1.

INTRODUCTION

• What is a Solid?
• It is not a continuous rigid body, instead
it is composed of discrete basic units
(ATOMS).
• Crystalline & Amorphous solids.

• Solid State Physics: Study of the properties of

solid materials.
• Mainly concerned with crystalline

materials in this course.

• Study of crystals triggered by discovery

of X-ray diffraction by crystals.

• Why study solid state?

• Integral part of physics

• Important industrial applications, e.g.

electronics, solid state devices, materials.

2. CRYSTALLINE STATE
• A perfect crystal maintains the
periodicity of atoms from (∞) to (-∞).
• Imperfections and the reality of the

perfect crystal.
 3. BASIC DEFINITIONS
The Lattice: is a geometrical pattern for the atomic
arrangement in a crystal.
1. Bravais Lattice: all the lattice points (atomic sites)
are equivalent.
2. Non-Bravais Lattice: some of the lattice points
(atomic sites) are not equivalent.

Non-Bravais Lattice = Lattice + basis

The Basis: is a set of atoms located near each site of a

Bravais lattice.

Basis Vectors: are a set of vectors in term of which

the positions of all lattice points can be expressed.

The Unit Cell: In (2D), the area of the parallelogram

whose sides are the basis vectors is called a unit cell of
the lattice. There are two types of unit cells:
Primitive Unit Cell: which contains only one lattice
point.
Nonprimitive Unit Cell: which contains more than one
lattice point.
Useful Remarks:
* The same lattice may have more than one unit
cell depending on the chosen basis vectors.
* All primitive unit cells – in this lattice- have the
same area.
 * The area of nonprimitive unit cell is an integral
multiple of the primitive cell.

Non-Bravais Lattice Nonprimitive cell

In (3D)?
The same definitions BUT..

The lattice constant: (a) is the side length of the unit

cell.

Co-ordination number: (z) is the number of nearest

neighbours.

Packing fraction: ratio of the volume of atoms to

available space in a unit cell.
1. Bravais Lattices
 Elements Of Symmetry:

Each of the unit cells of the fourteen lattices has one

or more of the following elements of symmetry:

1. Inversion center: If there is a point at which

transformation (r → -r) can be preformed and the
cell remains invariant.

FACT: All Bravais lattices are inversion symmetric.

2. Reflection plane: If a mirror reflection is

performed on a plane and the cell remains invariant.

FACT: Not All Bravais lattices have a reflection plane

3. Rotation axis: If the cell rotated an angle (ϑ)

around an axis and remains invariant. This axis is
called n -fold axis of rotation

FACT: An angle 2π/n ⇒ n -fold axis of rotation

 2. Common Crystal Structures
2.1 Face Centered Cubic
• z = 12
• 4 atoms at 000, ½ ½ 0, ½ 0 ½ and 0 ½ ½.
• Examples: Cu, Au, Ag, Pb.
• Non-primitive unit cell.

2.2 Body Centered Cubic

• z = 8.
• 2 atoms at 000 and ½ ½ ½ .
• Examples: Na, Li, K .
• Non-primitive unit cell.

Example1:
Calculate the packing fraction for an fcc structure.

2.3. Diamond & Related Structures

• The unit cell is an fcc cell with a basis of two atoms.
• z = 4.

• 8 atoms, where (group1) atoms

located at 000, ½½0, ½0½, 0½½ ,

and (group2) atoms located at
¼¼¼, ¼¾¾, ¾¼¾, ¾¾¼.
• Examples:

(group 1) & (group 2) same (group 1) & (group 2) different

⇒ Diamond Structure: ⇒ Zincblende Structure:
C, Si, Ge GaAs, ZnS, InSb.

2.4. Ionic Structures

1. NaCl structure:
Non-Bravais lattice composed of two fcc sublattices
displaced relative to each other by ½a.
One made up of4 Na atoms (at 000, ½½0, ½0½, 0½½;)
and the other of 4 Cl atoms (at ½00, 0½0, 00½, ½½½).
• z = 6.

2. CsCl structure:
Non-Bravais lattice composed of two sc sublattices
displaced relative to each other by 23 a.
One made up of 1 Cs atom (at 000) and the other of
1 Cl atom (at ½½½).

• z = 8.
 2.5 Hexagonal close-packed hcp Structure
• The unit cell is a simple hexagonal cell with a basis
of two atoms one at (000) and the other at
( 2/3 1/3 1/2 ) .

• z = 12.
• 6 atoms per unit cell.
• The ratio c/a =1.633.

3. Crystal Planes & Directions

• What are the lattice planes? sets of equally spaced

parallel planes within lattice.
• Each plane of a set has the same density of

lattice points.
• All lattice points are contained on each set

of planes.
• Lattice planes important in crystal

diffraction experiments.

• Miller Indices (hkl): Derived from the intercepts

made on the crystal axes by the plane that is
nearest to the origin.
 To determine the indices for a plane:
- Find its intercepts with the axes.
- Take their reciprocals.
- Reduce them to the smallest integers by multiplying
by a common factor.
- Write the set into round brackets ().
To determine a direction:
- Find the components of a vector in that direction.
- Reduce them to the smallest integers.
- Write them into square brackets [].

