Acknowledgement

Some of the contents in ZCT307 course

were obtained from lecture note by
Professor Haslan,  
Professor Tsymbal and
Prof. Beşire GÖNÜL.
With PERMISSION 1
 Solid State Physics I & II
• This course is intended to provide an introduction to the
physics of solids. 
• We will begin by characterizing the properties of static (crystal
structure) and dynamic (lattice vibrations) arrangements of
atoms. 
• Next we will study electrons in solids and will identify key
features distinguishing metals, insulators and
semiconductors. 
• We will continue with examples of macroscopic phenomena,
magnetism, superconductivity, optical process, surface and
interface physics, dielectrics and ferroelectrics, and a
discussion of current open questions during the Solid State
Physics II.
• Topics of current interest will be covered throughout the
course.  
 Learning Outcomes and Objectives
• Students are expected to develop a clear concept of
the crystal classes and symmetries and to understand
the relationship between the real and reciprocal
space.
• Students will be able to calculate the Braggs
conditions for X-ray diffraction in crystals.
• Students will become familiar with the free-electron
model for metals and use the concept of Fermi
energy and Fermi temperature.
• Students will master their skills for oral presentations
on the selected topics of the Solid State Theory.
Solid <-> Liquid <->Gas<->Solid

4
5
• In the gaseous state
– Molecules repeatedly collide
and bounce off of other
molecules.
• In the liquid state
– Atoms or molecules have
sufficient kinetic energy to
move independently, yet they
don't have enough energy to
separate completely from other
atoms.
• In the solid state,
– The atoms are locked into their
crystal lattice positions.
6
 States

Liquid Solid Gas Others

7
 Classification
of Solids
• Solids are classified according to regularity and structure of
their building blocks, typically atoms and can be the following:
• Amorphous
– No periodic structure at all.  All constituent atoms are
disordered.  An example of this category is glass.
• Crystal
– Periodical arrangement of constituent species. Perfect array of
atoms.  Examples are diamonds, metals and salt.
• Polycrystalline
– Many small regions of single crystals with various orientations
connected by grain boundaries. 
8
Crystal ?

9
 To describe crystals, we use the concepts of
lattice and basis:
• Lattice
– A collection of mathematical points in a periodic
arrangement.
 - infinite in extent
 - all points are identically  surrounded
 - mathematically described by translation vector
• Basis
– Set of atoms attached to each lattice point.  
– These are the actual physical things that make up the
material.
10
Crystal

11
 Crystal

Twinned Crystal Single Crystal Multiple Crystal

12
 States

Solid

Liquid Crystals
Gas Others
Amorhous
Multiple Crystal Single Crystal
Polycrystalline
Twinned Crystal

13
 Single Crystal
• A solid is said to be a crystal if atoms are arranged in such a
way that their positions are exactly periodic.
• This concept is illustrated in Figure below using a two-
dimensional (2D) structure.
• A perfect crystal maintains this periodicity in both the x and y
directions from - infinite to + infinite.
• As follows from this periodicity, the atoms A, B, C, etc. are
equivalent.
• In other words, for an
observer located at any of
these atomic sites, the
crystal appears exactly the
same.
14
 Single Crystal -cont
• The same idea can be expressed by saying that a crystal
possesses a translational symmetry.
• The translational symmetry means that if the crystal is
translated by any vector joining two atoms, say T in the
previous figure, the crystal appears exactly the same as it did
before the translation.
• In other words the crystal remains invariant under any such
translation.

15
 1 Crystal Structure
1.1 Crystal structure and lattice translation vectors
• An ideal crystal can be built by arranging an
infinite number of unit structures to form a
periodic structure
• For an ideal crystal of cubic shape, its unit
structure is also cubic
• Generally, the shape of a unit structure is
parallelepiped

16
 z

Periodic structure

x Unit structure (cubic)

17
 z

Periodic structure

x Unit structure (cubic)

18
 z

Periodic structure

x Unit structure (cubic)

19
Periodic structure

Unit structure (parallelepiped)

20
21
• The frame of the units formed what is called the
lattice (a periodic lattice)
• It is a grid that has translational symmetry
• If we move from a point of position r in one unit
cell to an equivalent point of position r’ in
another unit cell, the neighbours surrounding
both points are the same
• Hence, lattice translation vectors can be used to
show that both points are the same

22
 z

Periodic structure
A’ = A+ 0x + 2y + 2z

A’
A’’ = A’+ -1x + 1y + -1z
A’’

A
y

x Unit structure (cubic)

23
• r’ = r + n1a + n2b + n3c (1.1)
• r’ = r + T (1.2)
• T = n1a + n2b + n3c represents the lattice
translation vectors
• n1, n2, n3 are integers indicating the number of
units required in x, y and z directions in order to
reach r’
• a, b, c are translation unit vectors (unit distance)
in x, y and z directions

24
• Set of r’ for all n1, n2, n3 defines a lattice known
as space lattice or Bravais lattice
r’

Translation Lattice
vector T

25
• Basis (atom, molecules, a group of atoms or a
group of molecules) can now be added to the
lattice, thus forming a crystal structure

+ =
(1.3)

Lattice + Basis = Crystal structure

26
 Bravias
or Non-Bravais ?

• There are two classes of lattices: the Bravais

and the non-Bravais.
• In a Bravais lattice all lattice points are
equivalent and hence by necessity all atoms in
the crystal are of the same kind.
• On the other hand, in a non-Bravais lattice,
combination of some of 2 or more Bravias
lattice, basis are of different kinds.
27
 States

Solid

Liquid Crystals
Gas Others
Amorhous
Multiple Crystal Single Crystal
Polycrystalline
Twinned Crystal

28
 Bravias or Non-Bravais ? -cont
• In the figure below, the lattice sites A, B, C are
equivalent to each other. Also the sites A1, B1,
C1, are equivalent among themselves.
• However, sites A and A1 are not equivalent:
the lattice is not invariant under translation
AA1 points are non-equivalent.

29
30
31
 Atoms are of different kinds.
Some lattice points aren’t equivalent.
A combination of 2 or more BL

32
 Crystal Lattice Types
-Bravais Lattice-

• An infinite array of discrete points with an

arrangement & orientation that appears exactly
the same, from whichever of the points the array
is viewed.
• A Bravais Lattice is invariant under a translation
T = n1a1 + n2a2 + n3a3
• In a Bravais Lattice, not only the atomic
arrangement but also the orientations must
appear exactly the same from every lattice point.
33
34
 Crystal Lattice Types
-Non Bravais Lattice-

2 Dimensional Honeycomb Lattice

• The red dots each have a neighbor to
the immediate left.
• The blue dot has a neighbor to its right.
• The red (& blue) sides are equivalent
& have the same appearance. But, the
red & blue dots are not equivalent.
• If the blue side is rotated through 180º
the lattice is invariant.
 The Honeycomb Lattice is NOT a
Bravais Lattice!!
Honeycomb
Lattice
35
Honeycomb
Lattice

36
1.2 Primitive lattice cell
• The parallelepiped defines the primitive lattice
cell with primitive axes a, b and c

Parallelepiped (unit cell)

Lattice point

c b

• This primitive cell has a minimum volume and

also known as unit cell
37
 States

Solid

Liquid Crystals
Gas Others
Amorhous
Multiple Crystal Single Crystal
Polycrystalline
Twinned Crystal

38
• There are several ways to choose the primitive
axes and the primitive cell, but the number of
atoms in the primitive cell is always the same
• For every primitive cell there is one lattice point
• Examples

b
b 1 2
a a 3
b
a

• 1, 2 and 3 have the same area, thus they can be

considered as primitive cell
39
 2-Dimensional Unit Cells
Unit Cell 
The smallest component of the crystal (group of
atoms, ions or molecules), which, when stacked together
with pure translational repetition, reproduces the whole
crystal.
S
b
a
S S

S S S

S S S S

S S S S S
Unit Cell 
The smallest component of the crystal (group of atoms,
ions or molecules), which, when stacked together with pure
translational repetition, reproduces the whole crystal.
The choice of unit cell is not unique!

41
 2-Dimensional Unit Cells
Artificial Example: “NaCl”

Lattice points are points with identical environments.

 2-Dimensional Unit Cells: “NaCl”
The choice of origin is arbitrary - lattice points need not be
atoms - but the unit cell size must always be the same.
 2-Dimensional Unit Cells: “NaCl”
These are also unit cells -
it doesn’t matter if the origin is at Na or Cl !
 2-Dimensional Unit Cells: “NaCl”
These are also unit cells -
the origin does not have to be on an atom!
 2-Dimensional Unit Cells: “NaCl”
These are NOT unit cells - empty space is not allowed!
 2-Dimensional Unit Cells: “NaCl”
In 2 dimensions, these are unit cells –
in 3 dimensions, they would not be.
 2-Dimensional Unit Cells
Why can't the blue triangle be a unit cell?
 Primitive or Non-Primitive?
• A primitive unit cell is the unit cell with the smallest area
which produces this coverage.
• In the two dimensional case the area of the unit cell is
given by S=|axb|.
• The choice of the unit cell is not unique and it is
dictated by convenience.
• The unit cell can be primitive and non-primitive (or
conventional).
• The unit cell discussed above is primitive.
• However, in some cases it is more convenient to deal
with a unit cell which is larger, however, it exhibits the
symmetry of the lattice more clearly. 49
• Vectors a1 and a2 can be chosen as primitive translation vectors for
the lattice shown in the figure below.
• In this case the unit sell is parallelogram.
• However, the lattice can also be regarded as adjacent rectangles,
– where the vectors c1 and c2 can be considered as translation
vectors. The unit cell in this case is larger.
• In the first case, there is only one atom in a unit cell, whereas in
the second case there is a lattice with a basis (2 atomes).
• The basis consists of the two atoms: one atom is located in the
corner of the unit cell and another atom in the center of the unit
cell.
• The area of the conventional
unit cell is larger by a factor of
two than the area of the
primitive unit cell.
50
• The 3-dimensional parallelepiped primitive cell
has lattice point at each corner
• Each lattice point is shared by eight other
primitive cells
• Hence, total lattice points in the primitive cell is
one
• 8 × (1/8) = 1
Number of lattice points Shared by eight other Total lattice points in
for one primitive cell primitive cells the primitive cell

• The volume of the parallelepiped primitive cell is

Vc = |a×b.c| (1.4)
51
Simple Cubic Body-Centered Cubic
(SC) (BCC)

Face-Centered Cubic
52
(FCC)
53
54
 14 Bravais lattices
• In his study of lattice, Bravais discovered some that were
more complex but still conformed to the symmetry of one of
the seven crystal systems.
• These non-primitive lattices contain two or more lattice points
(doubly primitive, triply primitive, etc.) per unit cell and can be
most simply viewed as the combination of a primitive lattice
with one or more offset identical copies of itself.
• Thus the lattice points and every symmetry element in the
primitive lattice are reproduced with a corresponding offset.
• The 14 Bravais lattices (Fig. 2.14) consist of seven primitive
and seven non-primitive lattices.

Auguste Bravais (French pronunciation: [oɡyst bʁavɛ];

23 August 1811, Annonay, Ardèche – 30 March
1863, Le Chesnay, France) was a French physicist,
well known for his work in crystallography (the Bravais
lattices, and the Bravais laws).

55
56
57
What is the total lattice points in the
primitive cell in 2-Dimensional?
Primitive? Bcc? Fcc??

58
• There is another way to determine the primitive
cell and the cell obtained is known as Wigner-
Seitz cell
1.Joint a lattice point to its neighbors using straight
lines
2.At the middle point and normal to these lines,
draw new lines/planes
• The area/volume enclosed by these new
lines/planes is the Wigner-Seitz primitive cell.
• The construction of the WZ cell in the reciprocal
lattice delivers the first Brillouin zone (important
for diffraction). 59
Wigner-Seitz
primitive cell

60
Wigner-Seitz
primitive cell 62
 Tutorial
1. Draw the Bravias lattice for the following
arrangements of atom/molecule (25/100)

63
64
 Tutorial
2. How do we classify solids into classes? What are the
three classes of the solid and describe their
charateristic. (20/100)
3. Describe crystal structure. (15/100)
4. Define Bravias, Non bravias, Primitive and Non
primitive cell. (20/100). What are the differences
between them?
5. What are the differences between primitive and W-
Z cell? (20/100).
6. What is the total lattice points in the unit cell of
face-centered, body-centered, C-based, B-based, A-
based and simple orthorhombic? (8/100).
7. How many space group, point group, Bravias lattice
and crystal system do we have in our world? (8/100)
65
67
560000 cubic Angstroms

68
 Symmetry

Combination of
Basic Symmetry
Symmetry
Operator
Operator

Inversion Points
Translation – Mirror +
Rotation

Rotoinversion –
Rotation Rotation +
Inversion

Screw axis –
Mirror Plane Translation +
rotation

Glide Plane-
Translation +
Mirror plane
69
 WHAT IS SYMMETRY?
• Symmetry is a common natural occurrence
and appears in art forms, architecture, natural
patterns

Tile from a Persian painting 70

 ELEMENTS OF SYMMETRY
• Crystal lattices are classified according to their
symmetry properties, such as inversion, reflection
and rotation.
– Translation : T=n1 a1+n2 a2+n3 a3
– Axis - Rotational symmetry : rotation through integral
multiples of 2π/n about axis where n=1,2,3….
– Plane - Reflection or mirror plane : whether the lattice
is identical on either side of an imaginary plane
– Point - Inversion : A point exists in the lattice such that
the operation r -> -r leaves the lattice unchanged.
71
 A symmetry operation is
a process of transforming an object
such that the initial and final states are
not able to be identified as different .

