The Solid State

Crystalline and Amorphous Solids

Ionic Crystals

“The universe consists only of atoms and the void: all else is opinion and
illusion.”–Edward Robert Harrison
 Chapter 10
The Solid State

10.1 Crystalline and Amorphous Solids

Crystalline and amorphous are the two major categories into
which solids are divided.

Crystalline solids exhibit long-

range order in their atomic
arrangements.

Silicon crystal surface.

http://www.aip.org/history/einstein/atoms.htm
The order in crystals is usually three dimensional, but
lower dimensionality order is possible.

Bonds in crystalline solids are more or less the same in

energy, and crystalline solids have distinct melting
temperature.

mercury

(Don’t try
this at
home!)
Amorphous solids exhibit only short-range order in their atomic
arrangements. They lack long-range order.

Their bonds vary in energy and are weaker; they have no

distinct melting temperature.

A good example is B2O3. Here’s figure 10.1b, crystalline B203.

All crystals have atoms which are

“equivalent;” the symmetry of all
equivalent atoms is the same.

For example, these two boron atoms

are equivalent; everything around
them looks the same.
Here’s how you tell if a solid is crystalline:

Imagine you are a nanohuman. If you build a house on some

boron atom and look out any window in some direction…

You’ll have exactly the same

view if you build your house on
an equivalent boron atom and
look out in an equivalent
direction.

Note that “equivalent direction”

does not mean “the same
direction.”
See Figure 10.1a for amorphous B2O3.

Every B is surrounded by a
“triangle” of 3 O’s, just as for
crystalline B2O3.

But you can’t find two B atoms

that give you an identical “view.”
Eventually the short-range order
breaks down, and every “view”
is different.

“Amorphous” means “formless” or “shapeless” but amorphous

materials still have short-range order. The appropriate
definition of “amorphous” for us is “lacking a distinct crystalline
structure.” (www.dictionary.com)
 Defects in Crystals

Image “borrowed” from http://comp.uark.edu/~pjansma/geol3513_25_defmechs1_04.ppt who

got it from “Davis & Reynolds 1996.”
It's easy to think of real crystals as having these ideal
structures.

In fact, no crystals are perfect; all crystals have defects.

Crystals can have:

• The "right" atoms in "wrong" places.

• "Wrong" atoms in "right" or "wrong" places.

• Missing atoms.

• Etc.

One type of defect is the point defect.

There are three basic kinds of point defects.

• (1) A vacancy.

Actually, a vacancy would probably look more like this:

 • (2) An interstitial.

There is likely a vacancy somewhere else in the crystal, which

supplied the interstitial atom.
• (3) An impurity, which could be either substitutional or
interstitial.

substitutional interstitial
Point defects makes diffusion in solids possible.

Either vacancies or interstitial atoms can migrate

through a crystal.

Diffusion is strongly temperature dependent.

Higher dimensional defects include edge and screw dislocations.

A dislocation occurs when a line of atoms is in the wrong place.

Dislocations are important but more difficult to deal

with than point defects.
Edge dislocation are relatively easy to draw and visualize. See
Figure 10.3.

http://uet.edu.pk/dmems/edge_dislocation.htm dead link spring 2005

Screw dislocation are more difficult to draw. See Figures 10.4
and 10.5.

http://www.techfak.uni-kiel.de/matwis/amat/def_en/kap_5/backbone/r5_1_1.html

Atoms in crystals are not static, and neither are dislocations.

edge dislocation
 edge dislocation

http://www.techfak.uni-kiel.de/matwis/amat/def_en/kap_5/illustr/a5_1_1.html
 screw dislocation

http://uet.edu.pk/dmems/screw_dislocation.htm
Work hardening (you have probably tried this at home).

Work hardening occurs when so many dislocations are

formed in a material that they impede each others'
motion.

Hard materials are usually brittle.

Annealing.

Heating (annealing) a crystal can remove

dislocations. The edge dislocation animation
from Germany we saw showed an edge
dislocation being annealed out.

Annealing makes metals more ductile, and can be used

to remove secondary phases in crystals.
10.2 Ionic Crystals
An atom with a low ionization energy can give up an electron to
another atom with a high electron affinity. The result is an ionic
crystal.
To calculate the stability of an ionic crystal, we need to consider
all of the energies involved in its formation.
+ Positive energy is required to ionize an atom.
Energy is released when a highly electronegative atom
- gains an electron (energy becomes more -).

 There are  contributions to the energy from the

Coulomb force between charged ions.
There is a + contribution to the energy from the overlap
+ of core atomic electrons (the Pauli exclusion principle at
work).
Remember that negative energies mean stable systems. If you
add up all the above energies and get a more negative energy
than for the separate, isolated atoms, then the ionic crystal is
stable.

We’ll go through that exercise soon.

Ionic crystals are generally close-packed, because nature

"wants" as many ions of different charge squeezed together as
possible.

Like-charged ions never come in contact.

There are two primary structures for ionic crystals.

Face-centered cubic (fcc).

http://members.tripod.com/shiner17/Crystals/BravaisLattice/
Cubic/FaceCenteredCubic.htm
An example of the fcc structure is sodium chloride (NaCl).

NaCl NaCl
a bit of the
front sliced off

http://sbchem.sunysb.edu/msl/nacl.html
The other main ionic crystal structure is body-centered cubic
(bcc).
An example of the bcc structure is cesium chloride (CsCl).

