Part 4

Band Theory of Solids

10/10/2021 Band Theory of Solids 1

OUTLINE

• Periodic Crystal Potentials

• Bloch Functions in Crystals
• The Kronig-Penney Model

10/10/2021 Band Theory of Solids 2

 Periodic Crystal Potentials
For a more realistic description of electron transport in crystals it is necessary to
consider the INTERACTIONS that arise between the electrons and the crystal
structure.
In general, the crystal is composed of POSITIVE ion cores that are ordered into
a REGULAR lattice.
 As an electron moves through the crystal its potential energy vary
PERIODICALLY as a function of position.
U(x)

+ x + + + +

ze 2
U ( x)  
4o x

Variation of potential energy with When many atoms combine and form a crystal the
distance for an electron near a atomic potentials overlap giving rise to a periodic
single ion core. variation.
10/10/2021 Band Theory of Solids 3
 Periodic Crystal Potentials
Crystal potentials exhibit the important property of TRANSLATIONAL
SYMMETRY.

For a one-dimensional linear lattice ,of (N) atoms of atomic spacing (d), this
periodic potential may be expressed mathematically as follows:
u ( x  nd )  u ( x ) , n  1, 2, 3,  , N
An important consequence of this translational symmetry is that the probability
(P) of finding the electron at two points shifted by a lattice translational vector
must be the SAME: d
1 2 3
+ + + +

P ( x  nd )  P ( x )
d

The probability of finding

an electron must be the
same at points 1, 2 & 3!

10/10/2021 Band Theory of Solids 4

 Bloch Functions in Crystals
Bloch’s theorem states that the wave function
for an electron in a crystal is a PLANE WAVE
that is MODULATED by a function with the Felix Bloch (1905-1983)
periodicity of the crystal Switzerland

 ( x )  u ( x )e ikx , u ( x  nd )  u ( x )

In this equation, u(x) is a function with the

SAME periodicity of the crystal and is related
to the STRENGTH of the crystal potential.

Bloch’s theorem may also be stated in an ALTERNATIVE form:

 ( x  nd )  u ( x  nd )e ik ( x nd )  u ( x )e ikx e iknd   ( x ) e iknd

10/10/2021 Band Theory of Solids 5

 The Kronig-Penney Model
(1930)
One Dimensional Motion of an Electron in a
Periodic Potential
Assumptions:
Ralph Kronig
• The periodic potential of the crystal is crudely
modeled as a square-well super-lattice.
• Each potential well can be considered to d
Uo
represent the potential associated with a
particular atom in the crystal.
• The period of the potential is d (d = a + b), E
where (b) is the barrier width and (a) is the U=0 x
width of the zero potential region. b
• The potential energy function is given by: a
0 0 xa
U ( x)  
U o  b  x  0
• The potential modulation Uo is taken to be large compared to the electron energy E

10/10/2021 Band Theory of Solids 6

 The Kronig-Penney Model
By applying the time independent Schrödinger equation in regions 1 & 2

 2 d 2 1 (x )
2
 E 1 (x )  0 for 0  x  a U
2m dx d
d 2 1 (x ) 2mE Uo
  2
1 (x )  0 where  ...(1)
dx 2 2 (2) (1)
E
 d 2 ( x)
2 2

2
 ( E  U o )2 ( x)  0 for  b  x  0
2m dx x
-b a
d 2 2 (x ) 2m
  2
2 (x )  0 where  (U o  E ) …(2)
dx 2
 2

Since the electron moves in a PERIODIC potential, its wave function must
satisfy BLOCH’S THEOREM which for:

 (x )  u (x )e ikx
10/10/2021 Band Theory of Solids 7
 The Kronig-Penney Model
By substituting in equations (1) and (2), we obtain:

 du1 (x ) 
 
d 2u1 (x ) 
 2ik 
   2
 k 2
u1  0 for 0 x a
dx 2 
 dx 
 du 2 (x ) 
 
d 2u 2 (x ) 
 2ik 
   2
 k 2
u 2  0 for  b  x  0
dx 2 
 dx 
The solutions of these equations are:
u1 ( x )  Ae i ( k ) x  Be i ( k ) x for 0  x a

u 2 (x )  Ce (  ik ) x  De (  ik ) x for  b  x  0

where A, B, C and D are constants that must be chosen in such a manner

that the following conditions are satisfied:

u 1 u 2 u 1 u 2
u1 (0)  u 2 (0)  u1 (a )  u 2 (b ) 
x x 0 x x x a x
x 0 x b

10/10/2021 Band Theory of Solids 8

 The Kronig-Penney Model
A  B C  D
i (  k )A  i (  k )B  (  ik )C  (   ik )D

e i (k )a A  e i ( k )a B  e (  ik )b C  e (  ik )b D

i (  k )e i (k )a A  i (  k )e i ( k )a B  (  ik )e (  ik )bC  (  ik )e (  ik )b D

• The equations above define a homogenous set of four equations with four unknowns.

 1 1 1 1  A 
 i (  k ) i (  k ) (   ik ) (   ik )   B 
 0
 e i (  k ) a e  i (   k )a e  (  ik )b e (   ik )b
 C 
 i (  k ) a  
i (  k )e i (  k )e  i (   k )a (   ik )e  (  ik )b (   ik )e (  ik )b   D 

• A nontrivial solution for A, B, C and D exists if and only if the determinant of the
matrix of coefficient is zero.

10/10/2021 Band Theory of Solids 9

 The Kronig-Penney Model
This requirement leads ,in turn, to the following conditions on the ALLOWED
electron energies and wave numbers:
 2  2
sin(a )sinh(b )  cos(a )cosh(b )  cos k (a  b ) (3)
2
To obtain a more convenient equation, Kronig and Penney assumed that:
• The probability of tunneling transition of an electron of energy E from
one atom to another depends on the shaded area (Barrier Strength). d
Uo
Barrier Strength  b  (U o  E )  bU o  b 2

• Uo   and b  0 but the Barrier Strength remains CONSTANT E

(potential barrier becomes a delta function).
x
Consequently β βb  0 b
a
sinh βb  βb Eq. (3) is  2b
By using
reduced to sin(a)  cos(a)  cos(ka) ...(4)
cosh βb  1 2
10/10/2021 Band Theory of Solids 10
 The Kronig-Penney Model
ab 2 mabU o
By introducing the NEW variable P 
P is called the “biding parameter”
2 2
sin(a )
From Eq. (4) P  cos(a )  cos(ka ) (5)
a
This is a DISPERSION RELATION for electrons since it provides a connection
between their wave number (k) on the RHS and their energy (α) on the LHS
• In the figure, a plot of the variation of the LHS of
Eq. (5) as a function of the parameter αa, is shown.
sin(a)
• In order for Eq. (5) to have a solution, P
a
 cos(a )

it is required that –1  LHS  1

• The shaded regions correspond to
ranges of aα for which solutions to the
Eq. (5) are POSSIBLE.
a
• The UNSHADED regions allow NO
solution for Eq. (5) and so correspond to
physically FORBIDDEN energies.
10/10/2021 Band Theory of Solids 11
 The Kronig-Penney Model
sin(a )
P
a

sin(a)
f (a)  P  cos(a)
a

10/10/2021 Band Theory of Solids 12

 The Kronig-Penney Model (cont.)
• The width of the allowed energy band increases with increasing a i.e. with
INCREASING the electron energy (E).

