1st Final Session G12

LO. 12- Solid state physics

 Section Concepts:

1- Solid-state physics
2. Crystal structure (Simple cube, fcc, bcc, hcp)
3. Coulomb forces
4. Phonons
5. Energy bands.
 Section Skills:
1. Explain typical metal crystal structures (Simple cube, fcc,
bcc, hcp)
2. Analyze vibration modes in a 1-D crystal structure
3. Miller indices.
4. Explain how photoelectron spectroscopy can be used to
probe electron energy bands in solids
Introduction: Solid State Physics
The serious study of solid state physics began With the
discovery of x-ray diffraction by crystals and the publication
of a series of simple calculations of the properties of crystals
and of electrons in crystals.
Why crystalline solids rather than non-crystalline solids?
The important electronic properties of solids are best
expressed in crystals. (Thus the properties of the most
important semiconductors depend on the crystalline
structure of the host) essentially because electrons have
short wavelength components that respond dramatically to
the regular periodic atomic order of the specimen.
Introduction: Solid State Physics
Non-crystalline materials, notably glasses, are important for
optical propagation because light waves have a longer
wavelength than electrons and see an average over the order,
and not the less regular local order itself.
Most solids have periodic arrays of atoms which form what
we call a crystal lattice. Amorphous solids and glasses are
exceptions. The existence of the crystal lattice implies a
degree of symmetry in the arrangement of the lattice, and
the existing symmetries have been studied extensively.
One of the implications of the symmetric lattice of atoms is
that it can support resonant lattice vibration modes. These
vibrations transport energy and are important in the thermal
conductivity of non-metals, and in the heat capacity of all
solids.
Crystal Structure:
An ideal crystal is a periodic array of structural units, such
as atoms or molecules.
It can be constructed by the infinite repetition of these
identical structural units in space.
Structure can be described in terms of a lattice, with a
group of atoms attached to each lattice point. The group of
atoms is the basis.
Bravais Lattice:
An infinite array of discrete points with an arrangement and
orientation that appears exactly the same, from any of the
points the array is viewed from.
Crystal Structure:
Primitive Unit Cell:
A primitive cell or primitive unit cell is a volume of space
that when translated through all the vectors in a Bravais
lattice just fills all of space without either overlapping itself
or leaving voids.
A primitive cell must contain precisely one lattice point.
Crystal Structure:
BCC Structure
BCC: stands for Body-Centered Cubic
Crystal Structure:
BCC Structure

BCC Crystal
Crystal Structure:
BCC Structure

BCC Lattice
Crystal Structure:
BCC Structure
ATOMIC PACKING FACTOR:
It represents the ratio between the size (volume) of the
filling atoms to the size (volume) of the crystal unit cell.

×
No. of atoms Volume of atom
in unit cell in unit cell
Volume of unit cell
Crystal Structure:
BCC Structure
ATOMIC PACKING FACTOR: BCC
• APF for a body-centered cubic structure = 0.68

Unit cell contains:

1 + 8 x 1/8
= 2 atoms/unit cell

R
a
Crystal Structure:
FCC Structure
FCC: stands for Face-Centered Crystal
Crystal Structure:
FCC Structure

FCC Lattice
Crystal Structure:
FCC Structure

FCC Lattice
Crystal Structure:
FCC Structure
Don’t Forget: ATOMIC PACKING FACTOR:
It represents the ratio between the size (volume) of the
filling atoms to the size (volume) of the crystal unit cell.

×
No. of atoms Volume of atom
in unit cell in unit cell
Volume of unit cell
Crystal Structure:
FCC Structure
ATOMIC PACKING FACTOR: FCC
Unit cell contains:
6*1/2 + 8*1/8
= 4 atoms/unit cell

×
Crystal Structure:
FCC Structure
ATOMIC PACKING FACTOR: FCC
• APF for a Face-centered cubic structure = 74.048%