72
 2 Symmetry
2.1 Lattice symmetry operations
• There are several symmetry operations that can act on a
crystal structure
1. Translation T = n1a + n2b + n3c
2. Axis or plane
• Rotation – n-fold axis
 Reflection – mirror plane
3. Inversion center
• For three dimensional patterns, two additional symmetry
elements exist. These are non point symmetry elements
and are based on the translation operation.
4. Screw axis
5. Glide plane
73
2.2 Rotation
• This occurs at an axis and this axis can be
represented by several symbols

n Symbol Name Meaning

1 monad
2 diad Rotation
3 triad by
4 tetrad 2π/n
6 heksad

• 5-fold axis (n = 5) does not exist in crystal structure

• It could exist in complex molecules symmetry
74
 Symmetry

Combination of
Basic Symmetry
Symmetry
Operator
Operator

Inversion Points
Translation – Mirror +
Rotation

Rotoinversion –
Rotation Rotation +
Inversion

Screw axis –
Mirror Plane Translation +
rotation

Glide Plane-
Translation +
Mirror plane
75
76
77
2.3 Reflection
• A reflection plane is known as a mirror plane and
is represented by m and graphical symbol

Crystal with
reflection
operation
Mirror plane
m (reflection)

78
 Symmetry

Combination of
Basic Symmetry
Symmetry
Operator
Operator

Inversion Points
Translation – Mirror +
Rotation

Rotoinversion –
Rotation Rotation +
Inversion

Screw axis –
Mirror Plane Translation +
rotation

Glide Plane-
Translation +
Mirror plane
79
80
• If an object is reflected in a mirror, the image and the
object are related by a symmetry transformation,
denoted by m.
• Mirror images of molecules are very common in
inorganic and organic
chemistries.
• The molecule and its mirror
image are called enantiomers.
• The molecule does not have an
enantiomorphic pair is said
to exhibit chirality.

81
82
 Chirality in Life
• Nearly all biological polymers must be
homochiral
(all its component monomers having the
same handedness.
Another term used is optically pure or
100 % optically active)
to function.
• All amino acids in proteins are ‘left-
handed’, while all sugars in DNA and
RNA, and in the metabolic pathways, are
‘right-handed’.
• A 50/50 mixture of left- and right-handed
forms is called a racemate or racemic
mixture.
• Racemic polypeptides could not form the
specific shapes required for enzymes,
because they would have the side chains
sticking out randomly.
• Also, a wrong-handed amino acid
disrupts the stabilizing α-helix in
proteins.
 Thalidomide
• Thalidomide is a sedative drug that was prescribed to
pregnant women, from 1957 into the early 60's.
• It was present in at least 46 countries under different brand
names.
• "When taken during the first trimester of pregnancy,
Thalidomide prevented the proper growth of the foetus,
resulting in horrific birth defects in thousands of children
around the world"
• Why? The Thalidomide molecule is chiral.
• There are left and right-handed Thalidomides, just as there
are left and right hands.
• The drug that was marketed was a 50/50 mixture.
• One of the molecules, say the left one, was a sedative,
whereas the right one was found later to cause foetal
abnormalities.
• Examples of rotation and reflection operations

Basis

1 n=1 Rotation 1m Reflection

2 Rotation only 2mm Reflection twice

87
2.4 Inversion
• Occurs at an point known as the inversion point.
• Relates crystal planes using a combination of
rotation and reflection operations through a
centre point of inversion.
• A point of inversion or an inversion operation is
denoted by bar-1.
• It is also called a centre of symmetry.
• Objects with a centre of symmetry cannot
exhibit electric polarizability, optical activity
 Symmetry

Combination of
Basic Symmetry
Symmetry
Operator
Operator

Inversion Points
Translation – Mirror +
Rotation

Rotoinversion –
Rotation Rotation +
Inversion

Screw axis –
Mirror Plane Translation +
rotation

Glide Plane-
Translation +
Mirror plane
89
90
91
A point of inversion or
an inversion operation
is denoted by bar-1.

92
93
 Combination of
Translation <+/-> Axis <+/-> Plane <+/-> Point
produce

Roto-inversion - Axis <+/-> Point

Screw Axis - Translation <+/-> Axis
Glide Plane - Translation <+/-> Plane

94
 Symmetry

Combination of
Basic Symmetry
Symmetry
Operator
Operator

Inversion Points
Translation – Mirror +
Rotation

Rotoinversion –
Rotation Rotation +
Inversion

Screw axis –
Mirror Plane Translation +
rotation

Glide Plane-
Translation +
Mirror plane
95
96
97
98
99
100
101
 Screw Axes
• A screw axis, nm, is defined as a rotation around
the n-fold axis, followed by a translation of m/n
along the direction of the axis.

• Types of Screw Axes

– 2-fold screw axis 21
– 3-fold screw axis 31, 32
– 4-fold screw axis 41, 42, 43
– 6-fold screw axis 61, 62, 63, 64, 65

103
 Symmetry

Combination of
Basic Symmetry
Symmetry
Operator
Operator

Inversion Points
Translation – Mirror +
Rotation

Rotoinversion –
Rotation Rotation +
Inversion

Screw axis –
Mirror Plane Translation +
rotation

Glide Plane-
Translation +
Mirror plane
104
105
106
 Symmetry

Combination of
Basic Symmetry
Symmetry
Operator
Operator

Inversion Points
Translation – Mirror +
Rotation

Rotoinversion –
Rotation Rotation +
Inversion

Screw axis –
Mirror Plane Translation +
rotation

Glide Plane-
Translation +
Mirror plane
107
108
SYMMETR
Y
2.5 Two-dimensional lattices
• There are 5 Bravais lattices in 2-dimensions.
• For each of them the rotation axes and/or mirror planes
occur at the lattice points.
• However, there are other locations in the unit cell with
comparable or lower degrees of symmetry with respect
to rotation and reflection.
1. Oblique

b
γ
a

a ≠ b, γ ≠ 90° 112
2. Rectangular

γ
b
a

a ≠ b, γ = 90°

3. Centered rectangular

b
a ≠ b, γ = cos(a/2b)
γ

113
4. Square

a = b, γ = 90°
b γ

5. Hexagonal

a = b, γ = 120°
γ
b

a
114
• The oblique lattice is the general lattice while the
others are special lattices for the 2-dimensional
case
• All the lattice properties we discussed for two
dimensions can be extended to three
dimensions.
• The lattice vectors are in this case (3D)
T = n1a1 + n2a2 + n3a3
where a1, a2 and a3 are the primitive translation
vectors, and (n1,n2,n3) are a triplet of integers
whose values depend on a particular lattice site.
115
2.6 Three-dimensional lattices
• There are 14 types of Bravais lattices and
grouped in 7 crystal systems as building blocks
• The 7 crystal systems or types of cells are
triclinic, monoclinic, orthorhombic, tetragonal,
cubic, trigonal and hexagonal.
• The general lattice is triclinic while the others are
special lattices.

116
• The axes for a 3-dimensional lattice are
c

β α
b

a γ

• The division into 7 systems is expressed in terms

of the axial relations that describe the cells
• Each of the 14 lattices has one or more types of
symmetry properties with respect to reflection
and rotation.
– The 14 Bravais lattices contain one-, two-, three-,
four- and six-fold rotation axes and mirror plane. 117
118
119
α’ and γ’ not equal to 90º
2.7 Cubic lattices
• There are 3 types of cubic lattices
1. Simple cubic (sc)
2. Body-centered cubic (bcc)
3. Face-centered cubic (fcc)

124
• The conventional cubic cells of sc, bcc and fcc
have 1, 2 and 4 lattice points, respectively
• However, their primitive cells have one lattice
point
• The characteristics of sc, bbc and fcc are
summarized in the next table
125
126
127
128
• The primitive cell for bcc lattice is as below

• The primitive cell for fcc lattice is as below

130
• The primitive cell volume of bcc

131
• The primitive axes are

x y z
a’= 1 1 -1
b’= -1 1 1
132
• Similarly, by defining the primitive axes of fcc,
the primitive cell volume is

133
2.8 Hexagonal system
• a = b ≠ c and α = β = 90°, γ = 120°

(0,0,0) (a/2,a/2,0)

(a,0,0) 134
 Packing fraction
• Cubic unit cell is defined as unit cell for which
a = b = c and α = β = γ = 90°,
• Simple cubic or primitive unit cell
• In primitive unit cell one atom is present at
each corner of the unit cell.
• Atom present at corner in primitive
contributes 1/8th of its total volume to the
unit cell, hence effective atom(s) in unit call
is/are given by   
 where ‘r’ is the radius of atom and ‘a’ is edge length of the
unit cell, because in primitive unit cell a = 2r, 

• This indicates that the void fraction in primitive unit cell is

48% and rest is occupied by atoms.
Body centered cubic unit cell (BCC)
• In BCC, one atom is present at each corner
and contributes 1/8th of its volume to the unit
cell and one is present at centre and
contributed 100% to the unit cell, total atoms
can be calculated as 
• In given unit cell body diagonal is given by = 
Sqrt(3) X a
or a x Sqrt(3) = 4r
or a = 4r/ Sqrt(3)

• If means in above unit cell 68% volume is

occupied by atoms and rest 38% is void.
• For FCC -- 0.740
 Tutorial
1. Define symmetry. (15/100)
2. Give and describe all basic symmetry operations (25/100).
3. List, draw and describe 5 Bravais lattices in 2-dimensional
lattice. (20/100)
4. Describe 7 crystal systems in 3-dimensional lattice.
(25/100).
5. Show inversion center and mirror plane are equivalent to
roto-inversion of one-fold and two fold respectively.
(20/100).
6. Describe types of cubic lattices and their characteristics.
(35/100).
7. Prove that primitive cell volume and packing fraction of (i)
simple cubic, (ii) body-centered cubic and (iii) face-centered
cubic are (i) a3, 0.524 (ii) ½a3, 0.680 and (iii) ¼ a3, 0.740,
respectively. (5,10,15/100).
8. Calculate the number of nearest atoms and nearest
distance for s.c, b.c.c. and f.c.c cell. (5,10,15/100). How
about the second neighbors atoms? (10/100) 139
 Miller Index
• In Solid State Physics, it is important to be able to
specify a plane or a set of planes in the crystal.
• This is normally done by using the Miller indices.
• The use and definition of these Miller indices are
shown in the below figure

Miller indices of the plane are (233). 140

 Index System
3.1 Miller indices (hkl)
• Determination of position and orientation of
crystal planes
• Need to know the coordinates of any 3 points in
a crystal plane
• Consider the cubic lattice with a = b = c and α = β
= γ = 90°
• Then consider a plane that intercepts the a, b
and c axes at vector points a, b/2 and c/3,
respectively
141
 c

1/3

b
1/2

1
a

• The plane is define as (hkl) where h, k and l are the

reciprocals of the intercepts of the plane on the
axes a, b and c, reduced to three integers having
the same ratio
• The reciprocals of the above intercepts are 1, 2
and 3
• Thus, the Miller indices for the above plane are
(hkl) = (123) 142
• For an interception on the negative side of the
origin, a minus sign is place above the index, such
as
• For further examples, let us consider planes
intercepting the a, b and c axes at

1. 3a, 2b, 2c
Miller indices = (hkl) = (⅓½½)
х 6 to reduce to smallest three integers
(hkl) = (233)

143
2. 4a, 2b, 3c
Miller indices = (hkl) = (¼½⅓)
х 12 to reduce to smallest three integers
(hkl) = (364)

3. 4a, b, 2c
Miller indices = (hkl) = (¼1½)
х 4 to reduce to smallest three integers
(hkl) = (142)

144
4. Cubic
1 1 1

1 1 1
1 1 1

1 1

-1
O
1
1
1

145
• Miller indices for the surfaces of a cubic crystal

(001) c

(100)
a

(010)
b

• http://www.chem.qmul.ac.uk/surfaces/scc/scat1_1b.htm
• http://www.gly.uga.edu/schroeder/geol6550/millerindices.html

146
 Plane or Direction?
• The direction of any general vector can also be
expressed in terms of a set of indices h, k and l.
• These indices are the smallest integers that are
proportional to the components of the vectors along the
axes of the crystal (same as the translation vectors of
the unit cell).
• Unlike the Miller indices above, these integers used for
defining the direction of the general vector are not
derived from the reciprocal.
• To distinguish from the Miller indices for planes, i.e.
(hkl) or {hkl}, the direction indices are enclosed in
square brackets, hence [hkl].
147
 Plane or Direction?
• The indices [hkl] are used to denote many sets of
equivalent directions similar to the plane designations
above.
• For a cubic system, it can be shown that the vector [hkl]
is normal to the planes defined by the Miller indices {hkl}.
• This fact happens to be extremely useful in the analysis
of X-ray diffraction.
• The position of basis or atoms in the conventional cell is
often expressed in terms of the axes defining the cell.
– For instance, the position of the body-centred atoms is 1/2,
1/2, 1/2 and the face-centred atom is 1/2, 1/2, 0.

148
3.2 Direction indices [hkl]
• The indices are define as [hkl], to represent the
direction in a crystal
• For cubic, Normal
 [100] represent the direction of a axis to (100),
 [010] represent the direction of b axis (010) and
 [001] represent the direction of c axis (001)
planes
 represent the direction of –a axis
 [110] represent what?

149
3.3 Hexagonal system
• The 3 primitive axes can still be used to determine
the Miller indices of its crystal planes
• Normally 4 primitive axes of the hexagon are used to
represent a plane (hkil)
• h+k+i=0
• i = – (h + k)
h = –1
k=0
i=1 l
l=0
k
h
• For this plane, h + k + i = 0 120°
i
• Thus plane is
• http://www.uwgb.edu/DutchS/symmetry/millerdx.htm 150
152
Tutorialhttp://en.wikipedia.org/wiki/File:Miller_Indices_Felix_Kling.svg

153
Tutorialhttp://en.wikipedia.org/wiki/File:Miller_Indices_Felix_Kling.svg

154
155
 4 Simple Structures
4.1 Some examples of simple crystal structures
• Cu, Al, Pb and Ni have fcc crystal structure
• Each atom has 12 nearest neighbors

4.2 NaCl structure

• The underlying Bravais lattice is fcc
• Each atom has 6 atoms of the opposite kind as
nearest neighbors
• The shape of the primitive cell is rhombohedron
• Other examples are LiH, KCl, KBr, MgO …
156
 z
y

a = 5.63 Å
x

• Positions of atoms

Cl 000 ½½0 ½0½ 0½½

Na ½½½ 00½ 0½0 ½00
158
• The NaCl crystal is face centered cubic (fcc)
unit cell with the counter ion filling the
octahedral holes in the structure.
• It does not matter which ion is taken to be at
the vertices of the cell and which in the holes,
the same pattern is obtained, as can be seen
in the figure below:

159
160
Cl
Na

161
4.3 CsCl structure
• The underlying Bravais Cs
lattice looks like bcc, but
actually it is sc
• Thus the primitive cell is Cl ½½½
also sc
• Each atom is at the center
of a cube of atoms of the 000
opposite kind a = 4.11 Å

• Thus the number of nearest neighbor is 8

• Other examples are CuZn (β brass), TlBr,
AlNi, AgMg, BeCu …
162
163
 Why the number of
nearest neighbor is 8?
• CsCl structure, like the NaCl structure, the Cl
frame is displaced by one half of the body
diagonal of the conventional cubic cell.
• Here the nearest neighbour distance is that
between the Cl at the centre of the cube and
the Cs ion at one of the cube corners.
• Thus there are eight nearest neighbours.

