Lecture 11: Introduction to the

Physics of Solids
U(r) a r

6

5

4

3

2

1
 Content
 Energy levels in a solid
 “Bloch wavefunction”
 Energy Bands
 Electrical conductivity and the free-electron model
 Filling the bands with the Pauli Principle
 metals
 semiconductors
 filling energy states in solids

Atom Solid

+e r

n = 3
EF

n = 2
n = 1

Discrete atomic states  band of crystal states  Fill according to Pauli Principle
 Bonding between atoms
-- How can two neutral objects bind together?
H + H  H2

Continuum of free
+e electron states.
r
We represented an atom by
its Coulomb potential n=3
centered on the proton (+e): n=2
e 2
U( r )  
n=1 r

+e +e
The potential energy r
of the two protons in
an H2 molecule look
schematically like this: e 2 e 2
U( r )   
r  r1 r  r2

The wavefunctions for the molecule were the sum of 2 atomic wavefunctions.
 Molecular Wavefunctions and Energies -- H2

+e
r
Atomic ground state: e 2
U( r )  
A r
n=1  ( r )  e  r / a0

Molecular states:
+e +e +e +e
r r

even odd

Bonding state Antibonding state

Remember: These are single-electron states.

Now we will use the Pauli Exclusion principle to fill these states.
 Molecular Wavefunctions and Energies -- H2
The splitting between even and odd states increases as atoms get closer together:

d d
+e +e +e +e
r r

Anti-bonding
Eodd
Bonding Eeven

Now we fill these states with the 2 available electrons Pauli Principle puts
(one from each hydrogen atom) both electrons in
the bonding orbital.
 Simple model of a crystal
with covalent bonding
+e
r
Again start with
simple atomic state: A
n=1

Bring N atoms together together forming a 1-d crystal (a periodic lattice).

(N atomic states N crystal states):

Energy
band

What do these crystal states look like?

-- linear combinations of atomic orbitals.
 Simple model of a crystal
with covalent bonding

N

Highest energy orbital (N-1 nodes)

1

Lowest energy orbital (zero nodes)

 The “in between" states
Length of crystal, L

n
Lattice spacing, a

Envelope: eikx

The wavevector k has N possible values from k = /L to k = /a.

n
kn  n  1,2, ..... L/a N = L/a states
L
Bloch Wavefunction for u(x) depends on the
electron in a solid:
 n (x)  u(x)e ik n x atomic states involved:

2s-states

u(x) x

1s-states
x
 Bloch Wavefunctions and the Energy Band
ik n x For N = 6 there are six different
 n (x)  u(x)e superpositions of the atomic states
that form the crystal states
Highest energy wavefunction
6 Energy

5

4

3

2
Closely spaced
1 energy levels in
this “1s-band”
Lowest energy wavefunction
Bloch Wavefunctions and the Free Electron Model
 n (x)  u(x)e ik n x
2

Envelope: eikx

 Bloch wavefunction acts almost like free electron wavefunction:

ikx  2k 2  p2 
Free electron:  (x)  Ae Energy E   
2m  2m 
 

ik n x  2 k n2
Bloch wave:  n (x)  u(x)e Energy E  m*  " effective mass"
2m *

e-
 In a perfectly periodic lattice, an
electron moves freely without
scattering from the atomic cores !!
It’s in a stationary state –-
the Bloch wavefunction.
 Free Electron Model
 (x )  u(x )e ikx (Bloch wavefunction)

 Electron in a periodic potential has a well defined wavevector

and momentum:
p  k (  h/  )
even though it is traveling in a complicated potential.

 If there is a defect in the crystal, the electron may scatter to

another Bloch state:

e-

 Also lattice vibrations break the periodicity – electrons in

metals scatter more at higher temperatures.
 Semi-classical Picture of Conduction

n = # free electrons/volume
e-  = time between
scattering events
E
Wire with
cross section A J = current density = I/A
J  nev drift
F = force = -eE
F eE
vdrift  a     a = acceleration = F/m
m m
ne 2 ne 2
J E  E    conductivity
m m
Metal: scattering time gets
Resistivity shorter with increasing T
1 m
  2
 ne 

Temperature, T
Why do some solids conduct
current and others don’t?