 The diagonal of one face of the cube as a two-dimension view equals to 4R

 Then L= 4R/root 2

𝟔𝟒𝑹𝟑
 𝑪𝒖𝒃𝒆′ 𝒔 𝒗𝒐𝒍𝒖𝒎𝒆 =
𝟐 𝟐
𝟏𝟔
 𝑨𝒕𝒐𝒎𝒔′ 𝒗𝒐𝒍𝒖𝒎𝒆 = .𝝅 𝑹𝟑
𝟑

 APF = 74.048%
Crystal Structure:
HCP Structure

HCP Crystal
Crystal Structure:
HCP Structure
HCP: stands for Hexagonal Close Packing
Bonding in Molecules:
One of the great successes of quantum mechanics was to
give scientists, at last, an understanding of the nature of
chemical bonds. Because it is based in physics.
By a molecule, we mean a group of two or more atoms that
are strongly held together so as to function as a single unit.
When atoms make such an attachment, we say that a
chemical bond has been formed.
There are two main types of strong chemical bond:

Covalent Ionic
Bonds Bonds
Many bonds are actually intermediate between these two
types.
Bonding in Molecules: Covalent Bonds
To understand how covalent bonds are formed, we take the
simplest case, the bond that holds two hydrogen atoms
together to form the hydrogen molecule.
The mechanism is basically the same for other covalent
bonds.
As two H atoms approach each other, the electron clouds
begin to overlap, and the electrons from each atom can
“orbit” both nuclei. (This is sometimes called sharing
electrons.)
Bonding in Molecules: Covalent Bonds
If both electrons are in the ground state (n=1) of their
respective atoms, there are two possibilities: their spins can
be parallel (both up or both down), in which case the total
spin is (S= ½ + ½ = 1) or their spins can be opposite (ms= + ½
for one, and ms= - ½ for the other), so that the total spin
S = 0.
We shall now see that a bond is formed only for the state,
when the spins are opposite.
Coulomb forces

It is useful to analyze the interaction between two objects—

say, between two atoms or molecules—with the use of a
potential-energy diagram, which is a plot of the potential
energy versus the separation distance.
For the simple case of two point charges, and the potential
energy PE is given by:

Where r is the distance between the charges, and the

constant k is equal to 9 x 109 N.m2/C2.
If the two charges have the same sign, the potential energy
PE is positive for all values of r.
Coulomb forces

and a graph of PE versus r in this case is shown here.

The force is repulsive (the charges
have the same sign) and the curve
rises as r decreases; this makes sense
because if one particle moves freely
toward the other (r getting smaller),
the repulsion slows it down so its KE
gets smaller, meaning PE gets larger.
Coulomb forces

If, on the other hand, the two charges are of the opposite
sign, the potential energy is negative because the product
q1q2 is negative.
The force is attractive in this case, and the graph of PE
( α 1/r )versus r looks like this.
The potential energy becomes more
negative as r decreases.
Now let us look at the potential-
energy diagram for the formation of
a covalent bond, such as for the
hydrogen molecule H2.
Coulomb forces and pair wise
interactions: Van der Waal’s Forces/Effect
o In 1873, the Dutch physicist Johannes Diderik van der
Waals postulated a type of intermolecular forces in
developing a theory to account for the properties of real
gases.
o He named this type of forces after him.
o They are relatively weak electric forces that attract neutral
molecules to one another in gases, in liquefied and solidified
gases, and in almost all organic liquids and solids.
o Solids that are held together by van der Waals forces have
lower melting points and are softer than those held
together by the stronger ionic, covalent, and metallic bonds.
Coulomb forces and pair wise
interactions: Van der Waal’s Forces/Effect

What is being attracted?

d+ attracted to d- → electrostatic attraction of e- s

of one atom to another atom’s nucleus.
Evidence on the force: Non-polar molecules
can form gases, liquids and solids.
e-
+ +
e-
Coulomb forces and pair wise
interactions: Van der Waal’s Forces/Effect

Sources of VDW Forces

1. dipole-dipole. ( 2 polar)
2. dipole-induced dipole ( HCl + Ar)
3. Dispersion (London dispersal effect) 2 non-polar
Coulomb forces and pair wise
interactions: Van der Waal’s Forces/Effect

Dipole-Dipole (Keesom Effect)

Two polar molecules align so that d+ and d-
are matched (electrostatic attraction)