165
166
4.4 Close-packed structures
• Two ways of arranging equivalent spheres of
atoms in a regular array so as to maximize their
packing fraction
• One produces fcc (cubic close-packed) structure
• The other leads to hexagonal close-packed (hcp)
structure
• Both produce 74% packing fraction (fraction of
the total volume filled by the spheres)
• Consider the plan view of a close-packed layer of
spheres as shown below
167
• A closed-packed structure is created by placing a
layer of spheres B on top of identical close-packed
layer of spheres A.
• There are two choices for a third layer.
– If it goes in over A the sequence is ABABAB. . . and the
structure is hcp.
– If the third layer goes in over C the sequence is
ABCABCABC. . . and the structure is fcc.
168
170
171
172
• Cubic close-packed
 First layer of atoms at A
 Second layer of atoms at B
 Third layer of atoms at C
 Thus an ABCABC … arrangement
with a rhombohedral primitive cell
173
The fcc structure with one
corner sliced off to expose a
(111) plane. The (111) planes
are close-packed layers of
spheres.
(After W. G. Moffatt, G. W.
Pearsall, and J. Wulff,
Structure, Vol. 1 of Structure
and properties of materials,
Wiley, 1964.)

174
• Hexagonal close-packed
 First layer of atoms at A
 Second layer of atoms at B
 Third layer of atoms at A
 Thus an ABABAB … arrangement
with a hexagonal primitive cell

c/2
c = 1.633a

a a 175
• The coordination number (number of nearest neighbor)
is 12 for both structures
• The c/a ratio for an ideal hcp is
1.633 (show this!)
• Some hcp crystals have c/a
ratio > 1.633, indicating that the
crystal structure is less
close-packed
• Examples of hcp structures are
He, Mg, Zn, Co, Zr (Zirconium),
Gd (Gadolinium ) …
176
 4.5 Diamond structure C C
C
• The underlying Bravais lattice is fcc
C Tetrahedral C
C B bond

C
C
¼¼¼

000 ¼AB C
A a = 3.56 Å
View C
• AB is the body diagonal
• Other examples are Si, Ge …
177
 4.6 Cubic ZnS structure
• The underlying Bravais lattice is fcc
Zn Zn Zn
B S

Tetrahedral Zn
S bond
¼¼¼
Zn
000 ¼AB
A a = 5.41 Å
View
• AB is the body diagonal
• Other examples are CuF, CuCl, SiC …
178
Atomic positions in the cubic cell of the diamond structure
projected on a cube face; fractions denote height above
the base in units of a cube edge.
The points at 0 and ½
are on the fcc lattice; those
at ¼ and ¾ are on a similar
lattice displaced among
the body diagonal by one-
fourth of its length.
With a fcc space lattice,
the basis consists of two
identical atoms at 000; ¼ ¼
¼

179
 Zn
B

S
¼¼¼
000 ¼AB
A
• Taking unity as the cube edge,
the numbers denote the
distances above the projected
face.
• The 0 and ½ numbers are for
the cube corner and face
centre atoms of the first sub-
lattice while the numbers ¼
and ¾ are those from the
second sub-lattice.
• This will give you a good idea
of the atom distribution in
such a structure.
181
4.7 Hexagonal ZnS (wurtzite) structure
Zn

• The vertical axis of hexagonal ZnS is a six-fold

screw axis, while for cubic ZnS it is a three-fold
axis
• The stacking sequences 012012 … and 010101 …
are similar to the fcc and hcp structures
182
 Tutorial
1. Determine the net number of Na+ and Cl– ions in the NaCl unit
cell. (15/100)
2. The geometric arrangement of ions in crystals of LiF is the same
as that in NaCl. The unit cell of LiF is 4.02 Å on an edge. Calculate
the density of LiF. The atomic mass unit can be obtained from
periodic table. (25/100)
3. Determine the “ideal” c/a ratio and packing fraction for an
hexagonal close-packed (hcp) crystal. (25/100)
4. NaCl has a density of 2.167 g/cm3. What is the distance between
adjacent atoms? (25/100) The atomic mass unit can be obtained
from periodic table.
5. Which stacking sequence of a planar triangular net of hard
spheres results cubic closet packing and hexagonal closet
packing. Elaborate the differences between these two closet
packing. (30/100)
6. Is face centered cubic a Bravais lattice? What about hexagonal
closet packing? What is the underlying lattice for the non Bravais
lattice (if it is) and how many atoms are there in the basis? (15/100)
184
 Introduction to X-ray Diffraction
• There are a number of methods for studying 3D structure.
• But we will concentrate on X-ray crystallography, which is
arguably the most effective of these techniques at present.

185
• If you think about how you determine the shape of
objects around you, the most obvious is just to look
at them.
• If they're small, you use a microscope.
• But there's a limit to how small an object can be seen
under a light microscope.
• The limit (the "diffraction limit") is that you can not
image things that are much smaller than the
wavelength of the light you are using.
• The wavelength for visible light is measured in
hundreds of nanometers, while atoms are separated
by distances of the order of 0.1nm, or 1Å.
Looking at the electromagnetic spectrum, X-rays
get us in the right wavelength range.

187
• But we can't build an X-ray microscope to look
at molecules, for two reasons.
– First, we don't have an X-ray lens.
– Second, even if we did have one, it would have to
be made with tolerances significantly less than the
distance between two atoms

188
 X-ray Crystallography
= X-ray + Crystals
Why X-rays?
• The use of electromagnetic radiation to visualise
objects requires the radiation to have a wavelength
comparable to the smallest features that you wish to
resolve.
• We often use X-rays emitted from copper targets
bombarded with high energy electrons, which emit
at several characteristic wavelengths: the one we use
is called CuKα, which has a wavelength of 1.5418 Å.
• This is very similar to the distance between bonded
carbon atoms, so it is well suited to the study of
molecular structure.
189
 What Is X-rays?
• X-rays are electromagnetic radiation with wavelengths
between about 0.1 Å and 100 Å (1Å = 10-10 meters).
• They are part of the electromagnetic spectrum that
includes wavelengths of electromagnetic radiation
called visible light in which our eyes are sensitive to
(different wavelengths of visible light appear to us as
different colors).
• X-rays have wavelengths similar to the size of atoms
and therefore able to explore within crystals.
• For X-ray diffraction, X-rays of wavelength about 1 Å is
normally used.

190
SMART APEX II Scheme
(Bruker, 2009)
SMART APEX II (left hand side) and APEX
II DUO (right hand side) System

(X-ray Crystallography Laboratory, School of Physics, Universiti Sains Malaysia)

 Diagram illustrating
X-ray diffraction techniques

193
 SMART Goniometer Components

(X-ray Crystallography Laboratory, School of Physics, Universiti Sains Malaysia)

 Data Collection
In X-ray diffraction measurement, a crystal is mounted on a goniometer and
gradually rotated while being bombarded with X-rays producing a diffraction pattern
of regularly spaced spots known as relections.

A sample prepared for X-ray Rotation photo for a good

crystallography. single crystal.
 Quinoline-2-carbonitrile–fumaric acid (1/0.5)

Scheme Diagram
Molecular View

[zigzag chains running along the

c-axis]

Packing Diagram
X-Ray Powder Diffraction

198
 X-ray Crystallography
= X-ray + Crystals

+ +

199
 5 Diffraction
5.1 Diffraction by crystal
• Diffraction provides information on the position
of atoms in the crystal
• Diffraction occurs when the wavelength, λ, of the
source used has a value ≤ the distance between
the atoms (≈ 1 Å)
• Sources that can be used are

200
• X-rays
 For photons in X-rays

 Or

 For λ = 1 Å, the energy required by the source is E

≈ 12 keV
 For X-rays crystal diffraction, the energy is
normally between 10 and 50 keV
201
• Most methods for determining the atomic structure of
crystals are based of the idea of scattering of radiation.
• X-rays is one of the types of the radiation which can be
used.
• Therefore, energy of x-rays are suitable for studying
the crystal structure.
• X-rays interact with electronic shells of atoms in a solid.
• Electrons absorb and re-radiate x-rays which can then
be detected.
• Nuclei are too heavy to respond.
• The reflectivity of x-rays is of the order of 10-3-10-5, so
that the penetration in the solid is deep.
• Therefore, x-rays serve as a bulk probe.
202
• Neutrons
 Analogous to radiation, particles; such as electrons,
protons, and neutrons have wave properties as
determined by the de Broglie equation

where lambda is wavelength, h is Planck's constant, and

p is the momentum of the particle.
 Or

 For λ = 1 Å, E ≈ 0.08 eV
203
 Electron microscopy
• Electrons diffract too, but they can also be focused by
magnetic fields, which allows the construction of electron
microscopes.
• The very best electron microscopes have resolving powers
near atomic resolution.
• There are special problems with sample damage, which
means that very low electron doses must be used to avoid
destroying the sample, so that the images have extremely
poor signal-to-noise and must be averaged.
• It turns out that electron microscopy tends to be most
useful for very large assemblies

204
 Calculate the wavelength of a free
electron with a kinetic energy of 2 eV
• The kinetic energy of an electron is related to its momentum by:

T = p2/2m, p = mv

from which we find the momentum, p:

p = (2mT)1/2 
= (2 x 9.1 x 10-31 x 1.6 x 10-19 x 2)1/2 
= 7.63 x 10-25 kg m/s.

• The de Broglie wavelength of the electron is then obtained from:

λ = h/p = 6.625 x 10-34 / 7.63 x 10-25 = 0.87 nm (8.7 Å)

• Electrons
 For electrons

 Or

 For λ = 1 Å, E ≈ 144 eV
 Transmission electron microscopy
 Scanning electron microscope

206
207
• The Nobel Prize in Physics 1915 was awarded
jointly to Sir William Henry Bragg and William
Lawrence Bragg "for their services in the
analysis of crystal structure by means of X-
rays"

208
Who Are
Them?

Richard Feynman
Albert Einstein
Stephen Hawking

Galileo Galilei
Isaac Newton
5.2 Bragg law

incident reflected

Atomic
planes

• The path difference between the two reflected

rays is

213
Diffraction is the slight bending of wave as it passes around the edge of an
object.
If the opening is much larger than the light's wavelength, the bending will be
almost unnoticeable.
However, if the two are closer in size or equal, the amount of bending is
considerable, and easily seen with the naked eye.
215
 Bragg law
• In 1913 Bragg found that crystalline solids
have remarkably characteristic patterns of
reflected x-ray radiation.
• In crystalline materials, for certain
wavelengths and incident directions, intense
peaks of scattered radiation were observed.
• Bragg accounted for this by regarding a crystal
as made out of parallel planes of atoms,
spaced by distance d apart.

216
• The conditions for a sharp peak in the intensity
of the scattered radiation were that:
– the x-rays should be specularly reflected by the
atoms in one plane;
– the reflected rays from the successive planes
interfere constructively.
• The path difference between the two x-rays is
equal to 2dsin.
• For the x-rays to interfere constructively this
difference must be an integer number of
wavelengths.
217
• Constructive interference for reflected rays
occurs when

• This is Bragg law where n is an integer .

• The integer n is known as the order of the
corresponding reflection (or order of
interference).
• Constructive interference occurs only for certain
values of angle 
• Bragg law is true for   2d
218
 Diffraction condition and
reciprocal lattice

• A crystal as composed of identical atoms

placed at the lattice sites T and assumed that
each atom can reradiate the incident radiation
in all directions.
• Sharp peaks are observed only in the
directions and at wavelengths for which the x-
rays scattered from all lattice points interfere
constructively.

220
• To find the condition of constructive interference we
consider two scatterers separated by a lattice vector T.
• Let x-rays are incident from infinity, along direction k̂
with wavelength λ and wavevector k = 2π/λ k̂ .
• We assume that the scattering is elastic, i.e. the x-rays
are scattered in k̂ ' direction with same wavelength λ, so
that the wavevector k = 2π/λ . k̂ '
221
 What is Wave Vector?
• k is just a convenient mathematical way of
expression both the direction of a wave and
it's wavelength.
• The wavevector  k  has magnitude equal to the
wave number k=2π/λ and a direction that is
the same as the direction of propagation of
the wave.
• The path difference between the x-ray scattered from
the two atoms should be an integer number of
wavelengths.
• Therefore, as is seen from previous figure, the
condition of constructive interference is

where m is an integer.
• Multiplying both sides of the Eq. by 2π/λ leads to a
condition on the incident and scattered wave vectors:

224
• Defining the scattering wave vector

the diffraction condition can be written as

where G is, by definition, such a vector for which

• A set of vectors G which satisfies this condition form a

reciprocal lattice.
• Vectors G are called reciprocal lattice vectors.

225
226
• There are a number of various setups for
studying crystal structure using x-ray
diffraction.
• In most cases, the wavelength of radiation is
fixed, and the angle is varied to observe
diffraction peaks corresponding to reflections
from different crystallographic planes.
• Using the Bragg law one can then determine
the distance between the planes.

227
• The Bragg law is greatly oversimplified
• It
– says nothing about intensity and width of x-ray
diffraction peaks;
– neglects differences in scattering from different
atoms;
– neglects distribution of charge around atoms.

