume values between +1 and -1. If we plot the left-hand side
of this equation against , it will be possible to determine those value of (and hence

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energy) which are permissible; that is, permit to take values between +1 and -
1. This has been plotted in Fig.4.

Fig. 4. Plot of =cosKa with P =3π/2.

3. Quasifree-Electron Approximation: Density of States

Function
3.1 Inferences
1. The permissible limit of the term lies between +1 to -1. By varying αa,
a wave mechanical nature could be plotted as shown in Fig. 5, the shaded portion of the
wave shows the bands of allowed energy with the forbidden region as unshaded portion.

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Fig. 5. Left hand side of Eqn. 28

2. With increase of αa, the allowed energy states for a electron increases there by
increasing the band width of the bands, i.e., the strength of the potential barrier
diminishes. This also leads to increase of the distance between electrons and the total
energy possessed by the individual electron.
3.Conversly if suppose the effect of potential barrier dominate i.e., if P is large, the

resultant wave obtained in terms of shows a stepper variation in the

region lies between +1 to -1. This results in the decrease of allowed energy and increase
of forbidden energy gap. Thus at extremities,

Case (i) when P∞, the allowed energy states are compressed to a line spectrum.
(Fig. 6b)

Case (ii) when P0 the energy band is

broadened and it is quasi continuous.
(Fig. 6c)

3.2 Energy Spectrum

Fig. 6b. Line spectrum of energy bands 6c. Quasi state spectrum

Case (i):At one of the extremities, p ∞

sinαa =0; or αa = ± n =>

on rearranging,

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(29)

Here the energy depends on the width of the potential rather than any other parameter.
The energy level of electron in the crystal lattice is discrete and is similar to the particle
in a potential box with an atomic dimensions. This is because with a large value of
potential strength barrier the tunneling effect is explicitly improbable.

Case (ii):When p0, with the same equation cosαa=coska => α= k

Substituting the values = on rearranging,

E= (30)

λ here refers to the wave nature of the electron and is equated as de Broglie’s wavelength

E= (31)

The energy obtained above corresponds to the energy of the completely free particles and
is depicted is Fig. 7.

Free Intermediate Tight

Electron case binding

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Fig. 7.Energy level structure for differentiating degrees of binding.

Thus using this model a system can beanalyzed from the free state condition to the
extremely bounded condition.

3.3 Number of Possible Wave Functions in a Band

Let us consider a one-dimensional crystal of N lattices. The length L of the lattice

is N(a+b). Imposing the periodic boundary conditions for obtaining the running wave
picture of the de Broglie wave, we find that the wave function must be periodic in ‘L”.
That is

The wave function in one dimensional periodic potential lattice is given by

and

Imposing the periodic boundary conditions, we get

(32)

We have already seen that the modulating function has the periodicity of the
lattice.

i.e.,

Where Na is the length ’L’ of the crystal.Substituting this in Eqn. (32), we get

or K= (33)

with n = ±1, ±2, ±3…..

Now n=

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Thus the number of possible wave functions in the interval dK is

dn =

Hence total number of possible states in a band is

n= =

n= ,

i.e., na = L (34)

with b 0, a+b Also length of the crystal L = N(a+b) = Na. Comparing this with
Eqn.6, we get n = N, where N is the number of unit cells. Thus the total number of
possible states in a band is the number of unit cells. Taking into account the spin of the
electron and Pauli’s exclusion principle, each state can be occupied at most by two
electrons, and hence the total number of electrons in a band is 2N.

3.4 Density of states

Density of states for electron is nothing but the number of available energy states
for the electron to occupy. Knowledge about this helps us to understand the electronic
transport phenomena. Let it be denoted as D(E) and this is dealt with in the energy range
of E and E+dE with the representation as D(E)dE.

The expression for density states of free electrons for in metals and in crystals are
the same except the considered mass in metals has been replaced by effective mass in
crystals.

The density of states in one dimension is given by the equation

2 dk
n( E ) = (35)
π dE

But the dispersion relation given by Kronig Penny is,

PSinαL
+ CosαL = CoskL (36)
αL

With the aid of this equation, the density of state equation becomes,

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  SinαL CosαL  
(2m)1 / 2  P −  + Sin α L 
  (αL )
2
αL  
n( E ) = 1/ 2
(37)
  PSinαL  
2

π E 1 −  + CosαL  
  αL  

The effective masses m e of electron in the range k=nπ/L are defined as,
1 1 d 2 E  nπ 
= 2   ; n=0,1,2… (38)
me  dk 2  L 

then with the dispersion equation the effective mass could be rewritten as

me = β mo
  SinαL CosαL  
1/ 2
1  2 
where, β =    P − 
 + Sin α L  x(CoskL)
−1

L  2mE    (αL)
2
αL  

where, k= nπ/L and E is the energy at the lower edge of the upper band at k= nπ/L.

4 References
1. Omar, M. A. Elementary Solid State Physics: Principles and Applications. 6th ed.
Delhi: Pearson Education, 2000. Print.
2. Kittel, Charles. Introduction to Solid State Physics. 7th ed. Delhi: John Wiley &
Sons, 1986. Print.
3. Pillai, S.O. Solid State Physics. 5th ed. Delhi: New Age International (P) Limited,
1995. Print.

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