We need to consider
how electrons fill

The Energy Bands in Solids

 Insulators, Semiconductors
and Metals
Energy bands and the gaps between them determine the conductivity and
other properties of solids.

 Insulators have a valence band which is

full and a large energy gap (few eV) E
 apply an electric field - no states of

higher energy available for electron

 Semiconductors are insulators at T = 0.

They have a small energy gap (~1 eV)
between valence and conduction bands,
so they become conducting at higher T.
insulators semi- metals
 Metals have an upper band which is only conductors
partly full
 apply an electric field - lots of states

of higher energy available for electron

 Electronic Conduction in a Semiconductor
--example: Si Z = 14 1s 2s 2p 3s 3p 2 2 6 2 2

Empty band at T = 0. valence electrons

(Conduction Band)

3s/3p Energy Gap  Poor conductor at T = 0

band Egap ≈ 1 eV

Filled band at T = 0
(Valence band)

The electrons in a filled band cannot contribute to conduction, because with

reasonable E fields they cannot be promoted to a higher kinetic energy.
Therefore, at T = 0, Si is an insulator. At higher temperatures, however,
electrons are thermally promoted into the conduction band:

Metal: scattering time  gets

Resistivity shorter with increasing T
1 m
  2 Semiconductor: number n of
 ne  free electrons increases rapidly
with T (much faster than 
decreases)
Temperature, T (This graph only shows trends. A semiconductor
has much higher resistance than a metal.)
 Summary
 Ability to conduct electricity is useful and common way to classify different
types of solids
Resistivity is defined by:
I 1


J  E
A 
where J = current density and E = applied electric field
 Resistivity depends on the scattering time for electrons.

 Resistivity depends on the number of free electrons (carriers).

Example properties at room temperature:

Material Resistivity Carrier Type
(m) Density (cm-3)
-8 23
Cu 2x10 10
conductor
Si 3x103 1010
semiconductor
 The structure as well as the 2x10
Diamond bonding
16
type determine
small the properties
insulator of a
solid.
 Exercise 1
Consider an electron in the valence band of semiconductor, e.g.,
silicon. Which of the following could be done to elevate it to the
conduction band?

a. heat the material

b. shine light on it

c. apply a magnetic field

 Exercise 1
Consider an electron in the valence band of semiconductor,
e.g., silicon. Which of the following could be done to
elevate it to the conduction band?

As we increase the temperature,

a. heat the material
such that kT  Egap, some
electrons are excited to the
conduction band.
b. shine light on it
As we shine light on the material
(with energy Ephoton > Egap),
electron-hole pairs are created.
c. apply a magnetic field

It was recently discovered that the magnetic fields can

alter the energy levels of some materials, converting
them from metals  semiconductors.
 Digital Thermometers
 Many modern digital thermometers use a
“thermistor”, a semiconductor device whose
conductance (and hence, whose resistance)
depends on temperature. When the temperature
increases, the thermal energy (~kT) is enough to
promote some of the electrons from the valence
band into the conduction band. The resistance of
the material drops markedly, and can be used to
determine the temperature.
 Photodetectors
 Shining light onto a semiconductor can excite electrons out of the
valence band into the conduction band. The change in resistance
can then be used to monitor the light intensity.
 Examples:
 photodiode
 electric eye

 optical power meter

 barcode scanner

 digital camera (each pixel)

 camcorder
 photovoltaic = “solar cell”
 etc.
 Exercise 2
The bandgap in Si is 1.1 eV at room temperature. What is
“reddest” color (i.e., the longest wavelength) that you could
use to excite an electron to the conduction band? (Hint: Si
is used in the pixels of your digital camera.)

a. 500 nm

b. 700 nm

c. 1100 nm
 Exercise 2
The bandgap in Si is 1.1 eV at room temperature. What is
“reddest” color (i.e., the longest wavelength) that you could
use to excite an electron to the conduction band? (Hint: Si
is used in the pixels of your digital camera.)
The photon energy must be at
least as great as the bandgap:
a. 500 nm
Ephoton > 1.1 eV

b. 700 nm
Ephoton = 1240 eV-nm/
c. 1100 nm
 = 1240/1.1 = 1130 nm