228
5.3 Applications of Bragg law
• Bragg law requires  and  which are matched

• Laue method
 X-rays or neutron radiation with  between 0.2
and 2 Å (non-monochromatic)
 The crystal will select and diffract suitable  (at
certain suitable ) according to Bragg law

229
 The diffraction pattern is represented by bright
spots
 The pattern shows the crystal
symmetry
 In this case, a 4-fold symmetry

230
• Rotating crystal method

 In this method,  is fixed, while  varies when the

crystal is rotated
 Constructive interferences are formed when  and
 are matched 231
• Debye Scherrer powder method
camera Rotated
powder
specimen

Circular lines for rays diffracted

by powder specimen

 X-rays diffracted by fine powder specimen

  is fixed, while  varies due to the fine powder
and rotation of specimen
232
• Powder diffractometer method
 Similar to the Debye Scherrer method, however
the film is replaced by a counter
 The counter position is varied around the powder
specimen
 The incident angle, w, is defined between the X-
ray source and the sample
 The diffracted angle, 2q, is defined between the
incident beam and the detector angle
 The incident angle w is always ½ of the detector
angle 2q
233
 Detector
X-ray tube

w q 2q
Sample

234
235
 Nobel Prize winners associated with
crystallography
• The Nobel Prize is an international award administered by the
Nobel Foundation in Sweden. It has been awarded every year
since 1901 for achievements in physics, chemistry, physiology
or medicine, literature and for peace. Over the course of its
history, many awards have been made for scientific
achievements directly related to, or involving the use of,
crystallographic methods and techniques.
• 2012 Chemistry
R. J. Lefkowitz and B. K. Kobilka
For studies of G-protein-coupled receptors
• 2011 Chemistry
D. Shechtman
For the discovery of quasicrystals
• 2010 Physics
A. Geim and K. Novoselov
For groundbreaking experiments regarding the two-dimensional material graphene
• 2009 Chemistry
V. Ramakrishnan, T. A. Steitz and A. E. Yonath
Studies of the structure and function of the ribosome
• 2006 Chemistry
R. D. Kornberg
Studies of the molecular basis of eukaryotic transcription
• 2003 Chemistry
R. MacKinnon
Potassium channels
1997 Chemistry
P. D. Boyer, J. E. Walker and J. C. Skou
Elucidation of the enzymatic mechanism underlying the synthesis of adenosine triphosphate (ATP) and
discovery of an ion-transporting enzyme
1996 Chemistry
• R.Curl, H. Kroto and R. Smalley
Discovery of the fullerene form of carbon
1994 Physics
• C. Shull and N. Brockhouse
Neutron diffraction
1992 Physics
• G. Charpak
Discovery of the multi wire proportional chamber
1991 Physics
• P.-G. de Gennes
Methods of discovering order in simple systems can be applied to polymers and liquid crystals
1988 Chemistry
• J. Deisenhofer, R. Huber and H. Michel
For the determination of the three-dimensional structure of a photosynthetic reaction centre
1985 Chemistry
• H. Hauptman and J. Karle
Development of direct methods for the determination of crystal structures
1982 Chemistry
• A. Klug
Development of crystallographic electron microscopy and discovery of the structure of biologically
important nucleic protein complexes
1976 Chemistry
• W. N. Lipscomb
Structure of boranes
1972 Chemistry
• C. B. Anfinsen
Folding of protein chains
• 1964 Chemistry
• D. Hodgkin
Structure of many biochemical substances including Vitamin B12
1962 Physiology or Medicine
• F. Crick, J. Watson and M. Wilkins
The helical structure of DNA
1962 Chemistry
• J. C. Kendrew and M. Perutz
For their studies of the structures of globular proteins
1954 Chemistry
• L. C. Pauling
For his research into the nature of the chemical bond and its application to the elucidation of the structure
of complex substances
1946 Chemistry
• J. B. Sumner
For his discovery that enzymes can be crystallised
1937 Physics
• C. J. Davisson and G. Thompson
Diffraction of electrons by crystals
1936 Chemistry
• P. J. W. Debye
For his contributions to our knowledge of molecular structure through his investigations on dipole
moments and on the diffraction of X-rays and electrons in gases
1929 Physics
• L.-V. de Broglie
The wave nature of the electron
1917 Physics
• C. G. Barkla
Discovery of the characteristic Röntgen radiation of the elements
• 1915 Physics W. H. Bragg and W. L. Bragg
Use of X-rays to determine crystal structure
1914 Physics M. Von Laue
Diffraction of X-rays by crystals
1901 Physics W. C. Röntgen
Discovery of X-rays
 Tutorial
1. Prove Bragg law using (30/100)
2. Why is X-ray the best choice to study the molecular
structure of a compound if compared with the neutron
and electron sources? Explain it. (15/100)
3. Among Mo (λ = 0.7 Å) and Cu X-rays sources (λ = 1.5 Å) ,
which gives better intensity when the same energy
applied and why? (20/100)
4. Calculate the wavelength of Neutron radiations when E
≈ 0.08 eV is applied. (15/100).
5. Define Diffraction. Explain the importance of diffraction
to elucidate the crystal structure. (20/100)

239
• If a, b and c are primitive translational vectors for
a crystal lattice, then the primitive translational
vectors for the reciprocal lattice are define as


A is perpendicular to b and c
 B is perpendicular to c and a
C is perpendicular to a and b

240
241
242
• Thus, A, B and C have the vector characteristics




• Can be shown that

Denominator in each equation is
the dot scalar product of the three
real primitive vectors. Note that

this defines the volume of the real
parallelepiped.

243


• 2-dimensional example

b
B Crystal/Bravais
lattice
a
A
Reciprocal
lattice

244
245
246
247
a* is perpendicular to b and c
b* is perpendicular to c and a
c* is perpendicular to a and b 248
Cross Product : A X B
• Translations in the reciprocal space are
represented by the reciprocal lattice vectors
–
• h, k and l are integers ( Miller indices)
• represents the lattice points in the
reciprocal space
Tutorial
1. Show that the Bragg law can be written in terms
of the reciprocal lattice vectors as
–
– k is the wave vector and G is the reciprocal lattice
vector
250
 Tutorial
2. Show that a (hkl) plane is perpendicular to
the reciprocal lattice vector
The crystal plane with Miller indices hkl is a plane
defined by the points,
Two vectors that lie in the plane may be taken as

But each of these vectors gives zero as its scalar

product with

so that must be perpendicular to the plane hkl.

251
 1/2

1/2 1/2

(222) 1
1
252
Vector Equation of a Plane

Ghkl = 1A + 1B + 0C
b

b/k = b/1
V1- V2 = a/1 – b/1
Reciprocal
Plane (hkl) or (110) Lattice
V2

Ghkl
a
r
V1 a/k = a/1
Equation of a Plane with three coordinates
lying on that plane

(4,0,0), (0,-5,0), and (0,0,3).

Ax + By + Cz = D 15x - 12y + 20z = 60

(4,0,0) ---> 4A + 0B + 0C = D 15X/60 -12Y/60 + 20Z/60 = 60/60

(0,-5,0) --> 0A - 5B + 0C = D
(0,0,3) ---> 0A + 0B + 3C = D x/4 + y/-5 + z/3 = 1

4A = D x/A + y/B + z/C = 1

-5B = D
3C = D

D = 60
A = 60/4 = 15
B = 60/-5 = -12
C = 60/3 = 20

254
 The Vector Equation of a Plane
• Here, we use our knowledge of the dot product to find the
equation of a plane in R3 (3D space).
• Firstly, a normal vector to the plane is any vector that starts at a
point in the plane and has a direction that is orthogonal
(perpendicular) to the surface of the plane.
• For example, k = (0,0,1) is a normal vector to the xy plane (the
plane containing the x and y axes). 
• Any three distinct points define our plane, or alternatively, a
single point in the plane and a given normal vector to the plane.
• We'll define it like this first.
• All we need is a way of checking whether a given point, with
position vector r lies in the plane or not. 

255
• Let a be the position vector of the given point in the
plane, and let n be the given normal vector to the
plane. 
• Then r is in the plane if and only if (iff) 
(r - a) . n = 0 
• Explanation: r - a is the vector from A to R, and any
vector that lies completely in the plane (like this one
does) must be orthogonal to n which implies their
dot product must equal 0.  256
 Tutorial
3. Show that

• If is the unit vector normal to the plane, the

inter planar spacing is
• But

whence
• Direction [hkl] perpendicular to plane (hkl)
• Therefore, Ghkl vector (direction) perpendicular with
plane (hkl)

Atom or
Lattice point
Real
Lattice
d2
d3
a
r
d1
 Tutorial
4. Show that for a simple cubic (sc)

–
• For a simple cubic lattice

whence,

259
= [hA hA cos0 + hA kB cos90 + hA lC cos90 +
kB hA cos90 + kB kB cos0 + kB lC cos90 +
lC hA cos90 + lC kB cos 90 + lC lC cos 0] 4π2
= 4π2 [hA hA cos0 + kB kB cos0 + lC lC cos 0]
= 4π2 (hA)2+ (kB)2 + (lC)2 [A=B=C=1/a, simple cubic]
= 4π2 (h2+k2+l2)(1/a)2
Wavenumber

k = 1 / λ, cycles per unit distance

(spectroscopic wavenumber )

k = 2 π / λ, radians per unit distance.

(angular or circular wavenumber or simply
wavenumber)
 Introduction to
First Brillouin Zone
• We have already learnt how the Wigner Seitz cell is
defined in the real lattice.
• The volume of this is equal to that of the primitive
parallelepiped.
• In fact such a construction is also adopted in the reciprocal
lattice space and the space so defined is called the first
Brillouin zone.
• The physical significance of this will be apparent in x-ray
diffraction and phonons.
• It is formed by constructing perpendicular bisectors for all
the reciprocal vectors radiating from the centre of the cell.
262
 b
b 1 2
a a 3
b
a

Reciprocal
Lattice :
Brillouin
Zone

Real Lattice :
Wigner-Seitz
primitive cell
 Brillouin gave another statement of the diffraction condition.

• Consider a two-dimensional lattice in the reciprocal

space.
• Let O be the origin of this lattice.
• Consider a reciprocal lattice vector, which connects
points O and another reciprocal lattice site.
• Now draw the line (in the
three dimensions it would
be a plane), which is
orthogonal to this vector
and intercepts it in the
midpoint. 264
• The x-ray will be diffracted if its wavevector k
has the magnitude and direction that is
required by the condition
which can be rewritten in the following way

• It is easy to see that any k vector connecting

the origin and the plane will satisfy the
diffraction condition (specific angle, sine theta).

265
 • In a similar way we can draw other lines (planes), which
satisfy the diffraction condition.
• The Brillouin construction exhibits all the wave vectors k
which can be Bragg-reflected by the crystal.
• The central part of the reciprocal
lattice is of special importance in
the theory of solids.
• It is the first Brillouin zone.
• The first Brillouin zone is the
smallest volume entirely enclosed
by the planes that are
perpendicular bisectors of the
reciprocal lattice vectors.
• In this construction it is the
rectangle about the origin.
266
7.1 1-dimensional lattice
• Brillouin zone is define as Wigner-Seitz cell in the
reciprocal lattice
Linear crystal O
lattice a x
a
• The primitive vector of the crystal lattice (real
lattice) is a of magnitude a

Reciprocal O
lattice A 2/a k

First Brillouin zone 267

• The primitive vector of the reciprocal lattice is A
of magnitude 2/a
• Since

• Thus the translational reciprocal lattice vector is

(in one dimensional).
• The first Brillouin zone is the minimum distance
(1-D), area (2-D) and volume (3-D) enclosed by
planes which are perpendicular bisectors to the
reciprocal lattice primitive vectors drawn from
the origin. 268
• The edge of the first Brillouin zone for the 1-D
lattice is

7.2 Two-dimensional lattice

b y
Crystal
lattice O a x
a=b= a

• This is actually a Bravais (real) square lattice

269
Reciprocal B
/a ky
lattice
First Brillouin O A kx
zone
-/a
A=B= 2/a
-/a /a
• The first Brillouin zone (area) is enclosed by
and
• Similar steps apply to other 2-D Bravais lattices in
the determination of their first Brillouin zones
• Second and third Brillouin zones?
270
Second (and higher) Brillioun Zone
• The second Brillouin Zone is
the region of reciprocal space
in which a point has one
Bragg Plane between it and
the origin.
• This area is shaded yellow in
the picture beside.
• Note that the areas of the
first and second Brillouin
Zones are the same.
271
2-D square / 2-D hexagonal
lattice

272
 2-D square lattice

5 4 3 4 5 1. Joint a lattice point to its

4 2 1 2
neighbors using straight
4
lines
3 1 1 3
2. At the middle point and
4 2 1 2 4 normal to these lines,
draw new lines (2-
5 4 3 4
5 D)/planes (3-D)

273
2-D square
lattice

274
2-D square / 2-D hexagonal
lattice

275
 2-D hexagonal
lattice

4 3 2 3 4

2 1 1 2

3 1 1 3

2 1 1 2

4 3 2 3 4

5 5

276
2-D square / 2-D hexagonal
lattice

277
2-D hexagonal
lattice

278
7.3 3-dimensional lattice
• See an example in Kittel for the first Brillouin
zone of a sc lattice
Shape of Shape of Shape of First
Crystal Lattice Reciprocal Brillouin Zone
Lattice
Simple cubic Simple cubic Cube
Body-centered Face-centered Rhombic
cubic cubic dodecahedron
Face-centered Body-centered Truncated
cubic cubic octahedron

279
281
 Determine the reciprocal lattice
of an FCC lattice
• Select a Cartesian coordinate system with unit
vectors i, j and k.
• Position the coordinate axes so that in this system
one of the corners of the FCC unit cell will be at
(0,0,0) and the edges starting there lie in the
positive i, j and k direction.
• Select the three a1, a2 and a3 vectors to point to
the center points lying on the three coordinate
planes.
• With these notation

282
• The formula for the three reciprocal vectors
b1, b2 and b3

284
 a1.(a2 x a3)
• Determine first the denominator, which is the
volume of the primitive cell

• Here we used the fact that i, j and k are

perpendicular to each other.
• Furthermore we know that i x j = k, j x k = i and k x
i = j.
• So, the denominator becomes
285
 Now the nominators:

The reciprocal base vectors:

These vectors correspond to the primitive

vectors of a body-centered cubic lattice
in the reciprocal lattice
286
287
• Γ: The centre of the zone (as before)
• X: Zone boundary along one of the axes, e.g. the x-axis
• L: Zone boundary along the diagonal
• K: Zone boundary in the middle of an edge
• W: Point between K and X, furthest away from Γ

288
289
• Tutorial: The primitive vectors of a hexagonal
space lattice are

1. Show that the volume of the primitive cell is

290
2. Show that the primitive vectors for the
reciprocal lattice are

3. Discuss and sketch the first Brillouin zone

292
 What holds a crystal together?
Interatomic forces + Pauli principles

Atoms bind due to the

Coulomb attractive and
repulsive forces
between electrons,
neighboring atomic ions
and nuclei.
293
 Introduction to Crystal Binding
• Solids are stable structures, and therefore there exist
interactions holding atoms in a crystal together.
• The arrangement of atoms in a solid (its 'structure') can be of
many different types, even for the same material.
• Its formation depends on 'external' parameters like
temperature T and pressure p and the 'route' in the phase
diagram which is followed during transition, e.g. from a liquid
to a solid.
• Important 'internal' parameters are the electronic configuration
of the atoms, or the atomic/ionic radii, which also determine
the nature and strength of binding between atoms.