Convention:
• General plane: (h k l)
• Negative intercept represented by bar above
number.
• Directions are conventionally represented with
square brackets, eg. [2 1 2], while Planes are
represented with round brackets, eg. (2 1 2).
 INTERATOMIC FORCES

It has been shown earlier that the atoms in

crystalline solids are arranged in neat ordered
structures. Now we will describe the nature of the
forces which hold those atoms together.

Consider, first, two identical atoms in their ground

states being brought together from an infinite
separation.

 Initially, the energy of their interaction is zero.

 As the atoms approach, the attractive forces
increase and the energy increases in a negative sense
(the energy of attraction is negative since the atoms
do the work, while that of repulsion is positive as
work has to be done on the atoms).
 At a separation of a few atomic radii, repulsive
forces begin to increase exponentially.
 The atoms reach an equilibrium separation r0 at
which the repulsive and attractive forces are equal
and the mutual potential energy is a minimum.

E(r) = − E +E
att rep

where
A
E =− n
att r
and
B -r
Erep = m or = B exp ( )
r ρ

Cohesive energy: the energy required to pull the

crystal apart into a set of free atoms.
Ionization Energy: Energy required to remove
electrons.
Note:
1- Forces which hold solids together are totally
electrostatic in origin.
2- Different bonds give rise to different physical
properties in solids.
3- Most real bonds are intermediate between the
'extreme' types classified below.
 1. THE IONIC BOND
Typical Example: NaCl whose melting point is 801oC
Strength: strong (~5 eV per bond)
Origin:
Transfer of electrons between two atoms
⇒ Formation of (+ve) & (-ve) ions
e2
⇒ Existing of Coulomb force
4πε 0 R 2

2. THE COVALENT BOND

Typical Example: Diamond whose melting point is

very high >3000oC
Strength: strong (~few eV per bond)
Origin:
Existing of 4 (or2) atoms with 4 (or7) valence
electrons ⇒Each atom contributes by one electron
⇒ Formation of a double-electron bond
 Cl2 C

Type of binding in GaAs:

31% Ionic & 69% Covalent

3. THE METALLIC BOND

Typical Example: Na whose melting point is 97.8oC
Strength: Somewhat weaker but not negligible

Origin:
Existing of atoms with one or two loosely bound
valence electrons
⇒ As atoms
become closer, those
electrons become free
⇒ Formation of
cores of (+ve) ions
dispersed in a see of
electrons.
 4. THE HYDROGEN BOND

Typical Example: Ice (H2O) whose melting point is

just 0oC
Strength: weak
Origin:
Electrons pulled more strongly toward one atom of a
molecule
⇒ Formation of an electric dipole
⇒ Molecules which are attracted to each

other
5. VAN DER WAALS BOND

Typical Example: Inert- Gas elements (e.g. He)

whose melting point is very low –272.2oC
Strength: very weak
Origin:
Existing of atoms have a completely full outer shell.
⇒ No exchange or sharing of electrons
 ⇒ Fluctuations of electrons symmetric
distribution around the nucleus
⇒ Formation of a fluctuating electric
dipole on each atom
 1. X-Ray (Nature & Generation)

* X-rays are electromagnetic waves with very short

wavelength ( λ ~ 1Ao).
i.e. of the same order of magnitude as the lattice
constant.
* When high kinetic energy electrons hit a metallic
target, X-rays will be emitted.
*Since,
Max. energy a photon can get = K.E of the incident electron

hνmax = eV
So, The min. wavelength can be obtained is

λmin = c/νmax = 12.3/V Ao.

2. Bragg’s Law
• Consider an incident beam being reflected by two
parallel lattice planes as shown.
• Bragg’s law states the condition for a constructive
interference as:
2d sinθ = nλ

Which means that diffraction can not be occurred

unless the incident wavelength is
λ < 2d

Interplanar distance (dhkl ):

The value of d, the distance between two adjacent
planes in the set (hkl) of a cubic system is given by,

1 = h 2 + k 2 +l 2
dhkl
2 a2
Or:

dhkl = a
h 2 + k 2 +l 2

where a is the length of the cube side.

Intensity of reflected waves depends on:

- No. of electrons in each atom.
- Density of atoms in the plane.
- The incident angle θ.
- The order number n.
 3. Diffraction by a Crystal
• Consider an incident wave being scattered by two
lattice points (atoms) as shown.
• Instead of wavelength, the concept of the
wavevector k , where k = 2π / λ , is often used to
characterize the plane-wave and show its direction.

D C

B
A

- Scattered amplitude is maximum for phase factors

equal to unity, ie.

∑ exp(iΔk.r ) = ∑ (cos Δk.r − i sin Δk.r ) = 1

r r
Or,

Solution for such set is of the form: G

~

where G with a~∗ = 2π ~b×c~

~ ~×c~
~a. b

~ is called the reciprocal lattice vector.

G
 1. Reciprocal Lattice
• Set of vectors, G defines new
~
lattice: Reciprocal Lattice.

