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INTRODUCTION
Crystalline Solids
How can this be? After all, they each contain a system of
atoms and especially electrons of similar density. And the
plot thickens: graphite is a metal, diamond is an insulator and
buckminster-fullerene is a superconductor.
CONTENT
CHAPTER 1.
CRYSTAL STRUCTURE
Elementary Crystallography
Elements of Symmetry
CHAPTER 2.
X-RAY CRYSTALLOGRAPHY
X-ray
Diffraction
Bragg equation
X-ray diffraction methods
Laue Method
Rotating Crystal Method
Powder Method
Neutron & electron diffraction
CHAPTER 3.
INTERATOMIC FORCES
NaCl
Covalent bonding
Metallic bonding
Van der waals bonding
Hydrogen bonding
CHAPTER 4.
CRYSTAL DYNAMICS
Sound wave
Lattice vibrations of 1D cystal
Heat Capacity
Density of States
Thermal Conduction
Energy of harmonic oscillator
CHAPTER 5.
FREE ELECTRON THEORY
REFERENCES
Core book:
Solid state physics, J.R.Hook and H.E.Hall,
Second edition (Wiley)
Other books at a similar level:
Solid state physics, Kittel (Wiley)
Solid state physics, Blakemore (Cambridge)
Fundamentals of solid state physics, Christman
(Wiley)
More advanced: Solid state physics, Ashcroft and
Mermin
CRYSTAL STRUCTURE
Elementary Crystallography
Typical Crystal Structures
Elements Of Symmetry
Objectives
By the end of this section you should:
18
matter
Matter
GASES
LIQUIDS
and LIQUID
CRYSTALS
Crystal Structure
SOLIDS
19
Gases
Crystal Structure
20
21
Crytals
22
ELEMENTARY CRYSTALLOGRAPHY
SOLID MATERIALS
CRYSTALLINE
POLYCRYSTALLINE
AMORPHOUS
(Non-crystalline)
Single Crystal
Crystal Structure
23
Types of Solids
Crystal Structure
24
Crystalline Solid
Crystal Structure
25
Crystalline Solid
Amorphous
Solid
Single Crystal
Crystal Structure
26
Polycrystalline Solid
Polycrystalline
Pyrite form
(Grain)
Crystal Structure
27
Amorphous Solid
Crystal Structure
28
Crystal Structure
29
CRYSTALLOGRAPHY
What is crystallography?
The branch of science that deals with the geometric
description of crystals and their internal arrangement.
Crystal Structure
30
Crystallography
Crystallography is essential for solid state physics
Crystal Structure
31
ELEMENTARY
CRYSTALLOGRAPHY
32
CRYSTAL LATTICE
What is crystal (space) lattice?
In crystallography, only the geometrical properties of the
crystal are of interest, therefore one replaces each atom by
a geometrical point located at the equilibrium position of
that atom.
Platinum
Platinum surface
(scanning tunneling microscope)
Crystal Structure
Crystal Lattice
y
An infinite array of
points in space,
Each
point
has
identical surroundings
to all others.
Crystal Structure
34
Crystal Structure
Crystal Structure
35
Basis
A group of atoms which describe crystal structure
y
y
B
C
F
b
O
D
E
G
A
b
O
Crystal structure
with
are
in
not
the
Crystal Structure
+ Basis
38
Crystal Lattice
Crystal Structure
39
Nb film
Crystal Structure
40
41
Rn = n1 a + n2 b
42
Lattice Vectors 2D
Crystal Structure
43
Lattice Vectors 3D
An ideal three dimensional crystal is described by 3
fundamental translation vectors a, b and c. If there is a
lattice point represented by the position vector r, there is
then also a lattice point represented by the position vector
where u, v and w are arbitrary integers.
r = r + u a + v b + w c
Crystal Structure
(1)
44
Crystal Structure
45
Unit Cell in 2D
Crystal Structure
S
46
Unit Cell in 2D
The choice of
unit cell
is not unique.
S
a
Crystal Structure
47
48
Crystal Structure
49
Crystal Structure
50
Crystal Structure
51
This is NOT a unit cell even though they are all the
same - empty space is not allowed!