294
 Crystal Binding
• A NaCl crystal is more stable than groups of free
Na and Cl atoms
• The condition for the stability of a crystal is
cohesive energy = free atoms energy – crystal energy
(The cohesive energy of a solid is the energy required to
break the atoms of the solid into isolated atomic species)
• Example
Si Ar
Cohesive energy 446 7.74
(KJ/mol)
Strength of binding Strong Weak 295
• The electrostatic attractive force interaction
between negative charge electron (atom A) and
positive charge nucleus (atom B) is the main
force that contributes to cohesion in the solid
• This force is strong if the atoms are far apart (but
not too far too).
• If the atoms are very close together, the
electronic charge distributions of the atoms
overlap, and the repulsive force between
electrons will be the main force.
• This is due to Pauli Exclusion Principle of which
 2 electrons cannot have the same quantum number
296
 Cohesive energy =
energy of free atoms – crystal energy
• The amount of energy which is required to pull
the crystal apart into a set of free atoms is
called the cohesive energy of the crystal.
• Magnitude of the cohesive energy varies for
different solids from 1 to 10 eV/atom, except
inert gases in which the cohesive energy is of
the order of 0.1eV/atom.
• The cohesive energy controls the melting
temperature.
297
 Binding Energy
• A typical curve for the potential energy (binding
energy) representing the interaction between two
atoms is shown in Figure below.
• It has a minimum at some distance R=R0.
• For R>R0 the potential increases gradually, approaching
0 as R-> infinite, while for R<R0 the potential increases
very rapidly, tending to infinity at R=0.

298
 Binding Energy -cont

• Since the system tends to have the lowest

possible energy, it is most stable at R=R0, which
is the equilibrium interatomic distance.
• The corresponding energy U0 is the cohesive
energy.
• A typical value of the equilibrium distance is of
the order of a few angstroms (e.g. 2-3Å), so that
the forces under consideration are short range.

299
 Binding Energy -cont
• The interatomic force is determined by the gradient of
the potential energy, so that

• If we apply this to the curve, we see that F(R)<0 for

R>R0.
• This means that for large separations the force is
attractive, tending to pull the atoms together.
• On the other hand F(R)>0 for R<R0, i.e. the force
becomes repulsive at small separations of the atoms,
and tends to push the atoms apart.
• The repulsive and attractive forces cancel each other
exactly at the point R0, which is the point of
equilibrium.
300
• The attractive interatomic forces reflect the presence of bonds
between atoms in solids, which are responsible for the stability
of the crystal.
• Magnetic force is weak while gravitational force has a very
small value
• Types of chemical binding in solids are
 Ion - Electrons localized among atoms
 Covalent
 Electrons shared by the neighboring atoms
 Metal Sometimes
 Electrons free to move through sample (e-sea) a mixture
 Molecule (Van der Waals) of these
 Electrons localized among atoms bindings
 Hydrogen
 Special bonding between polarized molecules 301
 Fundamental interactions
Universe is governed by four forces
• Gravity - This force acts between all mass in the
universe.

• Electromagnetic - This acts between electrically

charged particles. Electricity, magnetism, and
light are all produced by this force and it also
has infinite range.

• The Strong Force - This force binds neutrons and

protons together in the cores of atoms.

• Weak Force - This causes Beta decay (the

conversion of a neutron to a proton, an electron
and an antineutrino) and various particles are
formed by strong interactions but decay via
weak interactions .
8.1 Ion binding
• NaCl is an example of a crystal with ion binding
• In its crystalline state, each Na atom loses one
electron to its neighboring Cl atom
• Thus an ionic crystal is created with positive ions (Na+)
and negative ions (Cl-)
• The electrostatic interactions (attractive and repulsive
forces) between these ions contribute to the ion
binding
• The outer electrons for each ion is similar to the outer
electrons for atoms of inert gases, i.e. having closed
electronic shells
• Examples of outer closed shells 303
NaCl Na Cl
3s 3s23 p5
electron
Na+ Cl-
2s22p6 3s23p6
(Ne) (Ar)

KCl K Cl
4s 3s23 p5
K+ electron Cl-
3s23p6 3s23p6
(Ar) (Ar)
304
LiF Li F
2s electron
2s22 p5
Li+ F-
1s2 2s22p6
(He) (Ne)

CsCl Cs Cl
6s electron 3s23 p5
Cs+ Cl-
5s25p6 3s23p6
(Xe) (Ar)
305
306
307
 Properties of Ionic Crystals
• In an ionic crystal, the electrostatic bonding normally
comes from the transfer of electrons from alkali atoms
to halogen atoms, resulting in the bonding of positively
and negatively charged ions by the Coulomb attractive
force.
• Typical examples are alkali metals such as sodium and
potassium, in which each of these atoms has one extra
valence electron to transfer to the atoms of halogens
such as chlorine and bromine to form an alkali halide
salt (e.g., NaCl, KCl, NaBr, etc.).
• The ionic crystal usually has high binding energy due to
the strong Coulombic force between the positive and
negative ions.
308
• The electrical conductivity of an ionic crystal is usually
smaller than the electrical conductivity of a metal.
• Ionic crystals formed by the group- I and group- VII
elements (e.g., NaCl, KCl) in the periodic table belong
to this category.
• Although they are good electrical insulators at room
temperature due to their large binding energy, these
ions may become mobile at very high temperatures
and diffuse through the crystal, which results in an
increase of electrical conductivity.
• Because no free electrons to carry energy or charge
they are poor conductors of heat or electricity

• Because of the strong electrostatic forces between ions

they are hard and have high melting points
309
8.2 Madelung constant
• The largest energy contributor to cohesive
energy is from electrostatic and known as
Madelung energy
• For NaCl crystal

r0

310
• For one Na+ ion, there are
 6 Cl- ions at distance r0
 12 Na+ ions at distance r02
 8 Cl- ions at distance r03
 And so on …
 Thus the total Coulomb attraction energy (Madelung
energy) due to each ion pair is a summation of an
infinite series

 e is the charge of an electron (= 1.6022x10-19 C);

4πε0 = 1.11265x10-10 C2/(J m) 311
 where  is known as the Madelung constant
• Some values of Madelung constant
Crystal Madelung
Constant 
NaCl 1.747565
CsCl 1.762675
Cubic ZnS 1.638100
Wurtzite ZnS 1.641000
CuO2 4.115500
312
• The properties of ionic crystals depend on the
charge transfer
• The strength of ionic binding is high as compared
to other types of binding
• The binding strength of NaCl and KCl are 7.90
and 7.30 eV/molecule, respectively

8.3 Covalent binding

• Covalent or sometimes called valence binding is
the binding of a pair of electrons whereby two
atoms sharing two electrons
313
 Properties of Covalent Crystals
• The properties of covalent crystals depend on the
localization of the electrons that formed the
covalent bonding
• Covalent bonding in diamond
C

e- C Forming a
e-
e
e- - tetrahedron
C e-
e-
(a structure
e-
e- with 4 planes)
C
C
Covalent bonding 314
• Each bond has two electrons and each electron is
contributed by two different C atoms
• The sharing of electrons causes each C atom to
have eight electrons around it (closed outer
electronic shells), thus stable, (2s22p2 2s22p6)
• Other examples are
 Elements in Group IV of the Periodic Table, such
as Si, Ge and Sn
 Alloys of Group III and V, such as GaAs
 Elements of Groups V, VI and VII (complex crystal
structure) such as As, Sb, Te, I and Br
315
 Electrons shared by atoms
• Atoms that are bound by shared valence electrons
• Bonds are directional and determine the geometric
arrangements of atoms in the crystal structure
• The rigidity of their electron structure makes
covalent solids hard and difficult to deform, so, high
melting point
• No free electrons so not good heat or electrical
conduction
• Sometimes, as for silicon and germanium they are
semiconductors
• In diamond each carbon atom is bonded covalently
to 4 other carbon atoms
• In diamond the basic structure is tetrahedral
316
8.4 Mixed ion-covalent binding
• In compounds that have less electropositive
element (cation) and less electronegative
element (anion), the transfer of electron charge
from cation to anion (like ion binding) is
incomplete (less than 100 %)
• The electron binding is now a mixture of covalent
binding and ion binding wave functions
• electron binding = covalent binding + λion binding
• λ is the degree of ionization given by

317
• λ can be calculated if % ionization is known
• Calculate the λ for a compound which is 75%
ionized.
• The actual value of λ is usually calculated using
quantum mechanics, via the energy equation

• H is the Hamiltonian operator and τ the average

time
• λ is known when E has a negative minimum
value (indicating stability)
318
• Some values for % ionization and λ
Crystal % ionization Calculated λ
NaCl 94 ( ion bonding) 3.96
AgBr 85 2.38
ClTe 67 1.42
GaAs 31 ( covalent bonding) 0.67
Ge 0 ( covalent bonding) 0.00

319
8.5 Metal binding
• Metals have high electrical conductivity because
their electrons are non-localized (free electrons)
• These free electrons are known as conduction
electrons
• Some examples of metals

• Na metal
 Electron configuration
1s22s22p63s1
[Ne]3s1
320
 Each Na atom has one valence electron, which is
weakly bound to the atom
 When the solid is form, these electrons dissociate
themselves from the Na atoms and become free
to move inside the crystal
Gas state Solid State
3s1 e- e-
e-
e- 3s1
3s1
e-

3s1 Electron
Na e- Na atom wave
atom e -
(core ion) function
321
 Electron wave functions (Bloch functions) overlap
and create metal binding
 Can be considered as an arrangement of positive
charges (core ions) surrounded by a “sea” of
negative charges (electron gas)

• Fe metal
 Electron configuration
1s22s22p63s23p63d64s2
[Ar]3d64s2 Metal binding (free electrons)

Covalent binding (localized property) Magnetic property

322
• Almost all metals have bcc, fcc and hcp structures
• With respective packing fractions of 68%, 74%
and 74%, higher than the packing fraction of
diamond (34%) which has covalent binding
• Strength of metal binding is  strength of ion and
covalent bindings

Core ion Strength of binding

(eV/atom)
Na (bcc) 1.1
Ag (fcc) 3.0
Ni (fcc) 4.4
323
• Comparison of electrical conductivity for various
types of binding
Crystal (Binding) Electrical Conductivity
 (-cm)-1
NaCl (ion) 0.1
Diamond (covalent) 10-4
Ge (covalent) 40
Cu (metal) 6  105
• As temperature increases, there is an increase in
the vibrations of core ions, resulting in an
increase of electron scattering by core ions, thus
a smaller value for the electrical conductivity324
• Metallic solids are excellent conductors of electricity
or heat.
• The electrons easily absorb energy from incident
radiation or lattice vibrations and move under the
influence of an applied electric field or thermal
gradient
• One of the most striking features of a metal is its high
electrical conductivity.
• The binding energy of a metal comes mainly from the
average kinetic energy of its valence electrons, and
there is no tendency for these electrons to be
localized within any given portion of the metal.
8.6 Molecule binding (Van der Waals)
• Solid inert gases (He, Ar, Kr, Ne and Xe) and solid
molecules (H2, CH4 and Cl) have molecule binding
• This binding originates from the very small
attractive force between atoms whose outside
electron shells are full (closed)
• The electrons are unable to be transferred or
shared between atoms, thus there are no ion or
covalent bindings
• Hence, the weak molecule binding ( 0.2
eV/atom) becomes very important
326
• The melting point for solids with molecule
binding is low
Solid Melting Point C
He - 272.2
Ne - 248.7
Ar - 189.2
• Inert gases are fcc except for He3 and He4
• Molecule binding often occurs in structures that
have high number of nearest neighbors
• Solid molecules have strong electron localization
at each ion cores, thus they are electric insulators
327
8.7 Solids with covalent and molecule (Van der
Waals) bindings
• Tellurium
Each atom makes covalent
Te bonds with its nearest
Te neighbors up and down
the spiral chain

Inter-chain weaker forces

(Van der Waals molecule
bonding) hold the spiral
chains together
Spiral
chains 328
• Graphite Within a layer, each
atom makes three
strong covalent bonds
C
C
Weaker forces
(Van der Waals
molecule
bonding) hold
the layers
together

• The graphite planes can easily slide over each

other because of the weak molecule bonding
329
8.8 Hydrogen binding
• Extremely weak with binding strength between
0.1 and 0.5 eV/atom
• Occurs in solid molecules such as ice, hydrogen
fluoride (HF) and potassium hydrogen
phosphate (KH2PO4)
• The binding is between hydrogen atom and
atoms which are too negative (anion), such as F
(2s22p5), O (2s22p4 ) and N (2s22p3 )
• For ice, H2O

1s 2s22p4
1s 330
• Two covalent bindings exist between H and O
H 1s2 H 1s2
2s22p6O Hydrogen binding
H
H O
O
H H
Covalent binding
• Hydrogen binding exists between molecules of
H2O
• As a summary, there are crystals with mixed
bindings, and types of binding provide
information on the types of crystal structure,
and vice versa 331
 Tutorial
1. Illustrating with a graph, explain cohesive energy
(25/100).
2. List and explain all types of chemical binding in solid.
(15/100).
3. Give the differences between ionic and covalent bonds
(20/100).
4. Define degree of ionization, λ, and % ionization (10/100).
5. Explain the features of alkali-halide which is an ionic
bonded salt (20/100).
6. Compare the thermal and electrical conductivity for
various types of binding. (20/100).
7. Describe Metal binding. (20/100).
8. Describe Van der Waals binding. (15/100).
 Why do We Study Lattice Vibrations?
• When the lattice is at equilibrium each atom is
positioned exactly at its lattice site.
• Now suppose that an atom displaced from its
equilibrium site by a small amount.
• Due to force acting on this atom, it will tend to
return to its equilibrium position.
• This results in lattice vibrations.
• Due to interactions between atoms, various
atoms move simultaneously, so we have to
consider the motion of the entire lattice.

334
 LATTICE VIBRATIONS:
PHONONS
• In a real crystal atoms are not fixed at rigid sites
on a lattice, but are vibrating.
• In a periodic structure the vibrations have a
waveform (just like electronic wavefunctions)
with a spatial and temporal part:
• u(r, t) = uo exp (ik.r) exp(–iωt)
• k =2π/λ ; hω represents a “quantum” of vibration
energy.
• ω (2πf) vs. k (2π/λ) is the dispersion relation
(interrelations of wave properties).
335
 QUESTIONS
• What controls the ω vs. k relation?
• What is the amplitude of vibrations and how
does it depend upon temperature?
• What are the issues involved in second
quantization?
• What are phonons?

