Lecture 12: Introduction to the

Physics of Solids
U(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

Solid

Atom
+e

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
+e

We represented an atom by
its Coulomb potential
centered on the proton (+e):

r
n=3
n=2
n=1

The potential energy

of the two protons in
an H2 molecule look
schematically like this:

+e

Continuum of free
electron states.

+e

e 2
U( r )
r

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

Atomic ground state:

e 2
U( r )
r

( r ) e r / a0

n=1

Molecular states:
+e

+e

+e

+e

odd

even

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
+e

d
+e

Anti-bonding
Bonding

Now we fill these states with the 2 available electrons

(one from each hydrogen atom)

+e

+e

Eodd
Eeven

Pauli Principle puts

both electrons in
the bonding orbital.

Simple model of a crystal

with covalent bonding
+e

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

Highest energy orbital (N-1 nodes)

1
Lowest energy orbital (zero nodes)

The in between" states

Length of crystal, L

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
electron in a solid:

n (x) u(x)eikn x

u(x) depends on the

atomic states involved:

2s-states
x

u(x)
1s-states

Bloch Wavefunctions and the Energy Band

n (x) u(x)e

For N = 6 there are six different

superpositions of the atomic states that
form the crystal states

ik n x

Highest energy wavefunction

6

Energy

5
4
3
2
1
Lowest energy wavefunction

Closely spaced
energy levels in
this 1s-band

Bloch Wavefunctions and the Free Electron Model

2

n (x) u(x)eikn x

Envelope:

Bloch wavefunction acts almost like free electron wavefunction:

Free electron:
Bloch wave:

eikx

(x) Ae

2k 2
Energy E
2m

ikx

n (x) u(x)e

ik n x

p2

2m

2 k n2
Energy E
2m *

In a perfectly periodic lattice, an electron moves

freely without scattering from the atomic cores !!
Its in a stationary state the Bloch
wavefunction.

m* " effective mass"

e-

Free Electron Model

(x) u(x)eikx

(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:

Also lattice vibrations break the periodicity electrons in metals scatter more at higher temperatures.

Semi-classical Picture of Conduction

n = # free electrons/volume = time between

e-

scattering events

Wire with cross section A

J nevdrift
vdrift

F
eE
a

m
m

ne 2
J
E E
m

ne 2

conductivity
m
Metal:

scattering time gets shorter with

increasing T

Resistivity

J = current density = I/A

F = force = -eE
a = acceleration = F/m

1
m
2
ne

Temperature, T

Why do some solids conduct

current and others dont?
We need to consider
the 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)
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.

Metals have an upper band which is only

partly full
apply an electric field - lots of states of
higher energy available for electron

insulators

semimetals
conductors

Electronic Conduction in a Semiconductor

--example: Si
Z = 14
1s 2s 2p 3s 3p
2

Empty band at T = 0.
(Conduction Band)
3s/3p
band

Energy Gap
Egap 1 eV

valence electrons

Poor conductor at T = 0

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 shorter with

increasing T

Resistivity

1
m
2
ne

Semiconductor: number n of 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
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
(m)
Cu 2x10-8
Si 3x103
Diamond

Resistivity
Carrier Type
Density (cm-3)
1023
conductor
1010
semiconductor
2x1016 small
insulator

The structure as well as the bonding type determine the properties 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?
a. heat the material

b. shine light on it

c. apply a magnetic field

As we increase the temperature,

such that kT Egap, some
electrons are excited to the
conduction band.
As we shine light on the material
(with energy Ephoton > Egap),
electron-hole pairs are created.

It was recently discovered that the magnetic fields can

alter the energy levels of some materials, converting
them from metals semiconductors.

Carbon Nanotubes

We saw earlier that Carbon can be found in a soccer-ball

structure: a Buckyball (60C). More recently, it was discovered
that carbon can also exist in long molecular chains
nanotubes.
These have been observed to have extraordinary properties:

carbon nanotubes are very strong about 100 times stronger

than steel at 1/6 the weight!!
depending on the size/structure of the tube they can behave
like semiconductors or metals potential for molecular
electronics!
they can be filled with other molecules, which can then
alter their properties (peapod photo at right 60C inside
nanotube A. Yazdani, (UIUC Physics 2002)
in the presence of a strong magnetic field, they can change
from a metal into a semiconductor and back -- low-lying
levels make the system metallic, as in our nanotube when no
magnetic field is present. Passing a magnetic field through
the nanotube changes the energies of electrons and opens up
a gap, converting the nanotube into a semiconductor. Higher
fields reverse the effect." A. Bezryadin (UIUC Physics
2004)

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:

Ephoton > 1.1 eV

a. 500 nm
b. 700 nm
c. 1100 nm

Ephoton = 1240 eV-nm/

= 1240/1.1 = 1130 nm