It is not too difficult to calculate the energies involved in ionic

bonding, so let’s do it.

We begin by defining the cohesive energy of an ionic crystal

as “the reduction in the energy per ion of the ionic crystal
relative to the neutral atoms,” or “the energy per ion needed to
break the crystal up into individual atoms.”

Later Beiser implicitly generalizes this definition to all

crystals.

Let's calculate the contribution to the cohesive energy from the

Coulomb potential energy. Let's do it for an fcc structure, NaCl
for example.
Let’s add up all contributions to the Coulomb energy from ion-
ion interactions. Let's take a Na+ ion as the reference* ion
(NaCl is made of Na+Cl- ions). We get the same result if we
take a Cl- as the reference.

Here’s the reference ion.

Each Na+ ion has six Cl- nearest r

neighbors a distance r away. Here are
four of them.

Where are the other two Cl’s?

showing these 4 Na’s just to
help you get your bearings
here
and
*Remember, the energy is
here calculated per ion.
The contribution to the Coulomb potential from these six
nearest neighbors is

6 +e  -e  6 e2
U1 = =- .
4ε0r 4ε 0r
This represents a negative (more stable) contribution to the
total energy.

Each Na+ has 12 Na+ next-nearest

neighbors at a distance of 21/2r. These
r 2
are + ions, so the interaction is
repulsive, and the contribution to the
total energy is positive. This figure
shows four of the next-nearest
neighbors.
There are four more (red) in the plane above and four more in
the plane below.

“above”

“original” plane

“below”
The contribution from the twelve next-nearest neighbors is

12 e2
U2 = + .
4ε0r 2
This represents a positive (less stable) contribution to the total
energy.

You could keep on like this for shell after shell. Pretty soon a
pattern would emerge. After “many” shells, you get
2 2
e  12  e
U= -  6- + ... = -1.748
4ε 0r  2  4ε0r
2
e
U= -
4ε 0r
The constant  (which is constant only for a given type of
structure) is known as the Madelung constant. Beiser gives
values of  for a couple of other structure types.

 12 
 = 6 - + ... =  6 - 8.485281 + ...
 2 
The convergence of this series is very poor. You have to find a
clever way to do this series if you want to calculate  with a
reasonable amount of effort.

We've accounted for the Coulomb attraction. Beiser calls this

Ucoulomb (using U instead of V as in the previous edition) so let’s
make it official:
2
e
Ucoulomb = - 
4ε 0r
 12 8 12 24
  6     ...
2 3 2 2 5
This isn’t the whole story!
e2
Ucoulomb = -
4ε 0r
Note the - sign in the equation for U. The net coulomb
interaction is attractive.

In fact, the closer the ions, the more negative the energy. The
more negative, the more stable. What is the logical conclusion
from this observation?

As r gets smaller and smaller, electron shells start to overlap,

and electrons from different atoms share the same potential.

What does Pauli have to say about that?

Electrons would have to be promoted to higher energies to
allow atoms to come closer together. The result is a more
positive energy, i.e., a less stable crystal.

So we need to account for the repulsive forces that take over

when electron shells start to overlap, and different electrons
share the same set of quantum numbers.

We model this repulsive force with a potential of the form

B
Urepulsive = n
,
r
where n is some exponent. The exact value of n isn't too
critical (see the figure on the next page).
A simple scale factor change could make 1/r9 and 1/r10 look
nearly the same.
With the electron overlap repulsive energy accounted for, the
potential energy of interaction of our Na+ reference ion with all
the other ions is
e2 B
Utotal = Ucoulomb + Urepulsive = - + n.
4ε 0r r
Even though this says Utotal, we are not done!

For one thing, we have accounted for the total energy of

interaction of the ions (that’s what “total” means), but we
haven’t accounted for the energy required to ionize the neutral
atoms.
For another thing, we have this adjustable parameter, B. (You
do remember adjustable parameters?)
At equilibrium the energy is minimized, which allows us to find
B in terms of  and the equilibrium near-neighbor separation r0.

2
 U   e nB
0=  = 2
- n+1
 r  r = r 0
4ε 0r0 r0

2
e nB
2
= n+1
4ε 0r0 r0
2
e n-1
B= r0
4ε 0n
In a sense, we have “adjusted” B to get the right answer
(energy minimum at equilibrium).
Plugging B back into the expression for U gives the total
potential energy at equilibrium separation. Beiser used to call it
the lattice energy, Vlat. Now he calls it U0.

2
e  1
U0 = -   1-  .
4ε0r0  n 

U0 is the reduction in the energy of the ionic crystal relative to

the ions at infinite separation.

We set out to calculate the cohesive energy, so we are still not

done yet.

The cohesive energy, Ecohesive, takes into account the energy

needed to create the ions.
Beiser doesn’t give an equation for the cohesive energy, so I’ll
make one up. The energy of the ions is U0. The energy to
create a Na+ ion is the ionization energy of Na. I’ll call that
Uion.
When a Cl atom combines with an electron to form Cl-, energy
is actually released. Chemists call this energy the electron
affinity. I’ll write that Uea.

Ecoh, pair = U0 + Uion + Uea .

You’ll see what “pair” means in a minute. Also, the numerical

value of Ecoh had better be negative, right?