336
 9 Lattice Vibrations
9.1 Phonons
• Lattice vibrations are due to the thermal
properties of the crystal lattice
• The atoms are displaced with a very small
distance (obeying Hooke’s law) which is periodic
• The lattice vibrations have wave and particle
properties (similar to photons)
• The particle property of quantized lattice
vibrations is known as phonons, and the wave
transmission of lattice vibrations in a crystal is
assumed as the motion of one or more phonons
337
• Each phonon has energy h = ħ and momentum ħk
• Phonons have main effects on
– specific heat capacity
• (amount of heat per unit mass required to raise the temperature by
one degree Celsius )
– electrons scattering
• (process whereby an electron is deflected from its original trajectory)
– thermal conductivity
• (property of a material's ability to conduct heat).

9.2 Linear monoatomic lattice vibrations

• The objective is to obtain the dispersion relation, which
is the relationship between  (angular frequency) and k
(wave vector), for lattice vibrations
338
LATTICE VIBRATIONS :
RESTORING FORCE

339
Lattice in
equilibrium x
ur ur + 1
Atoms
displaced by
longitudinal
plane wave x
with
displacement
ui (a + ur – ur – 1)
• The plane wave transmission in x direction can be
represented by a periodic displacement equation
(9.1)
• This is a general equation for monochromatic wave
with amplitude A, wave vector k and angular
frequency 
340
• Displacement for atom r is
(9.2)
• The restoring force that acts on atom r is (-x
direction)

(F=ma) (9.3)
• To determine the dispersion relation of  versus
k, the “ball and spring” model for a monoatomic
lattice is used to obtain another equation for the
restoring force Fr.
• In this model, the force that acts on an atom
only depends on 341
 (extension or contraction) of nearest
neighbors distance only
• This is Hooke’s law where  is Hooke
proportional constant (F=-kx)
• Thus, the restoring force on atom r is

(9.4)
• Compare Eqs. (9.3) and (9.4)

(9.5)
342
• Substituting for , and into Eq. (9.5)

eika = cos ka + i sin ka

e-ika = cos ka - i sin ka

(9.6)

• Thus, the dispersion relation for longitudinal

wave in a monoatomic linear lattice according to
the nearest neighbor restoring force is

343
 (9.7)

• where  represent wave travelling to the right or

left and

• The dispersion relation of Eq. (9.7) is as below

344
 Group Velocity
• The group velocity of a wave is the velocity with which
the overall shape of the wave's amplitudes — known as
the modulation or envelope of the wave — propagates
through space.
• The function ω(k), which gives ω as a function of k, is
known as the dispersion relation.

http://resource.isvr.soton.ac.uk/spcg/tutorial/tutorial/T
utorial_files/Web-further-dispersive.htm

http://www.princeton.edu/~achaney/tmve/wiki100k/d
ocs/Group_velocity.html
 ka  1

ka = 3.14

First Brillouin Zone

346
• Consider the case for ka << 1
• This is the region for long wavelength, i.e.
acoustic wave
K = 2π/λ

• Thus

• The velocity of acoustic wave is

347
• For this nearly linear region
phase velocity = group velocity =
= =

• Case for ka >> 1 (large), i.e. λ small

• The maximum value for  is (when )

• The phase velocity is

348
• Group velocity

349
9.3 3-dimensional monoatomic lattice
• In general there are one longitudinal (L) and two
transverse (T) wave components for the
dispersion relation of solids.

Two T here
Two T here (degenerate)
(degenerate)
Quantum
degeneracy means
that more than one
quantum states
have exactly the
same energy.

351
• Thus, there exists dispersion branches, for
example in fcc metals such as Pb and Cu
• These branches are dependent on the direction
of k
• The center of the first Brillouin zone is at
coordinates (000)
• The data for the dispersion relation is obtained
using inelastic scattering of slow neutrons

352
9.4 Modes of vibration for a linear diatomic lattice
• Two types of atoms with different masses

x
m M m M m

• Mass of m < M, and the distance between two

similar atoms is 2a
• The small displacement of atom m is
(9.8)

353
• The small displacement of atom M is
(9.9)
• Since the displacements are small, Hooke’s law
can still be used
• Restoring force for atom m is

(9.10)
for atom M is

354
 (9.11)
• Substitute Eqs. (9.8) and (9.9) into Eqs. (9.10)
and (9.11)
(9.12)
(9.13)
• Rearrangement gives

• Elimination of A and B

355
• Using

• The dispersion relation becomes

(9.14)
• Thus for each k, there are two values for 
• Positive sign indicates upper branch (optic mode)
356
• Negative sign indicates lower branch (acoustic
mode)
Optic branch

Forbidden
frequency
range

Acoustic
branch
min = 0

358
First Brillouin zone
 LATTICE VIBRATIONS:
ACOUSTIC AND OPTICAL VIBRATIONS

359
9.5 Acoustic branch
•

  and k are small for large λ (long wavelength)

 Thus
361
  All atoms move in the same direction
Displacement

• When ↑, k↑ and B/A↑ as well

 When → 1, A →0 since k→π/2a
 Thus light atoms do not move and 1 is
independent of m
362
• k→0, →min = 0
• For k = π/2a, phase velocity

group velocity

• There is a range of forbidden frequencies

between the acoustic and optic branches, where
phonons do not exist

363
9.6 Optic branch
• So called optic branch because its phonon
modes are excited by light of suitable
frequencies
• For k=0,

 B/A is negative for all values of k

 Nearest neighbor atoms move in opposite
directions
364
 m
Displacement
M

M
m

• When →2, B/A→0 (from a negative value)

 Thus for small λ,  and k are large, and only light
atoms are moving

365
 Phase velocity

 Group velocity

• m/M determines
 the width of the forbidden frequency range and
 the width of the optic branch

366
 Phonon dispersion relation in GaAs.
The longitudinal (LO, LA) and transverse (TO, TA) optical
and acoustical modes are shown.

367
9.7 3-dimensional solids with polyatoms as basis
• If there are p atoms in a primitive cell, there will
be 3p branches/modes for the dispersion
relation
• Why 3p modes?
 Modes are determined by the atoms degrees of
freedom
 Each atom has 3 degrees of freedom (in x, y and
z directions)
 Therefore for p atoms, the total degrees of
freedom (modes) is 3p
 Out of these 3p modes, 3 are acoustic modes
and 3p-3 are optic modes
368
• Example for Ge
 There are 2 atoms in the primitive cell, thus a
total of 6 modes
 3 acoustic modes consisting of
o 1 longitudinal acoustic (LA)
o 2 transverse acoustics (TA)
 3 optic modes consisting of
o 1 longitudinal optic (LO)
o 2 transverse optic (TO)

• If there are N primitive cells, thus there will be

pN atoms
369
 The total degrees of freedom (branches/modes)
is 3pN
 3N acoustic modes consisting of
o N longitudinal acoustic (LA)
o 2N transverse acoustic (TA)
 (3pN – 3N) = 3(p – 1)N optic modes consisting of
o (p – 1)N longitudinal optic (LO)
o 2(p – 1)N transverse optic (TO)

370
 Thermal properties
• There are two contributions to thermal
properties of solids: one comes from phonons
(or lattice vibrations) and another from
electrons.
• This section is devoted to the thermal
properties of solids due to lattice vibrations
(the contribution from electrons in metals will
be considered separately).
 Some values for K and
T = 273 K T = 20 K
K (m) K (m)
(Wm-1K-1) (Wm-1K-1)
NaCl 6.4 6.7  10-9 45 2.3  10-6
Si 150 4.3  10-8 4200 4.1  10-4

• increases when T decreases

• and K are dependent on T
• Examples of the variation of and K with
temperature
 11 Free Electron Fermi Gas
11.1 Electrons in metals
• Characteristics of metals
1. Metals obey Ohm law that can be written as

where J is the current density (Am-2)

 is the electrical conductivity (-1m-1)
E is the electric field gradient (Vm-1)
For metals,  = 106 → 108 -1m-1
For insulators,  ≈ 10-16 -1m-1
For semiconductors,  = 10-4 → 105 -1m-1 373
2. Metals have high electronic thermal conductivity Ke
Metals that have good thermal conductivity are
also good electrical conductors – the Wiedemann-
Franz law of (Ke/)

3. At sufficiently low
temperatures,  reaches
a high plateau value which
is contributed by
impurities and lattice
imperfections, such as
shown by Cu
374
4. For a metal, the electrical resistivity (inverse of
electrical conductivity), ρ (m), follows the
Matthiessen rule, whereby the contribution by
impurities and lattice imperfections is the same
for all temperatures

At sufficiently low temperatures and if

, then impurities and lattice imperfections
becomes the main component (constant value)
Thus electrical resistivity ρ(low T) has a
constant value 375
5. Magnetic effects in metals of ferromagnets and
alloys also contribute to electrical resistivity
6. Free electron gas in metals has a small
electronic specific heat, Ce  T (small value)
376
11.2 Free electrons and positive ion cores
• Free electrons (electrons gas) formed metal
binding
Free electron

Average electron
charge

• Charge density
periodic

distance
377
• Electrostatic potential and electron velocity
Electron
velocity

distance

Electrostatic
potential
• Electron velocity increases to a maximum value
close to ion cores because of the decrease in
electrostatic potential
378
• Thus the electrons stay longer between the ion
cores
• The conduction electrons are not deflected by
the ion cores because particle wave propagation
is free in periodic lattices (for example by X-rays)
• A conduction electron is not scattered by other
conduction electrons due to Pauli Exclusion
Principle
• Electrons in a free electron Fermi gas are free to
move and do not interact with each other
according to the Pauli principle (two electrons
cannot have the same quantum numbers)
379
11.3 Classical theories for free electron gas
• Drude model
 Each electron has kinetic energy
(mono atomic gas, solid x 2), moving with the
same thermal velocity
 Thus the total kinetic energy for N electrons is

 The electronic specific heat is

• Lorentz model
 The electrons have different thermal velocity
380
 Using Boltzmann equation, the kinetic energy is

 The electronic specific heat is

• Failures of classical theories

 Values of are too high
 The mean free paths of electrons are also too high
compared to the distance between atoms
 The solution is to use Pauli Exclusion Principle
(quantized theory)
 The mean free path is the average distance traveled by
a moving molecule between collisions. 381
• Imagine a ball traveling in a box.
• Every time the ball hits a wall, a collision occurs and the direction
of the ball changes.
• The ball hits the wall five times, causing five collisions.
• Between every two consecutive collisions, the ball travels an
individual path. 
• It travels a total of four paths between the five collisions; each
path has a specific distance, d.
• The mean free path, l, of this ball is the average length of all four
paths.

382
11.4 Quantized free electron gas theory
• Consider a free electron gas in 1-dimension
where the potential energy is zero
• Thus the total energy is contributed only by the
kinetic energy of the electrons
• The electron of mass m is inside an infinite
potential barrier of length L
V→ V→
2
 L
n
1 n

 2L

383
• The wave function for the electron in the
barrier is a solution of the Schrödinger equation

where the Hamiltonian operator is

(kinetic energy)

E = (1/2)mv2= p2/(2m), so E = ћ2k2/(2m)

• Therefore
(11.1)

• The solution for can be written as

384
385
 (11.2)

where is the wave vector

• Boundary conditions at and give

(11.3)

386
• Substitute Eq. (11.2) into Eq. (11.1) and use Eq.
(11.3) to obtain the energy

2
 L
(11.4) n
1 n

 2L
where is the energy for level n
• This energy is for the case of one electron
387
Fermi Energy
-Basic idea-
• Let us say that there are N electrons
• The quantum numbers for an electron orbit are n
and ms where n is a positive integer and ms = +½
(spin ↑) or -½ (spin ↓)
• So a pair of electron orbits that have the same
quantum number n, according to Pauli Exclusion
Principle, can have two electrons with spin ↑
and spin ↓
• If nF is the highest level filled by electrons
n = nF (2)
n=3 (2) 2nF = N electrons
n=2 (2)
n=1 Fill in electrons (2) 389
• Energy at level nF is

(1-dimension) (11.5)

• is called the Fermi energy, which is the highest level

energy that is filled by electrons in the ground state
• In metals the value of the Fermi energy is of the order
of 5 eV.
• The ground state of the N electron system is illustrated
in Figure below:
– All the electronic levels are filled
up to the Fermi energy.
– All the levels above are empty.
390
11.5 In 3-dimension
• The Schrödinger equation for free electrons is
(11.6)

• If the electrons are in a cube of sides L, then the

wave functions are quantized stationary waves
(obeying the Schrödinger equation)
(11.7)

kx ky kz
where nx, ny and nz are positive integers
391
• The wave functions in 3-dimension must also
fulfill the periodic boundary conditions, for
example for the x coordinate
(11.8)
with period L in the x direction
• The same goes for coordinates y and z
• The wave functions that obey Schrödinger
equation and periodic condition are of the form
(11.9)
if the wave vector components k obey
(11.10)
392
• Meaning that each k component has the form
where n is a positive or negative integer

• Simple exercise: Using Eq. (11.9) show that Eq.