Ex: fluromethane
H H

H C F H C F
d+ d- d+
Dipole-Dipole
d-
H H
Coulomb forces and pair wise
interactions: Van der Waal’s Forces/Effect

Dipole-Induced Dipole (Deybe force)

o A dipole can induce (cause) a

temporary dipole to form in a non-
polar molecule
o The molecules then line up to match
d+ and d- charges
Coulomb forces and pair wise
interactions: Van der Waal’s Forces/Effect

Example
d+ d- d+ e- e e- ee- - e- d-
-
- - -
H Cl
-
ee - Ar
-
e e - e - e-
e-e
ee-- e e

non-polar
A DIPOLE
(it’s polar) INDUCED
DIPOLE
Dipole – Induced Dipole
(weak and short-lived)
Coulomb forces and pair wise
interactions: Van der Waal’s Forces/Effect
Dispersion (London dispersal effect)
o The nature of this attractive force in molecules, which
requires quantum mechanics for its correct description,
was first recognized (1930) by the Polish-born
physicist Fritz London.
o At any instant the center of negative charge of the
electrons and the center of positive charge of the
atomic nuclei would not be likely to coincide. Thus,
the fluctuation of electrons makes molecules time-
varying dipoles.
o They do induce properly aligned polarization in
adjacent molecules, resulting in attractive forces.
Band Theory of Solids:
We saw that when two
hydrogen atoms approach each
other, the wave functions
overlap, and the two 1s states
(one for each atom) divide into
two states of different energy.
(As we saw, only one of these
states, has low enough energy
to give a bound molecule.) the
next figure a, shows this
situation for 1s and 2s states
for two atoms: as the two
atoms get closer (toward the
left in the figure.)
Band Theory of Solids:
The 1s and 2s states split into
two levels. If six atoms come
together, as in Fig. b,
Each of the states splits into six
levels. If a large number of
atoms come together to form a
solid, then each of the original
atomic levels becomes a band
as shown in Fig. c.
The energy levels are so close
together in each band that
they seem essentially
continuous.
Band Theory of Solids:
The crucial aspect of a good
conductor is that the
highest energy band
containing electrons is only
partially filled.
Consider sodium metal, for
example, whose energy
bands are shown here.
The 1s,2s, and 2p bands are
full (just as in a sodium
atom) and don’t concern us.
The 3s band, however, is
only half full.
Band Theory of Solids:
To see why, recall that the exclusion principle stipulates that
in an atom, only two electrons can be in the 3s state, one
with spin up and one with spin down.
These two states have slightly different energy.
For a solid consisting of N atoms, the 3s band will contain
2N possible energy states. A sodium atom has a single 3s
electron, so in a sample of sodium metal containing N
atoms, there are N electrons in the 3s band, and N
unoccupied states.
When a potential difference is applied across the metal,
electrons can respond by accelerating and increasing their
energy, since there are plenty of unoccupied states of
slightly higher energy available.
Band Theory of Solids:
Hence, a current flows readily and sodium is a good
conductor.
The characteristic of all good conductors is that the highest
energy band is only partially filled, or two bands overlap so
that unoccupied states are available.
An example of the latter is magnesium, which has two 3s
electrons, so its 3s band is filled.
But the unfilled 3p band overlaps the 3s band in energy, so
there are lots of available states for the electrons to move
into.
Thus magnesium, too, is a good conductor.
Band Theory of Solids:
In a material that is a good insulator, on the other hand, the
highest band containing electrons, called the valence band,
is completely filled.
The next highest energy band, called the conduction band,
is separated from the valence band by a “forbidden” energy
gap(or band gap), of typically 5 to 10 eV.
So at room temperature (300 K), where thermal energies
(that is, average kinetic energy) are on the order of almost
no electrons can acquire the 5 eV needed to reach the
conduction band.
When a potential difference is applied across the material,
no available states are accessible to the electrons, and no
current flows.
Hence, the material is a good insulator.
 Phonon
A phonon is a definite discrete unit or quantum of vibrational mechanical
energy, just as a photon is a quantum of electromagnetic or light energy.