Uion is positive, because it is energy put into the crystal. Uea is

negative, because it is energy released from the crystal.
Oh, and one more thing. We’ve calculated the coulomb energy
for our reference Na+ with all other ions in the crystal, one pair
at a time. Thus, U0 is the energy per ion pair.

Also, Uion is the energy to make Na+ and Uea is the energy
released on making Cl-. Thus Uion + Uea represents the energy
needed to make a Na+Cl- pair.

Beiser defines the cohesive energy as “per ion.” Thus finally

(and officially):

U0 + Uion + Uea
Ecoh = .
2
Beiser on page 342 calculates the cohesive energy for
NaCl.

A “typical” value for n is 9. The equilibrium distance r0 between

Na+ and Cl- ions is 0.281 nm.

Beiser calculates numerical values for the different energies,

and then combines them to get the cohesive energy.

We know it’s better to do the problem algebraically first, and

get numerical results only at the very end.

Let’s do it Beiser’s way here.

 e2  1 
U0 = -   1- 
4ε0r0  n 
only for NaCl
structure!
2

U0 = - 1.748 
1.6  10 
-19
 1
1- 9 
4  8.85  10  0.281  10  
-12 -9


U0 = -1.27  10-18 joules = - 7.96 eV .

The ionization energy of Na is 5.14 eV and the electron affinity

of Cl is 3.61 eV. With the correct signs, the energies are +5.14
eV and -3.61 eV. Make sure you understand why! Many of you
will lose several points because of sign errors.
 U0 + Uion + Uea
Ecoh =
2

-7.96 eV + 5.14 eV - 3.61 eV

Ecoh =
2

Ecoh = - 3.21 eV

Great news! We got a – sign for the cohesive energy. You can
sleep well at night knowing that NaCl is stable.

Wonder how it compares with experiment? The measured

value is -3.28 eV. That’s a 2% error. For this kind of
calculation, the agreement is good.
Why did I bother with this rather lengthy calculation to show
that NaCl is stable, when we already know it is stable?

Stupid?

Physicists may do stupid things, but we are not stupid.

Designer molecules! If you have an application that needs a

compound with special properties, do you spend millions in the
lab and hope you stumble across it… or do you spend a few
hundred thousand on computational modeling that tells you
what kind of compound to make?

The calculation we did is your first step towards making

designer molecules.
Some properties of ionic crystals, which Beiser mentions briefly:

• They have moderately high

melting points.

• They are brittle due to

charge ordering in planes.

• They are soluble in polar

fluids.
 The Solid State

Covalent Crystals

Van der Waals Forces

The Metallic Bond

“It was absolutely marvelous working for Pauli. You could ask him
anything. There was no worry that he would think a particular question
was stupid, since he thought all questions were stupid.”—V. Weisskopf
Now we see how an ionic crystal dissolves in a polar fluid like
water:
10.3 Covalent Crystals

There are relatively few 100% covalent crystals in

nature.
Examples: diamond, silicon, germanium, graphite (in
plane), silicon carbide.

These materials are all characterized by tetrahedral

bonding, which involves sp3 hybrid orbitals.
Hybrid orbitals result when two or more atomic orbitals
of an isolated atom mix in covalently-bonded atoms
(we’ll discuss this in more detail later).

This is one of the four hybrid orbitals formed by

the hybridization of one s and three p orbitals.

tetrahedral bonding
http://www.siue.edu/
CHEMISTRY/resources/
orbitals/sp3.htm
Some properties of covalent crystals:
• They are brittle due to their highly directional
bonding.
• They have high melting points due to their high bond
strengths.

• They have low impurity solubility due to their

directional sp3 hybrid bonds.

• They are insoluble in polar fluids.

Diamond structure:
(two interpenetrating fcc
lattices)
Graphite structure (like diamond but only in planes)

http://cst-www.nrl.navy.mil/lattice/struk.xmol/olda9.xyz
10.4 Van der Waals Forces
Even inert gases form crystals at low temperatures.
What force holds them together?
• Ionic bonds? No, because inert gases don't ionize.
• Covalent bonds? No, because inert gases have no
"desire" to share electrons.
• Some kind of Coulomb attraction? Inert gases are are
electrically neutral, so they don't attract charged
particles.
• “Hydrogen bonding,” where asymmetry of the
molecule gives rise to a nonuniform charge distribution
and a polarity? Not if inert gas atoms are nonpolar
The answer is that, while on the
average inert gas atoms are nonpolar,
their electrons are in constant motion
and they can have instantaneous
nonuniform charge distributions.

The + and - portions of the atom can exert attractive force,

which is enough to bond at very low temperatures.

A dipole of moment p gives rise to an electric field E given by

  
      
1 p 3 p r 
E=  3 - 5 r .
4 ε0  r r 
This electric field can induce a dipole moment in a normally
nonpolar molecule.
The induced dipole moment is
 
p = αE ,
where  is the polarizability of the molecule or atom.

The energy of the induced dipole in the electric field is

 

U= -p E,
and it is not too difficult to show that U is proportional to -1/r6.

Things to note: the potential is negative (attractive, stable).

The force is proportional to dU/dr which is proportional to 1/r7,
so the force drops off very rapidly with distance.
Comments about van der Waals forces

• Van der Waals forces are responsible for hydrogen

bonding, such as occurs in water.

• Van der Waals forces are always present, but at even

moderate temperatures they are so relatively weak that
they can safely be neglected.