(11.10) obeys Eq. (11.8)
 For the x component

393
 Thus

 Similarly for components y and z

• Substitution of Eq. (11.9) into Eq. (11.6) gives

(11.11)

• In the ground state, the orbits that are filled by N

free electrons can be represented by points in a
sphere which is in the k space
394
 2π/L
2π/L
2π/L

• The energy at the surface of the sphere (Fermi surface)

is called Fermi energy
(11.12)
where kF is the wave vector at the Fermi surface
395
 Fermi Energy & Wavevector
• The Fermi energy and the Fermi wavevector
(momentum) are determined by the number of
valence electrons in the system.
• In order to find the relationship between N and kF,
we need to count the total number of orbitals in a
sphere of radius kF which should be equal to N.
• There are two available spin states for a given set of
kx, ky, and kz.
• The volume in the k space which is occupied by this
state is equal to (2π / L)3 .
If we have N electrons, and put them into the system,
what will be the highest occupied energy?

k-space Volume of a single electron

(ignoring spin):
• So, for a volume in k space, there is
only one set of wave vectors (for one point) that
is allowed, which is the triplet kx, ky and kz
• Therefore in a sphere of volume , the
total number of orbits is

• While the number of electrons is

(11.13)

399
• The factor 2 is due to the two values for ms (the
quantum number for spin) for each allowed k
• Therefore

(11.14)
where n = N/V is the electron concentration
• Thus kF is dependent on the concentration of
free electrons and Fermi energy becomes
(11.15)
400
• The electron velocity on the Fermi surface is
(11.16)

• Some values for n=N/V, kF, F, EF and TF=EF/kB

(Fermi temperature)
Metal n1022 k 108  108 EF T 10 4
F F F
(cm-3) (cm-1) (cms-1) (eV) (K)
Na 2.65 0.92 1.07 3.23 3.75
Cu 8.45 1.36 1.57 7.00 8.12
Zn 13.10 1.57 1.82 9.39 10.90
Al 18.06 1.75 2.02 11.63 13.49
401
11.6 Fermi-Dirac distribution
• The Fermi-Dirac distribution, f(E), for an ideal
electron gas gives the occupancy expectancy by
electrons of an orbit of energy E
(11.17)
E1 EF E2

(1)

(2)
402
 Fermi-Dirac distribution
• This is the ground state of the N electron system at
absolute zero.
• What happens if the temperature is increased?
• The kinetic energy of the electron gas increases with
temperature.
• Therefore, some energy levels become occupied which
were vacant at zero temperature, and some levels
become vacant which were occupied at absolute zero.
• The distribution of electrons among the levels is usually
described by the distribution function, f(E), which is
defined as the probability that the level E is occupied by
an electron.
• Thus if the level is certainly empty, then, f(E) = 0, while if
it is certainly full, then f(E) = 1.
• In general, f(E) has a value between zero and unity.
• At absolute zero temperature, T = 0 K
 Occupation of orbit is complete till energy E = EF

• At temperatures T > 0 K
 Occupation of orbit is complete till energy E1(< EF)
 Occupancy expectancy is zero for energy E2 (> EF )
 when E = EF at 300K
 The kinetic energy of electrons increases with the
increase in temperature
 Transfer of electrons from region (1) to (2) 404
• When the system is heated (T>0°K), thermal
energy excites the electrons (region 1  2).
• However, all the electrons do not share this
energy equally, as would be the case in the
classical treatment, because the electrons
lying well below (far below) the Fermi level EF
cannot absorb energy.
• If they did so, they would move to a higher
level, which would be already occupied, and
hence the exclusion principle would be
violated.
• Recall in this context that the energy which an
electron may absorb thermally is of the order kBT ( =
0.025 eV at room temperature), which is much
smaller than EF, this being of the order of 5 eV.
• Therefore only those electrons close to the Fermi
level can be excited (if E + kBT > EF), because the
levels above EF are empty, and hence when those
electrons move to a higher level there is no violation
of the exclusion principle.
• Thus only these electrons which are a small fraction
of the total number - are capable of being thermally
excited.
• The distribution function at non-zero temperature is
given by the Fermi distribution function.
– The derivation WILL NOT BE presented here.
• The Fermi distribution function determines the
probability that an orbital of energy E is occupied at
thermal equilibrium

• The quantity μ is called the chemical potential (fermi

energy when T = 0).
• The chemical potential can be determined in a way
that the total number of electrons in the system is
equal to N.
• At absolute zero μ = EF .
 An important quantity which
characterizes electronic properties
of a solid is the density of states,
which is the number of electronic states
per unit energy range.
11.7 Density of states, D(E), for electrons
• Compare with the density of states, g(), for
phonons
• The density of states D(E) for electrons is the
number of filled orbits in per unit range of
energy
• Total number of orbits that has energy  E is
(from Eq. (11.15))
(11.18)

• The density of states (orbits) is

409
 (11.19)

(11.20)

• The number of orbits per unit range of energy at

the Fermi surface is

where N is the total conduction electrons

410
 D(E)E1/2

(1) f(E)D(E)
T=0K

f(E)D(E)
T>0K

(2)
EF

• For T = 0 K, area with E < EF represents filled orbits

(states)
• For T > 0 K, area under the curve represents filled orbits
(states) 411
11.8 Specific heat, Cel, for electron gas
• The total energy of a system of N electrons at
temperature T is

density (11.21)
number

(11.22)

Fermi-Dirac integral 412

• The Fermi-Dirac integral can be written as

(11.23)

• For y0 large and positive

y0 >> 1

• Now back to Eq. (11.22), let , then

413
• Also , and for large y0,
•
• Then

414
y0
 EF >> kBT (11.24)

• Therefore the energy is

(11.25)

• For T > 0 K, the Fermi energy is

415
 (11.26)

where EF0 is the energy at T = 0 K

• So the energy becomes

(11.27)
416
• But

• Therefore Cel=dU/dT≈NkB(kBT/EF)

(11.28)

• Therefore
(11.29)
417
• Compare with

• Therefore

• The total specific heat for a metal is

418
Ctotal=Cel + Cph B = gradient
Cph

A
Cel

419
11.9 Electrical conductivity, , and Ohm law
• The momentum of a free electron is related to
its wave vector by

• The force acting on an electron of charge –e in

an electric field E and magnetic field B is
(11.30)

• If B = 0 and E constant, the Fermi sphere in k

space will be displaced at a uniform rate

420
 (11.31)
• At temperature T = 0 K (ground state)
 At time t = 0, the center of the Fermi sphere is at

kz
ky
Orbits filled
with electrons

(0,0,0) kx

421
• At time t > 0, the Fermi sphere is displaced
(interacting force acts on the electrons and they
moved as a group), with the center of the sphere
now at a new position
(11.32)

• The negative sign indicates that the direction of

the displacement k is opposite to the direction
of E
• If , then and

422
 F kz E
ky

(eExt/ħ,0,0)
kx
k = kx(i)

• Due to collisions of electrons with impurities,

lattice imperfections and phonons, the Fermi
sphere can be stationary in an electric field
• If  is the collision time, then the displacement is
(11.33)

423
• Therefore the drift velocity is
(11.34)

• If E is constant and there are n electrons of

charge q = e per unit volume, then the electric
current density is
(11.35)
(Ohm law)

• The electrical conductivity  is define as

• Thus
(11.36)
424
• The electrical resistivity  is define as the
reciprocal of electrical conductivity , thus
(11.37)

• For pure Cu
 Ratio of conductivities

↑ when T↓ because ↓
 Ratio of mean free path
↑ when T↓
because of
less collisions
425
11.10 Matthiessen’s rule
• The electrical resistivity at temperature T is
(11.38)
• is the resistivity due to the collisions of
conduction electrons with phonons, thus
dependent on temperature
• is the resistivity due to the collisions of
conduction electrons with impurities and lattice
imperfections, thus dependent on the purity of
metals
• When temperature T → 0,
→ 0 and
→  purity (a constant value) 426
• Thus
(11.39)

427
11.11 Electron motion in magnetic field B
• Please write short notes on cyclotron frequency

11.12 Hall effect and Hall electric field

• Hall electric field is produced by positive charges
and negative charges at two surfaces of a
conductor placed in a magnetic field
• Consider a bar conductor connected to an
electrical circuit
• When switch S is close, an electric current J flows
in the positive x direction inside the bar 428
• This means that conduction electrons move with
velocity  in the negative x direction
E = Exi  = x(-i) y(j)
J = Jxi
z(k) x(i)
e.m.f. S

• When a magnetic field B (in the z direction) is

introduced, a Lorentz force

acts on the electrons that force their motion to

bend downwards (negative y direction)
429
 E = Exi  = x(-i) y(j)

B
z(k) x(i)
B

B
• is in the positive y direction
• Thus for electrons, , the Lorentz
force is in the negative y direction
• This causes electrons to be accumulated at the
bottom surface of the bar, thus negatively
charged
• The top surface of the bar is positively charged
(lacked of electrons) 430
• These positive and negative charges produce an
electric field in the negative y direction called
the Hall electric field
E = Exi  = x(-i)
+++++++++++++++ y(j)
EH = EH(-j) B
___________ z(k) x(i)

• Note that
• The Lorentz force

(11.40)
431
• The Hall electric field creates a Hall force on the
electrons to counter the Lorentz force so that
the system is in the steady state

(11.41)
• In the steady state

• Therefore the Hall electric field is

(11.42)
432
• The electric current density is

• Therefore
(11.43)
• Substituting Eq. (11.43) into Eq. (11.42)
(11.44)

• The Hall constant is

(11.45)

• has units of volt m3 amp-1 weber-1

433
• Some values for Hall constant at room
temperature
•  for electrons Conductor Hall Constant
Li 1.710 -10
• + for holes
Na 2.50
Cu 0.55
Ag 0.84
Au 0.72
Zn +0.30
Cd +0.60
Al 0.30
434
11.13 Thermal conductivity for metals
• The electrons thermal conductivity is

where is the specific heat per unit volume for

electrons, is the mean velocity of electrons and
is mean free path of electrons
• From Eq. (11.29)

• Thus
435
• Substituting for
• Then
(11.46)

where is the collision time

• Typical graph of for Cu

• is maximum at temperature around 15 K

436
• For pure metals at all
temperatures

437
11.14 Wiedemann-Franz law
• This law says that for metals at temperatures
that are not too low, the ratio of thermal
conductivity and electrical conductivity for
electron gas is directly proportional to the
temperature

where L is a proportional constant independent

of the type of metals
• Substitute for K, and thermal = electrical = 
438
 (11.47)

• Therefore the proportional constant L or the

Lorentz number L is
(11.48)

439
 Why We Study Energy Bands?
• The free electron model gives us a good insight into many
properties of metals, such as the heat capacity, thermal
conductivity and electrical conductivity.
• However, this model fails to help us other important
properties.
– For example, it does not predict the difference between metals,
semiconductors and insulators.
– Also the relation between conduction electrons in the metal and
the number of valence electrons in free atoms is not always
correct.
• A more accurate theory is needed to answer these
questions.
• The problem of electrons in a solid is in general a
many-electron problem.
• The full Hamiltoniam of the solid contains not only
the one-electron potentials describing the
interactions of the electrons with atomic nuclei, but
also pair potentials describing the electron-electron
interactions.
• The many-electron problem is impossible to solve
exactly and therefore we need simplified
assumptions.
• The simplest approach we have already considered,
it is a free electron model.
• The next step in building the complexity is to
consider an independent electron approximation,
assuming that all the interactions are described by an
effective potential.
• One of the most important properties of this potential is that
it is periodic on a lattice
U(r) =U(r + T)
where T is a lattice vector.
• Qualitatively, a typical crystalline potential might be expected
to have a form shown in figure below, resembling the
individual atomic potentials as the ion is approached closely
and flattening off in the region between ions.
 12 Energy Bands
12.1 Free electron model
• The 3-dimensional quantized free electron gas
model with Schrödinger equation

shows that the equation for the allowed electron

energy is (derive the wave function gives)

443
• is the electron wave function

• A plot of E versus kx (energy band structure in x

direction) produces a parabola
Ek

Ek  kx2

kx (ky, kz = 0)

444
445
12.2 Nearly free electron model
• Electrons in real crystals experience small
perturbations due to the periodic potential
of ion cores
• Thus electrons are no longer free
• Their energy band structure can be explained by
quantized nearly free electron model with
Schrödinger equation

(12.1)
Kinetic energy Potential energy Total energy
446
• and are the wave functions and energy
of the electrons
• The term for the periodic potential causes
only certain electron energies to be allowed,
thus there exist forbidden
• For a linear monoatomic lattice with lattice
constant a and periodic potential, the shape of
its energy band structure is
E
Second allowed energy band

Forbidden energy band

E dependent on imaginary k
First allowed energy band
E dependent on real k
-/a First Brillouin zone+/a k 447
• In intrinsic semiconductors the forbidden gap is
narrow and, at normal temperatures, electrons at the
top of the valence band can move by thermal
agitation into the conduction band (at absolute zero,
a semiconductor would act as an insulator).
• Doped semiconductors have extra bands in the
forbidden gap.
• Above are a number of views demonstrating the lifting of the
degeneracy on the Bragg plane, and the creation of the
energy gap.
• The upper left picture represents the parabolic energy due to
a perfectly-free electron around the k-space origin.
• The next picture to the right shows two intersecting parabola
about two subsequent atoms in k-space. Notice the parabola
intersect halfway between the two atoms.
• The degeneracy at the Bragg plane halfway-point is lifted
because the electrons are MOSTLY free but not ALL free
(different state same energy).
• Redrawn to the right, getting rid of the duplicate information,
the original parabola, as shown in the left half, gets a
discontinuity on the right half at the Bragg plane. note that
nearby the plane the energy curves into the Bragg plane.
• These three pictures show three ways of presenting
the same information.
– The Extended-Zone Scheme shows the parabolic shape of
electron states extending out over many one-dimensional
Brillouin Zones, with the appropriate gaps at the Bragg
planes.
– The Reduced-Zone Scheme gives the same information,
but with all the higher-order Brillouin zones folded over
into the first zone. This portrayal of the band structure is
usually the one most often used.
– Finally, the Repeated-Zone Scheme shows the same
information of the Reduced-Zone Scheme repeated over
several Brillouin zones.
Reduced-Zone
Extended-Zone
Repeated-Zone
Scheme
Scheme
12.3 Bloch function
• Bloch theorem states that the solution for the
Schrödinger equation of Eq. (12.1) is a wave function
of the form
(12.2)
• This equation is called the Bloch function which is a
progressive wave equation
• is a periodic function where its period is the
same as the lattice period
• exist because of which has the same
period
• Subscript k indicates that is dependent on
wave vector k 453
 (12.3)
where T is a translational lattice vector
• For 2-dimensional lattice

b j
T2
T3 i
T1
a

och function combines a plane wave with a periodic seq

of atomic orbitals. 454
• For 1-dimensional lattice

x i
a
• Assuming there are N atoms, then from (12.3)

• The Bloch wave function for from Eq.

(12.2) is

455
• Where and
• If the monoatomic lattice is made into a circle
• Then the length is Na and
the new period is Na and

• The wave function at the point

k(x)=k(x+Na)
where the ends meet is now

456
• Therefore

(12.4)
where n = 0, 1, 2, 3 … N – 1
• Thus

457
• The Bloch wave function becomes
(12.5)

• Substitute this into the Schrödinger

equation of Eq. (12.1) and the allowed values for
can be determined provided is known.