With

2π 2π 2π
a∗ = (b×c) b∗ = (c×a) c∗ = (a×b)
Ω Ω Ω

Where Ω = a.(b×c) , the volume of the unit cell.

Note that:
a∗.a = 2π a∗.b = a∗.c = 0
b∗.b = 2π b∗.a = b∗.c = 0
c∗.c = 2π c∗.a = c∗.b = 0

•This is the lattice that is produced by

diffraction, ie. a diffraction pattern of a
crystal is the mapping of its reciprocal
lattice.
• Example: Simple cubic (real) lattice with side α.
In Cartesian co-ordinates, we have: a=αi, b =αj &
c =αk.
 Apply definition of reciprocal vector get:
a* = (2π/α)i, b* = (2π/α)j & c* = (2π/α) k
reciprocal lattice is simple cubic with side
2π/α.

Properties of the reciprocal lattice:

- A vector Ghkl drawn from the origin to any point
with coordinates hkl, is perpendicular to the (hkl)
plane in the real lattice.
- The length of the vector Ghkl is equal to the
reciprocal of the spacing d of the (hkl) planes, or

2π
G hkl =
d hkl
 2. Brillouin Zones
• Use 2-D (square) reciprocal lattice as illustration.

• Define volume in 3D, area in 2D as 1st Brillouin zone

(shaded), 2nd Brillouin zone etc.

3. Back to Bragg’s law

It was shown before that the condition for a
constructive interference between the scattered
waves is
G
~
and, from the following figure, it is easy to show that
for elastic scattering:

G
 1. Allowed X-ray diffraction
• Apart from the phase difference, the intensity of
the diffracted radiation depends on a number of
factors:
• Some are related to the electronic distribution in
the atom. And some are related to the structural
arrangement of atoms in the crystal.
• Those factors can be expressed by the structure
factor Fhkl

Fhkl = f a ∑ e
i 2π ( hu j + kv j + lw j )

where fa is the atomic form factor (or atomic

scattering factor).
Thus, if Fhkl is zero for certain indices, then the
intensity vanishes, even though the corresponding
planes satisfy Bragg’s condition.

Example:
The bcc unit cell has two atoms whose coordinates are
(u,v,w) = (0,0,0) & (½,½,½). The structure factor, for
such structure is

Fhkl = f a (1 + e iπ ( h + k + l ) )
Hence, if (h+k+l) is odd

Fhkl = f a (1 − 1) = 0
And, if (h+k+l) is even

Fhkl = f a (1 + 1) = 2 f a

In other words, for the bcc lattice, the diffraction is

absent for all planes in which the sum of (h+k+l) is odd
and is present for the planes in which the sum of
(h+k+l) is even.

2. Methods of X-ray diffraction

There are essentially three methods:
The rotating-crystal method,
the Laue method,
and the powder method.
Regardless of the method used, the quantities
measured are essentially the same:

i) The scattering angle 2θ between the diffracted

and incident beams.

ii) The intensity I of the diffracted beam. This

quantity determines the cell-structure factor,
Fhkl.
The rotating-crystal method
Sample: a single crystal.
Wavelength λ: A monochromatic beam.
Technique: The sample is rotated
until a diffraction condition occurs.
The diffracted beam, then, will be
recorded as a spot on a photographic film.
By recording the diffraction patterns (both angles and
intensities) for various crystal orientations, one can
determine the shape and size of the unit cell as well as
the arrangement of atoms inside the cell.

The Laue method

Sample: a single crystal.
Wavelength λ: A white x-ray beam.
Technique: The sample has a fixed orientation relative
to the incident beam. Since λ covers a continuous
range, the crystal selects that particular wavelength
which satisfies Bragg's law at the present orientation,
The diffracted beam is then recorded as a spot on a
photographic film.

But since the wavelength corresponding to a spot is

 not measured, one cannot determine the actual
values of the interplanar spacings but only their
ratios.

The powder method

Sample: a powder or polycrystalline.
Wavelength λ: A monochromatic beam.
Technique: Because of the large number of
crystallites which are randomly oriented, there is
always enough of these which have the proper
orientation relative to the incident monochromatic
beam to satisfy Bragg's law. Since both λ and θ are
measurable, one can determine the interplanar
spacing.

3. Neutron & Electron Diffraction

In addition to x-rays , there are some other forms of
radiation that can be used to characterize a crystal if:
- * It has a wave property, so it can interfere.
- *Its wavelength is of the same order of magnitude
as the lattice constant.
Since both neutron and electron satisfy those
conditions they can be used in diffraction
experiments.
The relation between λ (in Ao) and the applied field
E (in electron volts) is:

0.08
λ= For neutron
E

150
λ= For electron
E

Because electrons are light, charged

particles, they tend to interact more with
atoms and so mostly give information about
the surface planes of atoms in a crystal. X-
rays tend to interact more with the bulk of
the sample and may even pass completely
through thin samples. Neutrons interact
more with the nuclei of atoms and are
especially useful for investigating magnetic
interactions and isotopes.