• Our brief derivation is a classical one, and, as you

might suspect, not really correct at the atomic level.
However, a full quantum mechanical derivation gives
the same r-dependence. (Harmonic oscillators!)
Hydrogen bonding:

“The attraction of the partially positive end of one highly polar

molecule for the partially negative end of another highly polar
molecule is called a hydrogen bond.”
http://207.10.97.102/chemzone/lessons/03bonding/mleebonding/hydrogen_bonds.htm
The Lennard-Jones potential, which you may have
encountered in chemistry (also sometimes known as the
Lennard-Jones 6-12 potential or the 6-12 potential) describes
van der Waals forces.

 σ 12  σ 6 
ULJ  r  = 4ε   -    .
 r   r  

overlap (pauli) van der Waals

adjustable parameters

This potential models the interaction between pairs of atoms.

In section 10.2, we used an 1/r9 dependence for ionic crystals
instead of the 1/r12 dependence here. The difference can be
“absorbed” in our adjustable parameters.
H bond are typically about a tenth as strong as
covalent bonds.

Each H2O molecule can form

H bond with 4 other
molecules

H bond occur in biological

materials e.g. DNA
10.5 Metallic Bond
Metallic bonding is caused by electrostatic forces acting in
combination with the Heisenberg uncertainty principle and the
Pauli exclusion principle.

Metal atoms give up electrons (usually one or two,

sometimes three). The result is a lattice of positive ion
cores sitting in a "sea" or "gas" of electrons.

-
+ - + + + - + + +
- -
- -
- + - + + + - + - + -
- - + -
+ + - + - + + +
- - -
The electrons in the gas repel each other. The electron gas and
ion cores attract each other. Bonding occurs because the
reduction in energy due to the attraction exceeds the increase in
energy due to repulsion.

“Don't we have a problem here?”

If we bring 1022 or so atoms together and try to combine that

many electrons into a single "system," don't we have a problem
with the Pauli exclusion principle?

We sure do. It would seem that the energies of most of the

electrons would need to be so high (remember, energies go up
as we put electrons in successively further out shells) that the
net electron energy would be so great that bonding could never
occur.
How do we get around this? The energy levels of the
overlapping electron shells are all slightly altered. The energy
differences are very small, but large enough so that a large
number of electrons can be in close proximity and still satisfy
the Pauli exclusion principle.

We are describing the formation of energy bands, consisting of

many states close together but slightly split in energy.

These energy states are so close together that for all practical
purposes we can consider bands as a continuum of states,
rather than discrete energy levels like we have in isolated atoms
(and in the core electrons of atoms of metals).
“This sounds seriously artificial.” True, it sounds like an ad hoc
explanation. “Did you make it up—you know, just to keep from
having to explain it to us?” “Where do these bands come
from?”

We should first ask where the electronic energy

levels in atoms “come from.”

Remember, we solved the Schrödinger equation for an electron

in the potential of the hydrogen nucleus. This gave us our
energy levels and quantum numbers.

More complex atoms require more complex mathematics, but

the idea is the same: the energy levels come from the solution
of Schrödinger's equation for electrons in the potential of the
nucleus.
The same holds for metals, except now we have a periodic array
of nuclei, and a periodic potential. We still have to solve
Schrödinger's equation for an electron moving in this periodic
potential.

The problem can't be solved exactly, of course, but it can be

solved with quite reasonable accuracy.

The energy bands result quite naturally from the solution, just
as energy levels in atoms came naturally out of the solution to
Schrödinger's equation.

Actually, “we” don’t have to solve anything (unless we are

physicists). The electrons know how to do it. They solve
Schrödinger’s equation for us. We just have to discover what
they tell us.
This is a bit unsatisfying right now.
“Look, but don’t eat.” However, we
will discuss band theory in more
detail in later sections in this chapter.

Ohm’s Law

Any reasonable theory of the solid state should be able to come

up with Ohm's law. Since we are talking solids and metals, now
is a good time to give it a try.

Ohm’s law is not really a fundamental law. It is V

I=
an empirical relationship that (usually) works for R
(some) solids.
You’d feel a bit better about Ohm’s law if we could derive it,
wouldn’t you? Let’s try.

What do electrons in a conductor do in the absence of an

applied electric field?
-
+ - + + + - + + +
- - - -
- + - + + + - + - + -
- - + -
+ + - + - + + +
- - -

They move, very rapidly, but in random directions. There is no

net current.

I’m not going to put velocity vectors on all the electrons. I hope
you get the idea!
Let’s just follow one of the electrons. What happens when an
electric field is applied?

E electron drift velocity

+ + + + + + +

- + + + + + +

+ + + + + + +

Electrons accelerate and gain a net "drift" velocity in some

direction. We will see that the drift velocity is actually very small
compared to the Fermi velocity.
Since an electric field accelerates electrons, why don't they
move faster and faster? Or do they do just that?

E electron drift velocity

+ + + + + + +

- + + + + + +

+ + + + + + +

They don’t. Some force must eventually oppose the force due
to the electric field and bring the drift velocity into a "steady
state" condition.
What is this "force"? Collisions with + ions? Attractive idea,
and used in classical theory—which failed miserably.
Collisions with other electrons? No, electrons don’t “like” each
other (Pauli) and thus don’t interact like particles.

So what is this "force“ that causes resistance? Typically it is a

result of collisions of electrons with impurities.

