Band Theory of Solids

(Garcia Chapter 24)

Electrons in Solids
Considering electrons in metals as free
particles, electron gas in a box explains
many experimental results which?
Still, why are some solids metals and others
insulators?
For metals we assumed that electrons are free
We know, however, that there are no free
electrons in insulators
QM give us the answer!
Need a more realistic potential for electrons
reflecting periodic ionic structure of solids
Realistic Potential in Solids




n
i
are integers

Example: 2D Lattice

c n b n a n T
T r U r U

3 2 1
) ( ) (
+ + =
+ =
3 ; 2
2 1
2 1
= =
+ =
n n
b n a n T

Realistic Potential in Solids

For one dimensional case where atoms (ions)
are separated by distance d, we can write
condition of periodicity as
) ( ) ( n d x U x U + =
Realistic Potential in Solids
Multi-electron atomic potentials are complex
Even for hydrogen atom with a simple
Coulomb potential solutions are quite
complex
So we use a model one-dimensional periodic
potential to get insight into the problem
Blochs Theorem
Blochs Theorem states that for a particle
moving in the periodic potential, the
wavefunctions (x) are of the form



u
k
(x) is a periodic function with the periodicity
of the potential
The exact form depends on the potential
associated with atoms (ions) that form the solid
) ( ) (
function periodic a is ) ( , ) ( ) (
d x u x u
x u where e x u x
k k
k
ikx
k
+ =
=

Blochs Theorem
Blochs Theorem imposes very special
conditions on any solution of the
Schrdinger equation, independent of the
form of the periodic potential
The wave vector k has a two-fold role:
1. It is still a wave vector in the plane wave part of
the solution
2. It is also an index to u
k
(x) because it contains all
the quantum numbers, which enumerate the
wavefunction
Blochs Theorem
What is probability density of finding
particle at coordinate x?
2
* *
*
*
2
) ( ) (
) ( ) ( ) ( ) ( ) (
] ) ( [ ] ) ( [ ) (
) ( ) ( ) ( ) (
x u x P
x u x u e e x u x u x P
e x u e x u x P
x x x x P
k
k k
ikx ikx
k k
ikx
k
ikx
k
=
= =
=
= =

But |u
k
(x)|
2
is periodic, so P(x) is as well
2
) (x u
k
Blochs Theorem


The probability of finding an electron at
any atom in the solid is the same!!!

Each electron in a crystalline solid
belongs to each and every atom
forming the solid
) ( ) ( d x P x P + =
Covalent Bonding Revisited

When atoms are covalently bonded
electrons supplied by atoms are
shared by these atoms since pull of
each atom is the same or nearly so
H
2
, F
2
, CO,
Example: the ground state of the
hydrogen atoms forming a molecule
If the atoms are far apart there is very
little overlap between their wavefunctions
If atoms are brought together the
wavefunctions overlap and form the
compound wavefunction,
1
(r)+
2
(r),
increasing the probability for electrons to
exist between the atoms
0
/
3
0
1
1
a r
s
e
a

=
t

Covalent Bonding Revisited

Schrdinger Equation Revisited
If a wavefunctions
1
(x) and
2
(x) are
solutions for the Schrdinger equation for
energy E, then functions
-
1
(x), -
2
(x), and
1
(x)
2
(x) are also solutions
of this equations
the probability density of -
1
(x) is the same as for

1
(x)
)] ( ) ( [ )] ( ) ( )[ (
)] ( ) ( [
2
) ( )] ( )[ (
) (
2
2 1 2 1
2
2 1
2 2
2 , 1 2 , 1
2
2 , 1
2
2
x x E x x x U
dx
x x d
m
x E x x U
dx
x d
m

+ = + +
+

= +

Consider an atom with only one electron in s-state

outside of a closed shell
Both of the wavefunctions below are valid and the
choice of each is equivalent




If the atoms are far apart, as before, the
wavefunctions are the same as for the isolated
atoms
Band Theory of Solids
0
0
/
/
) ( ) (
) ( ) (
na Zr
s
na Zr
s
e r Af r
e r Af r

+
=
+ =

Band Theory of Solids

The sum of them is shown in the
figure
These two possible combinations
represent two possible states of
two atoms system with different
energies
Once the atoms are brought together the
wavefunctions begin to overlap
There are two possibilities
1. Overlapping wavefunctions are the same (e.g.,
s
+