• The width of a particular allowed band DECREASES E

with INCREASING the binding energy (P )

P    sin  a  0 n=2
 a  n where n  1, 2,...
 2 2 Energy Levels
 En  2
n2
2ma (Max. energy of the band) n=1
P
Physically, this could be expected because for a large
P, tunneling through the barriers becomes improbable
(particle in a box)

• For P = 0, the energy spectrum is (quasi) continuous (free electron model):

2k 2
P  0  cos  a  cos ka   k  E 
2m

10/10/2021 Band Theory of Solids 13

 The Kronig-Penney Model (cont.)
E
• From Eq. (5), it is possible to
obtain E as a function of k as
shown in the next figure

• The discontinuities in the E Forbidden

regions
versus k curve occur for: Free electron
Parabola
k  n / a n  1, 2,...
These k-values define the
boundaries of the first, second,
etc. Brillouin zones 
3

2

  2 3
k
a a a a a a

First Brillouin Reduced

zones
Second Brillouin Brillouin
zone zones

• It is frequently convenient to introduce the “reduced wave vectors” or “reduced

Brillouin zones” which are limited to the region
 / a  k   / a
10/10/2021 Band Theory of Solids 14
 The Kronig-Penney Model (cont.)
• The electron velocity in each band is equal to the group velocity of the waves
representing the particle.
d 1 dE Importance of
vg   ( E  hf   )
dk  dk E-k curve
vg
• At the top and the bottom of each
energy band vg= 0 since dE/dk = 0
• The absolute value of velocity reaches
maximum at the inflection points of the 
3

2


a a a
E-k curve.  2 3
k
a a a

• It is also important to note that, beyond

the maximum points, velocity decreases
First Band
with increasing energy.

• Totally FILLED BANDS do not contribute to the charge transport process.

10/10/2021 Band Theory of Solids 15

 The Kronig-Penney Model (cont.)
E

An important property of a full band is that it is unable to

carry a net current since for each state in the band, we can
identify a corresponding state with equal and opposite ENERGY GAP

momentum that is filled by an electron.

k
To drive a net current through the crystal, it is necessary to /a /a
induce an IMBALANCE in the filling of momentum states. NO or small applied electric field

E E

If the energy band is partially filled,

then it should be very EASY to generate ENERGY GAP ENERGY GAP
a net current flow in the crystal.

It is easy to use an electric field to

generate an imbalance in the filling k k
of momentum states. /a /a /a /a

No applied electric field A small electric field is applied

10/10/2021 Band Theory of Solids 16

 The Kronig-Penney Model (cont.)
Effective Mass
• Let an EXTERNAL FORCE (Fext) act on an electron for a small time dt.

 The electron gains an energy vg 

d

1 dE
dk  dk
dE  Fext dx  Fext vg dt
 1 dE  dk
 Fext   dt Fext  
  dk  dt

 The electron acceleration

1  1 dE  1 1  dk dE  1 dk d 2 E
dvg
a     
dt dt   dk   dt  dk dk   dt dk 2
1 Fext d 2 E Fext Fext Fext  Fint
a
   m ( real mass )
  dk 2
2 d E
2
m*
 / 2
dk
d 2E
 Thus an electron behaves as if it had an effective mass: m   * 2
dk 2
10/10/2021 Band Theory of Solids 17
 The Kronig-Penney Model (cont.)
The effective mass of an electron in a material takes into account the internal
influences of the lattice so that an electron can be treated as almost free.
E

If we consider an electron located in the first Fig. 1

Brillouin Zone, as shown in Fig. 1
/a /a k
vg
 The electron velocity is shown in Fig. 2
/a
Fig. 2
d 1 dE /a k
vg  
dk  dk dE2/dk2

Fig. 3
2
 Figure 3 depicts d E
dk 2 /a /a k

m*

 The electron effective mass is shown Fig. 4

in Fig. 4 2
/a /a
2 d E
m  / 2
* k

dk

10/10/2021 Band Theory of Solids 18

 The Kronig-Penney Model (cont.)
• The effective mass m* is POSITIVE near the bottoms of all bands

• The effective mass m* is NEGATIVE near the tops of all bands

• A negative effective mass simply means that, in response to an applied force, the
electron will actually decelerate, that is, moves more slowly (or accelerates in a
direction opposite to that expected from purely classical considerations).
• Mathematically, the effective mass is inversely proportional to the curvature of
the E-k plot
E

 Consider, for example, the two bands pictured (b)

in the next figure.
In the vicinity of the respective energy minima, the (a)

curvature of segment (b) [(d2E/dk2)b] is GREATER

than the curvature of segment (a) [(d2E/dk2)a]
One concludes that ma* > mb* k

10/10/2021 Band Theory of Solids 19

 The Kronig-Penney Model (cont.)
In general, the effective mass of an
electron is a function of the electron E

energy E.