“Impurities” means defects like we talked about earlier (point

defects, dislocations), the edges of the metal, or atoms
temporarily out of their equilibrium position because they are
vibrating like balls connected by springs.

Let's analyze this situation mathematically. Ohm's law had

better come out of the analysis.
Only electrons near the Fermi energy can be accelerated
(remember, all energy states below εF are occupied).

Those electrons near the Fermi level (which can be accelerated)

start with some random velocity (about vF in magnitude but
random in direction).

They gain “additional” velocity (in a direction opposite the

electric field direction) until they collide with an impurity.

The collision with the impurity “randomizes” the velocity, and the
process starts over again.

If we define λ as the mean free path of electrons between

collisions, then the average time between collisions is
λ
= .
vF
An applied electric field results in a force on the electron, and
therefore an acceleration
f eE
a = = .
m m
Since the electron is accelerated only during the time , after
which it undergoes a collision and has its velocity randomized
again, the average gain in velocity, or "drift velocity," is

eE 

vd = a = .
mv F
The current in the conductor is
I =  n   e  v d  A 

 eEλ 
I = n  e   A
 mv F 

n A e2 E λ
I =
mv F

The potential V across a length L of the conductor is related to

the electric field by E = V / L. Thus…
 V
2
nAe λ
I = L
mv F

 n e2 λ   A 
I =    V
 mv F   L 

V
I = ,
R

where
 mv F   L  L 
R =  2   = ρ   .
 n e λ  A  A

The resistivity, , of the metal is defined by the above equation.

We need to see if this works (we’ll do that in a minute). If it
does, a simple drift velocity theory, based on the electron gas
and some quantum mechanics (noninteracting electrons) has led
us to Ohm’s law.

This may not seem like much, but our inability to get within
even a factor of 10 of Ohm’s law at the start of the 20th century
was a major unsolved problem in solid state physics. See the
note on the Wiedemann-Franz law on page 354

Example 10.3 The resistivity of copper at 20 ºC is 1.72x10-8

·m. Estimate the mean free path between collisions of the
free electrons in copper at 20 ºC. (The temperature is specified here only
because resistivity is temperature-dependent, so you should give a temperature when
you give a resistivity.)
The density of free electrons in copper is n = 8.48x1028 m-3. I
could give you this, or give you the density and atomic mass of
copper and expect you to calculate this.

The Fermi energy may be given, or you may need to calculate it.
From the value of n above, you can calculate F = 7.04 eV.

The Fermi velocity may be given, or you may need to calculate it

from KE = F = (1/2) m vF2.
vF = 1.57x106 m/s.
Now that we have all the input parameters, we use our equation
for resistivity to calculate the mean free path.

I haven’t yet written down an expression for resistivity, so let’s

do it now, and make it “official.”

mv F
 = 2
.
ne λ
mass of what
“thing”?
mv F
λ =
n e2 ρ

λ =
 
9.11×10-31 1.57×106 
-19 2
 8.48×10 28

1.6×10   1.72×10-8 
keep everything SI so you don’t have
to worry about units
 λ = 3.83×10-8 m = 38.3 nm .

That’s the mean free path of the electrons in copper. Not very
far, huh?

“Hold it right there! The atoms in copper are about 0.26 nm

apart. An electron travels past about 38.3/0.26 = 150 of them
without being scattered!”

“So you’re saying the negative electrons don’t even know the
positive ions are there?” Yup.

Electron waves in a perfect periodic lattice interact with the

lattice only under very special circumstances.

Resistivity (which comes from collisions) is due to imperfections

in the lattice.
Resistivity comes from impurities and vibrations of atoms about
their equilibrium positions.

You can remove impurities to increase conductivity.

You can remove lattice vibrations (called “phonons”) by cooling

the conductor. This also increases conductivity.

You can cool a sample to a low enough temperature where

lattice vibrations add very little to the resistivity. The remaining
resistivity is due to impurities. The “residual resistivity ratio” is a
very important way of assessing the purity of your samples.
10.6 Band Theory of Solids

What happens in crystalline solids when we bring atoms so

close together that their valence electrons constitute a single
system of electrons?

“You do not really understand something unless you can explain it to your
grandmother.”—A. Einstein
The energy levels of the
overlapping electron shells
are all slightly altered.

The energy differences are

very small, but enough so
that a large number of
electrons can be in close
proximity and still satisfy the
Pauli exclusion principle.

The result is the formation

of energy bands,
consisting of many states
close together but slightly
split in energy.
The energy levels are so close together that for all practical
purposes we can consider bands as a continuum of states,
rather than discrete energy levels as we have in isolated atoms
(and in the core electrons of atoms of metals).

A detailed analysis of energy bands shows that there are

as many separate energy levels in each band as there are
atoms in a crystal.*

Suppose there are N atoms in a crystal. Two electrons

can occupy each energy level (spin), so there are 2N
possible quantum states in each band.

Let’s consider sodium as an example. Sodium has a single

outer 3s electron.

*Kind of. I need to explain.

When you bring two sodium
atoms together, the 3s
energy level splits into two
separate energy levels.

Things to note: 4 quantum

states but only 2 electrons.

You could minimize electron energy by putting both 3s electrons

in the lower energy level, one spin up and the other spin down.

There is an internuclear separation which minimizes electron

energy. If you bring the nuclei closer together, energy
increases.
When you bring five sodium
atoms together, the 3s
energy level splits into five
separate energy levels.