(r))
2. Overlapping wavefunctions are different
Tight-Binding Band Theory
of Solids
Garcia Chapter 24.4 and 24.5
Electron in Two Separated Potential Wells
Potential Wells Moved Closer
Tight-Binding Approximation
first two states in infinite and finite potential
wells
Symmetric and Anti-symmetric
Combinations of Ground State
Eigenfunctions
Six States for Six Atom Solid
Splitting of 1s State of Six Atoms
Atoms and Band Structure
Consider multi-electron atoms:
1. The outer electrons (large n and l)
are closer to each other than the
inner electrons
Thus, the overlap of the wave-
functions of the outer electrons is
stronger than overlap of those of
inner electrons
Therefore, the bands formed from
outer electrons are wider than the
bands formed from inner electrons
Bands with higher energies
are therefore wider!
Splitting of Atomic Levels in Sodium
Occupation of Bands Sodium
Splitting of Atomic Levels in Carbon
Occupation in Carbon at Large
Atomic Separation
Actual Occupation of Energy bands
in Diamond
Insulators, Semiconductors,
Metals
The last completely filled (at least at T = 0 K)
band is called the Valence Band
The next band with higher energy is the
Conduction Band
The Conduction Band can be empty or partially
filed
The energy difference between the bottom of
the CB and the top of the VB is called the
Band Gap (or Forbidden Gap)
Can be found using computer
In 1D computer simulation of light in a
periodic structure, we found the
frequencies and wave functions
Allowed modes fall into quasi-
continuous bands separated by forbidden
bands just as would be expected from the
tight binding model
Computer simulation can give
exact solution in simple cases
Insulators, Semiconductors,
Metals
Consider a solid with the empty
Conduction Band
If apply electric field
to this solid, the
electrons in the
valence band (VB)
cannot participate in
transport (no current)
Insulators, Semiconductors,
Metals
The electrons in the VB do not
participate in the current, since
Classically, electrons in the
electric field accelerate, so they
acquire [kinetic] energy
In QM this means they must
acquire slightly higher energy
and jump to another quantum
state
Such states must be available,
i.e. empty allowed states
But no such state are available in
the VB!
This solid
would behave
as an insulator
Insulators, Semiconductors,
Metals
Consider a solid with the half filled
Conduction Band (T = 0K)
If an electric field is applied
to this solid, electrons in the
CB do participate in
transport, since there are
plenty of empty allowed
states with energies just
above the Fermi energy
This solid would behave as
a conductor (metal)
Band Overlap
Many materials are
conductors (metals) due to the
band overlap phenomenon
Often the higher energy bands
become so wide that they
overlap with the lower bands
additional electron energy levels
are then available
Band Overlap
Example: Magnesium (Mg; Z =12): 1s
2
2s
2
2p
6
3s
2
Might expect to be insulator; however, it is a metal
3s-band overlaps the 3p-band, so now the
conduction band contains 8N energy levels, while
only have 2N electrons
Other examples: Zn, Be, Ca, Bi
Band Hybridization
In some cases the opposite occurs
Due to the overlap, electrons from different shells
form hybrid bands, which can be separated in
energy
Depending on the magnitude of the gap, solids
can be insulators (Diamond); semiconductors (Si,
Ge, Sn; metals (Pb)
Insulators, Semiconductors, Metals
There is a qualitative difference between
metals and insulators (semiconductors)
the highest energy band containing electrons is
only partially filled for Metals (sometimes due to
the overlap)
Thus they are good conductors even at very low
temperatures
The resisitvity arises from the electron scattering from
lattice vibrations and lattice defects
Vibrations increases with temperature higher
resistivity
The concentration of carriers does not change
appreciably with temperature
Insulators, Semiconductors, Metals
The difference between Insulators and
Semiconductors is quantitative
The difference in the magnitude of the band gap
Semiconductors are Insulators with a
relatively small band gap
At high enough temperatures a fraction of electrons
can be found in the conduction band and therefore
participate in transport
Insulators vs Semiconductors
There is no difference between Insulators and
Semiconductors at very low temperatures
In neither material are there any electrons in the
conduction band and so conductivity vanishes in
the low temperature limit
Insulators vs Semiconductors
Differences arises at high temperatures
A small fraction of the electrons is thermally
excited into the conduction band. These
electrons carry current just as in metals
The smaller the gap the more electrons in the
conduction band at a given temperature
Resistivity decreases with temperature due to
higher concentration of electrons in the
conduction band
*
2
1
m
n q t
o

= =
Holes
Consider an insulator (or semiconductor)
with a few electrons excited from the valence
band into the conduction band
Apply an electric field
Now electrons in the valence band have some
energy sates into which they can move
The movement is complicated since it involves
~ 10
23
electrons
Concept of Holes
Consider a semiconductor with a small number of
electrons excited from the valence band into the
conduction band


If an electric field is applied,
the conduction band electrons will participate in the
electrical current
the valence band electrons can move into the empty
states, and thus can also contribute to the current
Holes from the Band Structure
Point of View
If we describe such changes via
movement of the empty states the
picture can be significantly simplified
This empty space is a Hole
Deficiency of negative charge holes are
positively charged
Holes often have a larger effective mass
(heavier) than electrons since they represent
collective behavior of many electrons
Holes
We can replace electrons at the top of eth
band which have negative mass (and
travel in opposite to the normal direction)
by positively charged particles with a
positive mass, and consider all phenomena
using such particles
Such particles are called Holes
Holes are positively charged and move in
the same direction as electrons they
replace
Hole Conduction
To understand hole motion, one requires
another view of the holes, which represent
them as electrons with negative effective
mass
To imagine the movement of the hole think of
a row of chairs occupied by people with one
chair empty
To move all people rise all together and
move in one direction, so the empty spot
moves in the same direction
Concept of Holes
If we describe such changes via movement
of the empty states the picture will be
significantly simplified
This empty space is called a Hole
Deficiency of negative charge can be treated as
a positive charge
Holes act as charge carriers in the sense that
electrons from nearby sites can move into the
hole
Holes are usually heavier than electrons since
they depict collective behavior of many electrons
Conduction
Electrical current for holes and electrons in the same direction