Near the top or the bottom, the band Band edges

edge is approximated by a Parabolic
curve as visualized in the next figure. Parabolic fit

d 2E
 CONSTANT ( near Eedge )
k
and therefore 2
dk

Thus, carriers in a crystal with energies near top or bottom of an energy

band typically exhibit a CONSTANT (energy-independent) effective mass.

10/10/2021 Band Theory of Solids 20

The Concept of a “hole”
 Consider the E-k curve for a full band.
There is no net contribution to the current. There are equal
numbers of electrons (e.g., at b and b' ) with opposite momenta.
N
The current density J N  e Vgi  0
i 1

where Vgi is the group velocity of electron (i) and (N) is the total number of electrons in the band.

 If there is an empty state (hole) at b at the top of the band, ℰx

F
then the electron at b' contributes to the current.

If an electric field ℰx (along +x direction) affects the electron b’

that has a negative mass -|m*|, the acceleration is given by:

Fext e e

a   a in direction of ℰx
effective mass  m *  m *

This means that the acceleration of an electron with a negative effective mass is
equivalent to acceleration of a positive charge +e with effective mass +|m*|.

10/10/2021 Band Theory of Solids 21

Suppose that the jth electron is missing (b in the
next figure). The net current density is due to N -
1 electrons in the band, so:
N
J N 1  e V
i 1,i  j
gi

We can write the sum as the summation to N including the jth electron minus
the missing jth electron contribution:
N
J N 1  e Vgi  ( eVgj )
i 1

that is: J N 1   eVgj

We see that when there is a missing electron, there is a net current due to that
empty state (jth) which is what we call a hole. The current appears as the motion of
a charge (+e) with a group velocity Vgj

10/10/2021 Band Theory of Solids 22

 The Kronig-Penney Model
Insulators, Semiconductors and Metals

• At T = 0 K, the band of highest energy that is

completely filled with electrons is called the
valence band.
 The top of the valence band corresponds to
energy Ev.
ETop
CONDUCTION
BAND
• The next higher band that must not be
Ec
completely filled with electrons is called the
conduction band. ENERGY GAP Eg

 The bottom of the conduction band is Ec.

Ev

VALENCE
BAND
• The separation in energy between Ec and Ev is
EBot
the width of the energy gap Eg

POSITION x

10/10/2021 Band Theory of Solids 23

 Empty
Conduction Band
Insulators
 The bandgap energy Eg of an insulator is usually on
the order of 6 eV or larger, so that at room
temperature, the valence band remains completely Eg > 6 eV
full.
 If an electric field is applied, there will be no current.
Full
Valence Band
Semiconductors
T=0K & T>0K
 Semiconductors have an energy band
structure resembling that of insulators
but Eg are relatively smaller (0.6–1.5
eV). Empty Partially full
Conduction Band Conduction Band
 At ordinary room temperatures, a small
proportion of electrons in the valence Eg  1 – 1.5 eV Eg  1 – 1.5 eV
band have sufficient energy to cross the
narrow energy gap and enter the Full Partially empty
Valence Band
conduction band.. Valence Band

T=0K T>0K
 These electrons are sufficient to permit a
limited amount of current to flow when
an electric field is applied.

10/10/2021 Band Theory of Solids 24

Metals Partially Filled
Conduction Band
The energy-band diagram for a metal may be in one
of two forms:
 The case of a partially full band in which there
Full
are many electrons available for conduction, so Valence Band
that the material can exhibit a large electrical
conductivity.
 Another possible energy-band diagram shows a
case in which the conduction and valence bands Upper Band

overlap.
Lower Band

Overlapping allowed energy

bands

10/10/2021 Band Theory of Solids 25