The three new energy

levels fall in between the
two for 2 sodiums.

There are now 5 electrons occupying these energy levels.

I’ve suggested one possible minimum-energy configuration.

Notice how the sodium-sodium internuclear distance must
increase slightly.
When you bring N (some
big number) sodium atoms
together, the 3s energy
level splits into N separate
energy levels.

The result is an energy

band, containing N very
closely-spaced energy
levels.

There are now N electrons occupying this 3s band. They go

into the lowest energy levels they can find.

The shaded area represents available states, not filled states.

At the selected separation, these are the available states.
Now let’s take a closer look at
the energy levels in solid
sodium.

Remember, the 3s is the 3s band

outermost occupied level. begins to
form

When sodium atoms are

brought within about 1 nm of
each other, the 3s levels in the
individual atoms overlap
enough to begin the formation
of the 3s band.

The 3s band broadens as the

separation further decreases.
Because only half the states in
the 3s band are occupied, the
electron energy decreases as
the sodium-sodium separation
decreases below 1 nm. 3s electron
energy is
minimized
At about 0.36 nm, two things
happen: the 3s energy levels
start to go up (remember
particle in box?) and the 2p
levels start to form a band.

Further decrease in interatomic

separation results in a net
increase of energy.
What about the 3p and 4s
bands shown in the figure?
Don’t worry about them—there
are no electrons available to
occupy them!
Keep in mind, the bands do
exist, whether or not any
electrons are in them.

What about the 1s and 2s

energy levels, which are not
shown in the figure?
The sodium atoms do not get
close enough for them to form
bands—they remain as atomic
states.
Figure 10-20 (the one on the last three slides) shows energy
levels as a function of interatomic separation.

Energy levels for a crystal structure with fixed interatomic

distances vary with different directions in space.

http://www.chem.brown.edu/chem50/Notes/classpics/onefig.html, sorry about the picture

quality.
As an aid to visualization, we often represent energy bands like
this (using sodium as an example):

This is highly schematic. Real

bands aren't boxes or lines. εF
3s
Sodium has a single 3s
electron, so the 3s energy 2p
band contains twice as many 2s
states as there are electrons.
The band is half full.
1s
At T=0 the band is filled exactly halfway up, and the Fermi
level, εF, is right in the middle of the band.

Sodium is a metal because an applied field can easily give

energy to and accelerate an electron.
Magnesium has two 3s electrons.
You expect the 3s band to be full, 3p
the 3p band to be empty, with a
forbidden gap in between.
Magnesium should be an insulator.
(Why?)
3s
But magnesium is a metal
(actually, a “semimetal”).

The 3p and 3s bands overlap.

3p
There are many empty states
nearby into which electrons can be
accelerated. 3s
Materials which have bands either 3p
completely full or completely
empty are insulators (unless band
overlap occurs, as was the case for
magnesium).
3s

In a carbon atom, the 2p shell contains 2 electrons. There

are 6 available states, so one would expect the 2p band to be
1/3 full* and carbon to be a conductor.
But carbon is an **insulator. Why?

*2N 2p electrons in a crystal with N atoms. 6N 2p states, when you include spin.

**If the diamond in your diamond ring conducts electricity, it’s time to take it back!
Figure 10.23 shows energy
bands in carbon (and
silicon) as a function of
interatomic separation.

At large separation, there is

a filled 2s band and a 1/3
filled 2p band.

But electron energy can be lowered if the carbon-carbon

separation is reduced.
There is a range of carbon-carbon separations for which the 2s
and 2p bands overlap and form a hybrid band containing 8N
states (Beiser calls them “levels”).
But the minimum total
electron energy occurs at
this carbon carbon
separation.

At this separation there is a

valence band containing 4N
quantum states and
occupied by 4N electrons.

The filled band is separated by a large gap from the empty

conduction band. The gap is 6 eV—remember, kT is about
0.025 eV at room temperature. The gap is too large for
ordinary electric fields to move an electron into the conduction
band. Carbon is an insulator.
  electrons 
charge    charge 
=  volume  
time time   electron 
 
 distance 
   cross - section 
×  traveled   
   area of conductor 
 by electron 

charge  electrons   charge 

=   
time volume   electron 
 distance traveled   cross - section 
×   
time   area of conductor 

I =  n   e  v  A 
d
 The Solid State

Band Theory of Solids

“You do not really understand something unless you can explain it to your
grandmother.”—A. Einstein
10.6 Band Theory of Solids

What happens in crystalline solids when we bring atoms so

close together that their valence electrons constitute a single
system of electrons?

Band structure of diamond. http://home.att.net/~mopacmanual/node372.html

The energy levels of the
overlapping electron shells
are all slightly altered.

The energy differences are

very small, but enough so
that a large number of
electrons can be in close
proximity and still satisfy the
Pauli exclusion principle.

The result is the formation

of energy bands,
consisting of many states
close together but slightly
split in energy.
The energy levels are so close together that for all practical
purposes we can consider bands as a continuum of states,
rather than discrete energy levels as we have in isolated atoms
(and in the core electrons of atoms of metals).

A detailed analysis of energy bands shows that there are

as many separate energy levels in each band as there are
atoms in a crystal.*

Suppose there are N atoms in a crystal. Two electrons

can occupy each energy level (spin), so there are 2N
possible quantum states in each band.