Crystal Structure
52
Crystal Structure
53
Crystal Structure
54
Unit Cell in 3D
Crystal Structure
55
Unit Cell in 3D
Crystal Structure
56
Crystal Structure
57
UNIT CELL
Primitive
Single lattice point per cell
Smallest area in 2D, or
Smallest volume in 3D
Simple cubic(sc)
Conventional = Primitive cell
58
59
Crystal Structure
60
1
a1 ( x y z )
2
1
a2 ( x y z )
2
1
a3 ( x y z )
2
a
Crystal Structure
62
c
a
c
a
63
b
a
Crystal Structure
64
Unit Cell
65
V = a1.(a2 x a3)
(vector products)
Crystal Structure
The primitive unit cell must have only one lattice point.
There can be different choices for lattice vectors , but the
volumes of these primitive cells are all the same.
a1
Crystal Structure
67
Wigner-Seitz Method
A simply way to find the primitive
cell which is called Wigner-Seitz
cell can be done as follows;
1. Choose a lattice point.
2. Draw lines to connect these
lattice point to its neighbours.
3. At the mid-point and normal
to these lines draw new
lines.
The volume enclosed is called as a
Wigner-Seitz cell.
Crystal Structure
68
Wigner-Seitz Cell - 3D
Crystal Structure
69
Crystal Structure
70
Crystal Directions
Fig. Shows
[111] direction
71
Examples
210
X= ,Y=,Z=1
[ 1]
[1 1 2]
X=1,Y=,Z=0
[1 0]
[2 1 0]
Crystal Structure
72
Negative directions
Z direction
[n1n2n3 ]
R = n1 a + n2 b + n3c
Direction must be
smallest integers.
(origin) O
- X direction
- Y direction
Y direction
[n1n2n3 ]
X direction
- Z direction
Crystal Structure
73
X=1,Y=0,Z=0
[1 0 0]
X = -1 , Y = -1 , Z = 0
Crystal Structure
[110]
74
Examples
X =-1 , Y = 1 , Z = -1/6
[-1 1 -1/6]
[6 6 1]
Crystal Structure
75
Crystal Planes
The set of
planes in
2D lattice.
Crystal Structure
76
Miller Indices
Miller Indices are a symbolic vector representation for the orientation of
an atomic plane in a crystal lattice and are defined as the reciprocals of
the fractional intercepts which the plane makes with the crystallographic
axes.
To determine Miller indices of a plane, take the following steps;
1) Determine the intercepts of the plane along each of the three
crystallographic directions
2) Take the reciprocals of the intercepts
3) If fractions result, multiply each by the denominator of the smallest
fraction
Crystal Structure
77
Example-1
Axis
Intercept
points
Reciprocals
Smallest
Ratio
(1,0,0)
1/1 1/ 1/
1
Miller ndices
Crystal Structure
(100)
78
Example-2
Axis
Intercept
points
Reciprocals
(0,1,0)
Smallest
Ratio
1/1 1/ 1 1/
1
Miller ndices
(110)
(1,0,0)
Crystal Structure
79
Example-3
(0,0,1)
Axis
Intercept
points
Reciprocals
(0,1,0)
(1,0,0)
Smallest
Ratio
1/1 1/ 1 1/ 1
1
Miller ndices
Crystal Structure
1
(111)
80
Example-4
Axis
Intercept
points
1/2
Reciprocals
(0,1,0)
(1/2, 0, 0)
Smallest
Ratio
1/() 1/ 1 1/
2
Miller ndices
Crystal Structure
(210)
81
Example-5
Axis
Intercept
points
Reciprocals
1/1
1/
1/()
Smallest
Ratio
Miller ndices
Crystal Structure
(102)
82
Example-6
Axis
Intercept
points
-1
Reciprocals
1/-1
1/
1/()
Smallest
Ratio
-1
Miller ndices
Crystal Structure
(102)
83
Miller Indices
[2,3,3]
2
3a , 2b , 2c
1 1 1
Reciprocal numbers are:
, ,
3 2 2
b
2
(200)
(110)
(100)
Crystal Structure
(111)
(100)
84
Crystal Structure
85
Example-7
Crystal Structure
86
87
88
Crystal Structure
89
Coordinaton Number
A simple cubic has coordination number 6; a bodycentered cubic lattice, 8; and a face-centered cubic
lattice,12.
Crystal Structure
90
c
a
Crystal Structure
92
Crystal Structure
93
Crystal Structure
94
Many
metals (Fe,Li,Na..etc),
including the alkalis and several
transition elements choose the
BCC structure.