12.4 Kronig-Penney model

• This 1-dimensional model is used to obtain the
relationship between E and k (allowed and
forbidden energies) when V(x) is known
458
• The periodic potential V(x) has square wells
arrangement such as below
Barrier with
maximum Well
potential V0

x
• The Schrödinger equation of Eq. (12.1) for free
electrons becomes
(12.6)

459
• If V0 and b are small, the electrons are free to
move (free electron gas) and their E  k2
(parabola)
• If b is too large and the electron energy E < V0,
the probability of tunneling by the electrons
through the barriers is zero, and the electrons
will be in the wells with quantized energies
(values of allowed k given by stationary wave
functions in the wells)
• What if b is small and E < V0 (V0 → )?
• Is there a complete tunneling by the electrons
through the barriers? 460
• In the range 0<x<a (inside the well), V = 0
• The wave function for Eq. (12.6) is
(12.7)
 Combination of two progressive plane waves to
the right and to the left
 Thus creating a stationary wave
• The energy of the electron is
(12.8)

461
 -b 0 a a+b x
Stationary wave Exponential decay wave

• In the range a<x<a + b (inside the barrier), the

wave function for Eq. (12.6) is
(12.9)
 Combination of two exponential decay waves (to
the right and to the left) due to tunneling
• The energy of the electron is
462
 (12.10)outside
For the region
of the box, since the
potential is
• The factors A, B, constant, V(x) 
C and D are chosen so that
and are continuous at x = 0 and x = a
• Condition I
 Continuity at x = 0
 For ,

(12.11)
 For ,

463
 (12.12)
• Condition II
 Continuity at x = a
 For ,

(12.13)
 For ,

464
 (12.14)
• Condition III
 From Bloch theorem

where and lead and

(a+b) =periodicity
respectively with phase factor
[x+(a+b)] [x-(a+b)]
 The left side of Eq. (12.13) becomes
465
 (12.13a)
 The left side of Eq. (12.14) becomes

(12.14a)
• The solution for Eqs. (12.11), (12.12), (12.13a)
and (12.14a) can be obtained if the determinant
of the factors A, B, C and D becomes zero
• The solution is

(12.15)
466
467
468
• Q is the wave vector in the barrier, K is the wave
vector in the well and k is the overall wave vector
for the electron
• Consider a high barrier (V0 large) and narrow
(b0) so that bV0 has a finite value and Q>>K,
then

0

469
• The barrier strength is defined as

• Therefore
(12.16)

• If

(free electron)
• If
(quantized electron energy)
470
• Let us consider P with a finite value,
• The graph of versus
has the form

Ka region that produced

real k (allowed)

Ka region that produced

imaginary k (forbidden)471
Ka region that produced
real k (allowed)

Ka region that produced

imaginary k (forbidden)472
• Equation (12.16) has a solution for k (real k)
when
(12.17)
which is
(12.18)
• Therefore the allowed overall electron wave
vectors k (real) have values between

• Thus the graph for the overall electron energy

has the following shape
473
• It is clear the equation (12.17) has gaps where it
cannot be satisfied.
• It follows that in these gaps, there will be no solution
to the wave equation.
• Effectively, there are no wave functions (or
corresponding energy states), that can satisfy the
boundary conditions.
• Without the barriers in the potential, the wave
function would have been the plane wave.

• The effect of the periodic barriers has lead to gaps in

this energy spectrum.
 Extended
zone Free electron
scheme
(black) Forbidden energy
or forbidden gap
Reduced for Eoverall of
zone which k is
scheme imaginary and
(red) occurs at the
boundary of
Brillouin zones
First Brillouin
zone 475
 Effective Mass
• Suppose you have 100 electrons mutually interacting through
a coulombic potential.
• The model cannot be solved exactly because of the mutual
coupling between all the electrons.
• To uncouple this many body system, we convert it into a
system where you have "new electrons" interacting in a
background potential.
• So, you look at the problem as if the new electrons are no
longer interacting with each other but with some background
potential.

476
 Effective Mass
• To make sure that new systems (electron-
background) are equivalent with the old
system (electron-electron), we change the
mass of the electrons in the new system
• This new mass is the effective mass, which can
be defined as the electron mass ± some
interactions (ie energy of those interactions)
to uncouple the many body problem into
many one body problems.
477
12.5 Effective mass of electron
• Group velocity for an electron wave function is
given as
(12.19)

where the angular frequency

• Therefore
(12.20)

478
• Consider an electron in a periodic solid and an
external electric field E acting on the electron
• The external force on the electron is
(momentum/time) (12.21)

(12.22)

• The acceleration of the electron is given as

(12.23)
479
 where is the effective mass
• Compare Eq. (12.23) with the equation for the
acceleration of free electron in an electric field E
(12.24)

• Thus the magnitude of electron effective mass in

a periodic solid is

(12.25)
480
• is responsible for the curvature of the
graph of at the edge of the Brillouin
zone (via the periodic potential)


Like free electron (red)

k

m*

481
 Tutorial
• The volume of the unit cell of a beryllium
alkaline is 14.32 Å3 with atomic number and
atomic mass of 4 and 9.01, respectively. The
Debye temperature is θD = 1690 K. Consider a
sample of 1.2 mm3 of beryllium.
• Compute the
(1) fermi energy and total number of
electrons in moles
(2) contribution of the electrons to the heat
capacity of the 1.2 mm3 sample at room
temperature. (in JK-1)
(3) contribution of the acoustic phonons to
the heat capacity of the sample at room
temperature using the Debye model. (in JK-1)
 13 Semiconductor Crystals
13.1 Energy bands for metals, insulators and
semiconductors
• At temperature T = 0 K (reduced zone scheme)
• Metals
E Electron Conduction band
 In an electric field,
Partially filled
the electrons in (10 – 90%)
the conduction
band are free to k
move, thus Valence band
producing current Fully filled
483
 Insulators
E Conduction band
Zero occupancy
 When temperature
is increased, there
E  7 eV k
is no transition g

from valence band

Valence band
to conduction band Fully occupied
because Eg is large
 A complete band does not carry electric current
even with the presence of an electric field

484
• Semiconductors
E Conduction band
 At temperature Zero occupancy
T = 0 K, it is an
insulator
Eg  1 eV k
 When temperature
T is increased,
Holes Valence band
electrons in the Fully occupied
valence band are thermally excited to the
conduction band and become mobile
 Excitation of electrons creates holes in the
valence band
485
 The electrons in the conduction band and holes
in the valence band are responsible for the
electrical conduction in the semiconductor


13.2 Semiconductor energy bands

E Conduction
Lowest point of the conduction band
band is called the edge of the Eg
conduction band k
Valence
Highest point of the valence band
band is called the edge of the
valence band 486
• The energy difference between the conduction
band edge and valence band edge is called the
energy band gap Eg
• The energy of the conduction band is given as

where k is the wave vector and me* the electron

effective mass
• The zero energy level is at the edge of the
valence band
• The energy of the valence band is given as
487
 where mh* is the effective mass of hole
• Energy gap can vary with
 Temperature (small changes)
 Pressure (due to changes to the lattice constant)

13.3 Energy gap

• Direct energy gap
 Occurs when the edge of the conduction band
and the edge of the valence band are at the
same value of k
488
 
electron

Eg photon Same value of k

hole

 The value of Eg can be obtained using optical

absorption (photon energy absorbed by
electron)
 In this direct absorption process, a photon with
very small wave vector is absorbed to create an
electron (conduction band) and a hole (valence
band) 489
• The energy gap for a semiconductor varies with temperature,
but the variation is usually slight.
• That a variation with temperature
should exist at all can be appreciated
from the fact that the crystal, when it is
heated, experiences a volume
expansion, and hence a change in its
lattice constant.
• This, in turn, affects the band structure,
which is a sensitive function of the
lattice constant.
• The band structure in figure beside is
the simplest possible structure.
• Band structures of real semiconductors
are somewhat more complicated.

490
 The difference in wave vector between electron
and hole is essentially zero
 The direct energy band gap, , is
determined by the threshold frequency
 For example GaAs
Conduction
band

1.43 eV

Valence band

491
• Indirect energy gap
 The conduction band edge and valence band
edge are at different values of k
phonon electron

Different
values of k photon Eg

hole

 The change in wave vector associated with the

direct photon absorption is essentially k = 0
492
 While the electron transition from valence band
edge to the conduction band edge requires a
large change in k
 This can be achieved if phonon (lattice vibration)
energy is also absorbed by the electron
 This transition process is called indirect
absorption due to the indirect energy gap

(phonon absorbed)
(phonon emitted)
where is the phonon frequency
493
 For example Si and Ge

Conduction
band

= 1.14 eV 0.67 eV =

Valence
band

494
13.4 Holes
• In semiconductors, electrons that are excited to
the conduction band leave vacancies or holes
which are positively charged in the valence band
• The electrons and holes are called free carriers,
and are responsible for the current flow in the
semiconductor
• The number of free carriers is important because
it determines the electrical conductivity of a
semiconductor
• The electrical conductivity
495
 where n and p are electrons and holes
concentration, respectively, while e and h are
electrons and holes mobility, respectively
• Mobility is

•  is defined as positive for electrons and holes

even though e and h are of opposite directions
• For a charge q, , thus

• and
496
13.5 Intrinsic carrier concentration
• In pure semiconductors, electrons and holes
carrier concentrations are the same
• This is due to each electron being excited to the
conduction band creates a hole in the valence
band
• The semiconductor is called an intrinsic
semiconductor
• For Eg >> kBT (13.1)

(Tutorial – Prove Equation 13.1) 497

• Fermi-Dirac distribution,
1 1
f electron ( E )  f hole ( E ) 
e ( E   ) / k BT  1 e (   E ) / k BT  1

• At low temperatures, ( E   )  k BT and (   E )  k BT

• The Fermi-Dirac distribution are
( E   ) / k BT
f electron ( E )  e  ( E   ) / k BT
e (   E ) / k BT and f hole ( E )  e
• The energy of an electron and hole are
 2k 2  2k 2
EK  EC  EK  EV 
2me 2me
• Density of states for electron and holes are
D(E) = = dN/dE =
3 3
1  2me  2 1 1  2mh  2 1
2  2 
( E  Ec ) 2
  ( E v  E ) 2
2    2 2   2 
• Concentration of electrons and holes in the
conduction and valence bands, respectively.

nelectron   D( E ) f electron ( E )dE
Ec
3 
1  2me  2  / k BT 1
 
2   
2 2  e 
Ec
( E  E c ) 2  E / k BT
e dE

3   Ec
 me k BT  2 ( )
 2 2 
exp k BT

 2 

Ev
phole   D( E ) f hole ( E )dE

3 Ev
1  2mh  2   / k BT 1
 
2   
2 2  e 

( EV  E ) 2 E / k BT
e dE

3 EV  
 mh k BT  2 ( )
 2 2 
exp k BT

 2 
 3   Ec 3 EV  
m k T  2 ( ) m k T  2 ( )
nelectron  2 e B2  exp k BT phole  2 h B2  exp k BT

 2   2 
nelectron  phole
3 EV   3   Ec
 mh k BT  2 ( )
 me k BT  2 ( )
 2 2 
exp k BT
 2 2 
exp k BT

 2    2  
3  EV       Ec 
   
 k BT 
 mh me  exp k BT   k BT
3
 4 2 
2 

 2 
3  EV  Ec 
 
 k BT 
 mh me  exp
3 k BT
 4 2 
2 

 2 
3   Eg 
 
 k T 
 4 B 2   mh me 
3
 k BT 
2 exp
 2 
3  Eg 
 
 k BT 
 mh me  2 exp k BT 
3
Intrinsic semiconduc tor, n  p  4 2 


 2 
3   Eg 
 
 k T  2
 mh me 
3  2k T 
 2 B 2  4 exp  B 

 2 
 where me and mh are the effective masses of
electrons and holes, respectively
• Therefore for intrinsic semiconductors, the
carrier concentrations are

(13.2)
• ni and pi rapidly increase exponentially when the
temperature is increased

501
• The Fermi energy level in the energy gap Eg is
(13.3)

(Tutorial – Prove Equation 13.3)

If the electron mass equals the hole mass,
me=mh, then

(13.4)
• The Fermi level is in the middle of the gap
• The energy bands of “pure” or intrinsic
semiconductors do not show energy levels
associated with impurities (donors or acceptors)
and lattice imperfections 502
when nelectron  phole ,
3   Ec 3 EV  
 me k BT  2 ( )
 mh k BT  2 ( )
2 2 
exp k BT
 2 2 
exp k BT

 2    2  
  Ec EV  
( ) ( )
 me    mh 
3 k BT 3 k BT
2 exp 2 exp
  Ec
( )
 mh  2   Ec E 
3 k BT
exp ( ) ( V )
  exp k BT k BT

 me  2
3 EV  
( )
k BT
exp
3
m  2
  Ec E 
ln h  ( )( V )
 me  k BT k BT

3 k T ln mh   (   E )  ( E   )  2   ( E  E )
2 B m  c V c V
 e
EV  0 since we measure the fermi level from the top edge of the
valence band. Therefore, Ec  E g and Ec  EV  E g .

3 k T ln mh   2 E  E
2 B m  F g
 e
m 
EF  1 E g  3 k BT ln h 
2 4
 me 
• Energy bands of an intrinsic semiconductor

504
13.6 Extrinsic carrier concentration
• A semiconductor is said to be extrinsic when it is
not pure (there exist impurities)
• Impurities can provide extra electrons or holes
as free carriers
• Thus producing higher values for electrical
conductivity compared to intrinsic
semiconductors
• There are two types of extrinsic semiconductors,
n-type and p-type
• Consider the semiconductor Si
505
• n-type Si (with As (arsenic) as the impurity)
Covalent
bonding
Si

An extra electron
e from an As atom
for conduction

As
+
• Si atom has 4 valence electrons
• As atom has 5 valence electrons
• As atom is called a donor because after
ionization it donates one electron to the
conduction band of Si
506
 E electrons
e e e e  e 


Ionization Eg Conduction band

energy Ed Donor (As)
energy level

0 Valence band

k
• Therefore electrical conductivity is controlled by
the negatively charged electrons and the
extrinsic semiconductor is n-type

507
• p-type Si (with B (boron) as the impurity)
Positively
charged hole e
Ionization happens Original Hole
+ Si
New hole created
Covalent
bonding

_B
• Si atom has 4 valence electrons
• B atom has 3 valence electrons
• To complete the B – Si bonding, an electron from
Si – Si covalent bonding is used, thus a hole
exists at that Si – Si bonding
508
 • B atom is called an acceptor because when
there is an ionization it receives electron from
the valence band of Si and a hole is created
E
Eg Conduction band

electrons Acceptor (B)

e e  e  e e


Ionization energy level

energy Ea 0 Valence band
+ + + + +
holes
k

509
• Here the electrical conductivity is controlled by
the positively charged holes and the extrinsic
semiconductor is p-type
• Conduction electron concentration from the
donors (no acceptors) is given by n  n  N
electron
2
i d
1
nelectron  (ni  N d ) 2

(13.5)

(13.6)

where is the donors concentration

510
• The conduction hole concentration is similar to Eq.
(13.6) if there are no donors

Wish U
aLL th3 b3sT
4 uR 3xAm