Let’s consider sodium as an example. Sodium has a single

outer 3s electron.

*Kind of. I need to explain.

When you bring two sodium
atoms together, the 3s
energy level splits into two
separate energy levels.

Things to note: 4 quantum

states but only 2 electrons.

You could minimize electron energy by putting both 3s electrons

in the lower energy level, one spin up and the other spin down.

There is an internuclear separation which minimizes electron

energy. If you bring the nuclei closer together, energy
increases.
When you bring five sodium
atoms together, the 3s
energy level splits into five
separate energy levels.

The three new energy

levels fall in between the
two for 2 sodiums.

There are now 5 electrons occupying these energy levels.

I’ve suggested one possible minimum-energy configuration.

Notice how the sodium-sodium internuclear distance must
increase slightly.
When you bring N (some
big number) sodium atoms
together, the 3s energy
level splits into N separate
energy levels.

The result is an energy

band, containing N very
closely-spaced energy
levels.

There are now N electrons occupying this 3s band. They go

into the lowest energy levels they can find.

The shaded area represents available states, not filled states.

At the selected separation, these are the available states.
Now let’s take a closer look at
the energy levels in solid
sodium.

Remember, the 3s is the 3s band

outermost occupied level. begins to
form

When sodium atoms are

brought within about 1 nm of
each other, the 3s levels in the
individual atoms overlap
enough to begin the formation
of the 3s band.

The 3s band broadens as the

separation further decreases.
Because only half the states in
the 3s band are occupied, the
electron energy decreases as
the sodium-sodium separation
decreases below 1 nm. 3s electron
energy is
minimized
At about 0.36 nm, two things
happen: the 3s energy levels
start to go up (remember
particle in box?) and the 2p
levels start to form a band.

Further decrease in interatomic

separation results in a net
increase of energy.
What about the 3p and 4s
bands shown in the figure?
Don’t worry about them—there
are no electrons available to
occupy them!
Keep in mind, the bands do
exist, whether or not any
electrons are in them.

What about the 1s and 2s

energy levels, which are not
shown in the figure?
The sodium atoms do not get
close enough for them to form
bands—they remain as atomic
states.
Figure 10-20 (the one on the last three slides) shows energy
levels as a function of interatomic separation.

Energy levels for an actual crystal structure also vary with

different directions in space.

http://cmt.dur.ac.uk/sjc/thesis/thesis/node39.html, band structure of silicon

As an aid to visualization, we often represent energy bands like
this (using sodium as an example):

This is highly schematic. Real

bands aren't boxes or lines. εF
3s
Sodium has a single 3s
electron, so the 3s energy 2p
band contains twice as many 2s
states as there are electrons.
The band is half full.
1s
At T=0 the band is filled exactly halfway up, and the Fermi
level, εF, is right in the middle of the band.

Sodium is a metal because an applied field can easily give

energy to and accelerate an electron.
Magnesium has two 3s electrons.
You expect the 3s band to be full, 3p
the 3p band to be empty, with a
forbidden gap in between.
Magnesium should be an insulator.
(Why?)
3s
But magnesium is a metal
(actually, a “semimetal”).

The 3p and 3s bands overlap.

3p
There are many empty states
nearby into which electrons can be
accelerated. 3s
Materials which have bands either 3p
completely full or completely
empty are insulators (unless band
overlap occurs, as was the case for
magnesium).
3s

In a carbon atom, the 2p shell contains 2 electrons. There

are 6 available states, so one would expect the 2p band to be
1/3 full* and carbon to be a conductor.
But carbon is an **insulator. Why?

*2N 2p electrons in a crystal with N atoms. 6N 2p states, when you include spin.

**If the diamond in our diamond ring conducts electricity, it’s time to take it back!
Figure 10.23 shows energy
bands in carbon (and
silicon) as a function of
interatomic separation.

At large separation, there is

a filled 2s band and a 1/3
filled 2p band.

But electron energy can be lowered if the carbon-carbon

separation is reduced.
There is a range of carbon-carbon separations for which the 2s
and 2p bands overlap and form a hybrid band containing 8N
states (Beiser calls them “levels”).
But the minimum total
electron energy occurs at
this carbon carbon
separation.

At this separation there is a

valence band containing 4N
quantum states and
occupied by 4N electrons.

The filled band is separated by a large gap from the empty

conduction band. The gap is 6 eV—remember, kT is about
0.025 eV at room temperature. The gap is too large for
ordinary electric fields to move an electron into the conduction
band. Carbon is an insulator.
Silicon has a similar band
structure. The forbidden
gap is about 1 eV.

The probability of a single

electron being excited
across the gap is small,
proportional to
exp(-Egap/kT).

However, there are enough 3s+3p electrons in silicon that some

of them might make it into the conduction band. We need to
consider such a special case.
On page 355 Beiser says there are as many levels in a band (N) as there are atoms
in a crystal. In figure 10.23 the caption implies there are 2N levels in a 2s band.
This is inconsistent. Let’s call a “level” an energy level and a “state” a quantum
state, including spin. Then figure 10.23 should talk about 2N states in a 2s band.
A semiconductor is a material which has a filled (at T=0)
valence band separated by a small gap from an empty (at
T=0) conduction band.

conduction
band
A semiconductor at
T= 0 K.
valence
band

Because the gap is small, at room temperature there will be a

few electrons in the conduction band. These electrons can be
accelerated by an applied electric field.
A semiconductor at room
temperature. CB

Although e(-Egap/kT) is small,

F
Ne(-Egap/kT) can be significant.