Crystal Structure
c
a
95
APF BCC
Crystal Structure
V atoms
= 0.68
V unit cell
(0,433a)
96
There are atoms at the corners of the unit cell and at the
center of each face.
Face centered cubic has 4 atoms so its non primitive cell.
Many of common metals (Cu,Ni,Pb..etc) crystallize in FCC
structure.
Crystal Structure
97
Crystal Structure
V atoms
0,74
= 0.68
APF BCC
FCC =
V unit cell
Crystal Structure
(0,353a)
99
Shared Between:
8 cells
2 cells
1 cell
2 cells
cell contents
1
[=8 x 1/8]
2
[=(8 x 1/8) + (1 x 1)]
4
[=(8 x 1/8) + (6 x 1/2)]
2
[=(8 x 1/8) + (2 x 1/2)]
Crystal Structure
100
Crystal Structure
101
2 - HEXAGONAL SYSTEM
Crystal Structure
102
2 - HEXAGONAL SYSTEM
Crystal Structure
Crystal Structure
104
3 - TRICLINIC
4 - MONOCLINIC CRYSTAL SYSTEM
Triclinic (Simple)
90
oa b c
Monoclinic (Simple)
= = 90o, 90o
a b c
Crystal Structure
5 - ORTHORHOMBIC SYSTEM
Orthorhombic (Simple)
= = = 90o
a b c
Orthorhombic (Basecentred)
= = = 90o
a b c
Orthorhombic (BC)
= = = 90o
a b c
Crystal Structure
Orthorhombic (FC)
= = = 90o
a b c
106
6 TETRAGONAL SYSTEM
Tetragonal (BC)
= = = 90o
a = b c
Tetragonal (P)
= = = 90o
a = b c
Crystal Structure
107
108
Crystal Structure
109
Sodium
chloride
also
crystallizes in a cubic lattice,
but with a different unit cell.
Sodium
chloride
structure
consists of equal numbers of
sodium and chlorine ions
placed at alternate points of a
simple cubic lattice.
Each ion has six of the other
kind of ions as its nearest
neighbours.
Crystal Structure
110
If we take the NaCl unit cell and remove all the red Cl ions, we
are left with only the blue Na. If we compare this with the fcc /
ccp unit cell, it is clear that they are identical. Thus, the Na is
in a fcc sublattice.
Crystal Structure
112
This
structure
can
be
considered
as
a
facecentered-cubic Bravais lattice
with a basis consisting of a
sodium ion at 0 and a chlorine
ion at the center of the
conventional cell,
a / 2( x y z )
LiF,NaBr,KCl,LiI,etc
The lattice constants are in
the order of 4-7 angstroms.
114
a / 2( x y z )
8 cell
Crystal Structure
117
Crystal Structure
118
Packing
Close pack
A
A
B
BA BA BA B A
C
C
C
BA BA B A
A
C
C
C
C
A
B
A
A
B
BA BA B A B A
C
C
C
Sequence AAAA
- simple cubic
Sequence ABABAB..
-hexagonal close pack
Sequence ABCABCAB..
-face centered cubic close pack
Crystal Structure
Sequence ABAB
- body centered cubic
119
Crystal Structure
120
4 - Diamond Structure
Crystal Structure
121
4 - Diamond Structure
Crystal Structure
123
5- Zinc Blende
5- Zinc Blende
5- Zinc Blende
Zinc Blende is the name given to the mineral ZnS. It has a cubic
close packed (face centred) array of S and the Zn(II) sit in
tetrahedral (1/2 occupied) sites in the lattice.
Crystal Structure
126
ELEMENTS OF SYMMETRY
SYMMETRY
INVERSION
REFLECTION
Crystal Structure
ROTATION
127
Element
Inversion
Point
Reflection
Plane
Rotation
Axis
Rotoinversion
Axes
Crystal Structure
128
Inversion Center
Crystal Structure
129
Reflection Plane
Crystal Structure
130
Examples
131
Rotation Symmetry
We can not find a lattice that goes
into itself under other rotations
A single molecule can have any degree
of rotational symmetry, but an infinite
periodic lattice can not.
Crystal Structure
132
Rotation Axis
90
120
180
133
Axis of Rotation
Crystal Structure
134
Axis of Rotation
Crystal Structure
135
5-fold symmetry
136
Group discussion
Crystal Structure
137
Examples
90
Crystal Structure
138
Crystal Structure
139