The smaller the gap, the more VB

charge carriers in the
conduction band.

Thus, at very low temperatures, silicon is an insulator, but at

room temperature, it is a weak conductor (intermediate
between conductor and insulator, hence semiconductor).

A rough rule of thumb: a band gap of less than 3 eV gives rise

to a semiconductor.
It is possible to “engineer” properties of semiconductors to make
them more suitable for use in devices.

We do this by doping them with impurities.

Here’s an example: arsenic impurities in silicon.

As has an outer electron configuration of 4s2 4p3. After it

shares 4 of its outer electrons with neighboring silicon (3s23p2),
the remaining electron is very loosely bound. (0.05 eV in Si
and 0.01 for Ge)
Homework problems 10.21 and 10.22
-
(assigned although listed under section 10.8) +
show that kT at room temperature is more
than enough energy to ionize the fifth outer
electron.
The electrons from the As+ ions are then free to move
throughout the crystal.
The arsenic impurity creates a donor impurity level. Because it
takes only a few meV to ionize the As and place the resulting
electron in the conduction band, the donor impurity level sits just
below the conduction band.
A few donor impurities can
produce many electrons in the CB
conduction band and give rise
to significant conductivity.
F
The Fermi level lies somewhere
between the top of the valence
band and the highest-energy VB
electron in the conduction
band.

These semiconductors are n-type, because conduction is by

n egative electrons.
Here’s another example: gallium impurities in silicon.

Ga has an outer electron configuration of 4s2 4p1. It “wants” to

borrow 3 electrons from its 4 silicon (3s23p2) nearest
neighbors.

After a Ga “borrows” 3 electrons, it is

easy for the 4th silicon to “convince”
- +
the Ga to “borrow” one more
electron, creating a Ga- ion.

The lattice depicted here is

highly schematic, not
The gallium impurity creates an realistic, and should be used
acceptor impurity level. as a visual aid only!
Because the acceptor ionization energy is very small, the
acceptor levels sit just above the valence band (a small fraction
of an eV).

Electrons from the valence band CB

can easily get to the acceptor
bound states. That leaves holes
in the valence band.
F
The holes represent states into
which other electrons in the VB
valence band can move. Thus,
electrons can easily move around This is called a p-type
in the presence of an applied semiconductor because
field. “p”ositive holes are the charge
carriers.
Alternatively, we can look at the holes, say they move around,
and say that conduction is due to holes.
Electron doping: Phosphorus, antimony and Bismuth.
(All have 5 valance electrons and can be used as donor
impurities)

Hole doping: Indium, Thallium and Gallium

(All have 3 valance electrons and can be used as
accepter impurities)

A minute amount of impurity can produce a dramatic

change in the conductivity of a semiconductor. e.g. 1
part of donor impurity per 109 parts of germanium
increases its conductivity by a factor of nearly 103

Other examples of semiconductors:

GaAs, GaP, InSb, and InP
Again, it turns out that there don't have to be very many
acceptor atoms around to result in a significant number of
holes in the valence band.

What's all this fuss about holes. It seems like a hole is really
just an electron missing from the valence band and sitting in an
acceptor state.

Why don't we just talk about conduction by these electrons

moving from state to state, instead of worrying about holes?

Answer: holes really are more than just missing electrons. For
one thing, electrons in this case are "stuck" on acceptor atoms,
but the holes are free to move about in the valence band.

For another thing, we can dope semiconductors so that there

are excesses of holes and electrons. A "hole" really is more
than just a missing electron which is somewhere else.
Optical properties of solids are closely related to band
structures.

Visible photons have energies ranging from about 1 eV to

about 3 eV.

Metals can absorb visible photons

because there are many empty states
for electrons to move to.

In diamond, the valence band is full and the

conduction band is empty.

A 3 eV photon cannot excite an electron across

the 6 eV band gap. Diamond cannot absorb
visible photons. Diamonds are transparent.
“Shouldn’t all insulators be transparent?”

Yes. They are opaque because they contain impurities and

irregularities which scatter visible light.

Insulators are transparent to high-energy UV (ultraviolet)

photons.

Now, skipping ahead briefly…

Section 10.8 is a lengthy section which attempts to
give a better justification of energy bands.

The section is not required, but does contain a few key

points:
The periodicity of a crystal lattice leads naturally
(through the solution of Schrödinger’s equation)
to allowed and forbidden energy bands for
electrons.

Electrons cannot exist in forbidden energy states

because there are no solutions to Schrödinger’s
equation there.

Electrons do not (in general) scatter from a

perfect lattice, but they do interact with the
lattice.
Sometimes the lattice “holds” the “free” electrons
in place. These electrons act like they have an
unusually high mass (meffective > melectron).

Sometimes the electrons act like they have an

unusually small mass (meffective < melectron).

Sometimes the electrons even have a negative

effective mass.

Huh?

Sure! Push on an electron in one direction. If

the push gives it enough energy to Bragg scatter
off the lattice (the exception to the “no
scattering” rule), the electron goes in the
opposite direction. Negative mass!
Ceramics majors would benefit from studying section
10.8. The only material you are required to know (for
exam or quiz purposes) is that given above.

One more thing… the band structure I showed earlier:

Notice the gap that extends in all directions through

the crystal.